EP3331935A1 - Amine for low-emission epoxy resin compositions - Google Patents

Abstract

The invention relates to the use of an amine of formula (I) in a curing agent for epoxy resins, to a curing agent for epoxy resins containing the amine of formula (I) and to resultant epoxy resin compositions which can be used particularly as low-emission room-temperature-curing epoxy resin coatings demonstrating good workability, rapid curing, a high degree of hardness and high surface quality. The amine of formula (I) is low-odour, can be handled well at room temperature even without dilution, and can be produced at high purity in a simple process.

Description

 AMIN FOR EMISSIONSELECT EPOXY RESIN COMPOSITIONS

Technical area

 The invention relates to the field of amines, hardeners for epoxy resins, epoxy resin compositions, and their use, in particular as a coating, coating or coating.

State of the art

 For coating purposes suitable epoxy resin compositions should have the lowest possible viscosity so that they are easy to process at ambient temperature. Furthermore, they should harden as quickly as possible and without disruption, even in damp, cold conditions, and thereby form a level surface without turbidity, spots or craters. Finally, a cured coating should have a high hardness with low brittleness in order to withstand mechanical stress as well as possible. For optically demanding applications, such as floor coverings, a coating should also have a high degree of gloss and the lowest possible tendency to yellowing under the influence of light.

Prior art curing agents for epoxy coatings typically contain reaction products ("adducts") from the reaction of polyamines with epoxies, particularly bisphenol liquid resins. Such adducts allow for rapid cure, but are highly viscous, therefore the hardeners are for use in setting The non-adducted polyamines are typically odor-intensive and lead to increased occurrence of blushing effects. "Blushing effects" are hardening surface defects such as opacities, stains Roughness and stickiness, which are caused by blushing of amines with carbon dioxide (CO ₂ ) from the air and occur especially at high humidity and low temperatures The diluents typically reduce Blushing E. and improve the surface quality and brittleness of the coating, but are not incorporated into the resin matrix during curing and can be released by evaporation or diffusion processes. Today, however, increasingly low-emission products are desired, which have a low content of releasable substances after curing. For low-emission epoxy resin compositions, diluents, such as, for example, benzyl alcohol, can therefore only be used sparingly or not at all.

 The high viscosity and blushing susceptibility of the known adducts of polyamines with epoxides can be reduced not only by thinners but also in that the polyamine used in the adduction in large excess and the non-adducted excess is then removed by a separation process. However, the removal of the polyamines commonly used for adducting, such as IPDA, MXDA, DETA or TETA, is technically complicated and is usually incomplete, and the resulting reaction products are usually still highly viscous and / or prone to blushing, so that diluents are hardly dispensed with can.

 Known from the prior art are so-called aqueous epoxy resin coatings. These typically consist of an aqueous or water-dilutable hardener, which typically contains emulsified adducts of polyamines with epoxides, and an aqueous epoxy resin emulsion. Aqueous or water-dilutable hardeners typically have water contents in the range of 10 to 80% by weight. Aqueous epoxy resin products are usually low viscosity and low odor, but have other disadvantages. They are more expensive and considerably more expensive to produce than nonaqueous products, can be applied only at a sufficiently high temperature and in a relatively thin layer per operation, and have an increased water sensitivity during and after curing.

Presentation of the invention

The object of the present invention is therefore to provide a low-viscosity and low-odor amine for use in curing agents for room-temperature-curing epoxy resin compositions, which low-emission epoxy resin coatings with good processability and faster Curing allows coatings of high hardness and good surface quality.

 This object is achieved with the amine of formula (I) as described in claim 1. Surprisingly, the amine of formula (I) is so low viscosity that it is easy to handle at room temperature even without dilution. The amine of the formula (I) surprisingly scarcely tends to blushing effects. It can be prepared in a simple process in high purity, and reaction products from this process are low odor and good fluidity at room temperature and have a low content of unreacted diamine and not the formula (I) corresponding higher molecular weight by-products.

 Compared to similar known from the prior art adducts based on IPDA, MXDA, DETA or TETA, the amine of formula (I) is easier to produce in high purity, low viscosity and causes significantly less blushing effects.

 The amine of formula (I) enables low-emission epoxy resin compositions which are easy to process, cure rapidly, form high-quality plastics of high hardness and a regular, non-sticky surface with high gloss and surprisingly hardly yellow under the influence of light.

 Further aspects of the invention are the subject of further independent claims. Particularly preferred embodiments of the invention are the subject of the dependent claims.

Ways to carry out the invention

The invention relates to the use of an amine of the formula (I) in a curing agent for epoxy resins,

in which

m is 0 to 3, X is 1, 2-ethylene or 1, 2-propylene, and

 Y represents a mononuclear or polynuclear aromatic hydrocarbon radical.

Substance names beginning with "poly", such as polyamine, polyol or polyepoxide, refer to substances which formally contain two or more of the functional groups occurring in their name per molecule.

As the "primary amino group" is meant an NH ₂ group which is bonded to an organic radical and "secondary amino group" is an NH group which is bonded to two organic radicals, which may also be part of a ring together ,

 The term "amine hydrogen" refers to the hydrogen atoms of primary and secondary amino groups.

The term "amine hydrogen equivalent weight" denotes the weight fraction of a hardener or of an amine per amine hydrogen present in the hardener or in the amine.

 As a "thinner" is a soluble in an epoxy resin and its viscosity-reducing substance is referred to, which is not covalently incorporated into the resin matrix during the curing of the epoxy resin.

The term "viscosity" in the present document refers to the dynamic viscosity or shear viscosity, which is defined by the ratio between the shear stress and the shear rate (velocity gradient) and determined as described in the exemplary embodiments A dashed line in the formulas in this document in each case represents the bond between a substituent and the associated molecular residue. "Molecular weight" as used herein means the molar mass (in grams per mole) of a molecule. "Average molecular weight" refers to the number average M _{n of} an oligomeric or polymeric mixture of molecules, which is usually determined by gel permeation chromatography (GPC) against polystyrene as standard.

The term "room temperature" refers to a temperature of 23 ° C. Preferably, m is 0 or 1 or 2, particularly preferably 0 or 1, in particular 0. These amines allow particularly low-viscosity epoxy resin compositions.

The amine of the formula (I) is preferably in the form of a technical mixture which consists mainly of amines of the formula (I) in which m is 0 or 1.

 Preferably, m stands on the average for a value of less than 0.2.

With particular preference, m stands on average for a value in the range from 0 to 0.18, in particular 0 to 0.15.

The hardener is preferably a non-aqueous hardener. A "non-aqueous hardener" is a hardener which contains less than 5% by weight, preferably less than 2% by weight, in particular less than 1% by weight, of water.

Preferably, X is 1, 2-propylene. Its methyl group may be either in the 1-position or in the 2-position to the adjacent primary amino group. Such an amine of the formula (I) enables epoxy resin products with particularly low viscosity and particularly beautiful surfaces.

Y is preferably an aromatic hydrocarbon radical having 6 to 25, in particular 6 to 18, carbon atoms.

Y is particularly preferably an aromatic hydrocarbon radical

selected from the group consisting of and where R is a hydrogen radical or methyl radical.

Such an amine of formula (I) is particularly low viscosity, particularly accessible and particularly inexpensive. In the event that Y for the rest in particular, the amine of formula (I) is derived from a bisphenol A liquid resin or from a bisphenol F liquid resin or from a mixture of bisphenol A and bisphenol F liquid resin, as are commercially available are.

 These amines of formula (I) are particularly low viscosity, particularly easy to access, particularly inexpensive and particularly compatible in conventional epoxy resin compositions.

Particularly preferred is an amine of formula (I) wherein m is 0 to 1, X.

for 1, 2-propylene and Y is a radical of the formula

stand.

 Preferably, m stands on the average for a value of less than 0.2.

With particular preference, m stands on average for a value in the range from 0 to 0.18, in particular 0 to 0.15.

 Such an amine is particularly accessible and has a particularly low tendency to blushing effects.

An amine of formula (I) is preferably obtained from the reaction of at least one diamine selected from 1, 2-ethylenediamine and 1, 2-propylenediamine with at least one Di lycidylether of formula (II).

In the formula (II), m and Y have the meanings already mentioned. The amine of the formula (I) is preferably used for the described use in the form of a reaction product from the reaction of at least one diamine selected from 1,2-ethylenediamine and 1,2-propylenediamine with at least one diglycidyl ether of the formula (II).

Preferred diamine for the reaction described is 1,2-propylenediamine. Such a reaction product is particularly low viscosity and allows epoxy resin products with particularly beautiful surfaces.

Suitable diglycidyl ethers of the formula (II) are mononuclear or polynuclear aromatic diglycidyl ethers, in particular technical epoxy resins, in particular the glycidylation products of:

 - Bisphenol-A, bisphenol-F or bisphenol-A / F, where A is acetone and F is formaldehyde, which were used as starting materials for the preparation of these bisphenols. In the case of bisphenol-F, positional isomers may also be present, especially derived from 2,4'- or 2,2'-hydroxyphenylmethane.

- Dihydroxybenzene derivatives such as resorcinol, hydroquinone or pyrocatechol;

- Further bisphenols 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 (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) , Bis (2-hydroxynaphth-1-yl) methane, bis (4-hydroxynaphth-1-yl) methane or 1,5-dihydroxynaphthalene. Preferred diglycidyl ethers of the formula (II) are bisphenol A diglycidyl ethers, bisphenol F diglycidyl ethers, bisphenol A / F diglycidyl ethers, resorcinol diglycidyl ethers or hydroquinone diglycidyl ethers, in particular commercially available technical grades.

Particularly preferred are bisphenol A diglycidyl ether, bisphenol F diglycidyl ether or bisphenol-A F-diglycidyl ether, in particular Araldite ^® GY 240, Araldite ^® GY 250, Araldite ^® GY 281, Araldite ^® GY 282, Araldite ^® GY 285, Araldite ^® PY 304 or Araldite ^® PY 720 (all available from Huntsman), or DER ^® 330, DER ^® 331, DER ^® 332, DER ^® 336, DER ^® 351, DER ^® 352, DER ^® 354 or DER ^® 356 (all ex Dow) ,

In the reaction, the ratio between the number of primary amino groups and the number of epoxide groups is preferably in the range from 2.5: 1 to 25: 1, in particular 4: 1 to 15: 1.

The temperature in the reaction is preferably in the range from 40 to 120.degree. C., in particular from 60 to 100.degree.

 Excess unreacted diamine is preferably removed after the reaction by means of distillation, in particular by means of thin film or short path distillation in vacuo.

The reaction product from this preparation, in addition to the amine of formula (I) shares of higher molecular weight by-products, in particular in the form of multiply adducted diamine, as exemplified in the following formula for the case m = 0.

H ₂ NXN ^ ^{S /} ^ 0 -Y-0 ' ^{/ s'} ^ NXN ^ ^S ^^

 H I I H I I H

OH OH OH OH

A prepared in the manner described amine of formula (I) has a particularly low content of higher molecular weight by-products and is characterized by a particularly low viscosity and thus particularly good properties in the inventive use. The amine of formula (I) is thus preferably in the form of a reaction product of the reaction of at least one diamine selected from 1, 2-ethylenediamine and 1, 2-propylenediamine with at least one diglycidyl ether Formula (II) used, wherein the ratio between the number of primary amino groups and the number of epoxy groups is at least 2.5: 1 and excess diamine is removed by distillation after the reaction. The ratio between the number of primary amino groups and the number of epoxide groups is preferably in the range from 2.5: 1 to 25: 1, in particular 4: 1 to 15: 1. Surprisingly, a reaction product from this preparation is so low viscosity that it is easy to handle at room temperature even without dilution. Preferably, the reaction product is substantially free of 1, 2-ethylenediamine and / or 1, 2-propylenediamine. It contains in particular less than 1% by weight, preferably less than 0.5% by weight, particularly preferably less than 0.1% by weight, of 1, 2-ethylenediamine and / or 1, 2-propylenediamine. The amine of formula (I) is used in a curing agent for epoxy resins. The hardener is stable on its own; that is, it can be stored at room temperature in a suitable container for a prolonged period of time, typically for 3 to 6 months and longer, without its storage and application properties changing to a relevant extent and thus its utility as Hardener for epoxy resins loses.

In a curing agent for epoxy resins, the amine of formula (I) is preferably used in combination with other amines and / or accelerators.

Another object of the invention is accordingly a hardener, in particular a non-aqueous hardener, for epoxy resins containing at least one amine of formula (I) and at least one further amine and / or at least one accelerator.

The further amine is in particular not 1,2-ethylenediamine, not 1,2-propylenediamine, no amine of the formula (I), no amine of the formula (I) with values of m> 3 and / or no higher molecular weight by-product in the form of repeatedly adducted diamine. Such a hardener has a particularly low viscosity and / or a particularly high reactivity with respect to epoxy resins.

Suitable accelerators are substances which accelerate the reaction between amino groups and epoxide 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, other organic or inorganic acids such as in particular phosphoric acid, or mixtures of the abovementioned acids and acid esters; tertiary amines such as in particular 1, 4-diazabicyclo [2.2.2] octane, benzyldimethylamine, α-methylbenzyldimethylamine, triethanolamine, dimethylaminopropylamine, imidazoles such as in particular N-methylimidazole, N-vinylimidazole or 1, 2-dimethylimidazole , Salts of such tertiary amines, quaternary ammonium salts, in particular benzyltrimethylammonium chloride, amidines such as, 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 such as in particular 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol or polymers of phenol, formaldehyde and N, N-dimethyl-1,3 propanediamine, phosphites, in particular di- or triphenyl phosphites, or mercapto-containing compounds. Preferred accelerators are acids, tertiary amines or Mannich bases.

 Most preferred is salicylic acid or 2,4,6-tris (dimethylaminomethyl) phenol or a combination thereof.

Particularly suitable as a further amine are polyamines which have at least two, in particular at least three, amino acid reactive toward epoxide groups, in particular the following polyamines:

Polyamines having one or two secondary amino groups, in particular products of the reductive alkylation of primary aliphatic polyamines with aldehydes or ketones, in particular N-benzyl-1,2-propanediamine, N, N'-dibenzyl-1,2-propanediamine, N-benzyl Benzyl 1, 3-bis (aminomethyl) benzene, N, N'-Dibenzyl-1,3-bis (aminonnethyl) benzene, N-2-ethylhexyl-1,3-bis (aminomethyl) benzene, N, N'-bis (2-ethylhexyl) -1, 3 bis (aminonnethyl) benzene, or partially styrenated polyamines such as styrenated MXDA

(available as gas fireplaces ^® 240 from Mitsubishi Gas Chemical);

aliphatic, cydoaliphatic or arylaliphatic primary diamines, especially 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 (C1 1 -nododiamine), 1, 6-hexanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,2 (4), 4-trimethylhexamethylenediamine ( TMD), 1, 7-heptanediamine, 1, 8-octanediamine, 1, 9-nonanediamine, 1, 10-decanediamine, 1, 1 1-undecanediamine, 1, 12-dodecanediamine, 1, 2, 1, 3 or 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane (H ₂ -MDA), 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- or 4-methyl-1,3-diaminocyclohexane or mixtures thereof, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 2,5 (2,6) -Bis ( aminomethyl) bicyclo [2.2.1] heptane (NBDA), 3 (4), 8 (9) - Bis (aminomethyl) tricyclo [5.2.1 .0 ^{2 '6]} decane 1, 4-diamino-2,2,6-trimethylcyclohexane (TMCDA), 1, 8-Me N- thandiamin, 3,9-bis (3 -aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 1, 3-bis (aminomethyl) benzene (MXDA) or 1, 4-bis (aminomethyl) benzene;

Ether group-containing aliphatic primary di- or triamines, in particular bis (2-aminoethyl) ether, 3,6-dioxaoctane-1, 8-diamine, 4,7-dioxadecane-1, 10-diamine, 4,7-dioxadecan-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 these diamines, polytetrahydrofurans bis (3-aminopropyl) or other Polytetrahydrofurandiamine, cydoaliphatische ether groups-containing diamines of the propoxylation and subsequent amination of 1, 4-dimethylol cyclohexane, available as Jeffamine ^® particular RFD 270 (of Hunts- man), or polyoxyalkylenedi- or triamines, which typically represent products from the amination of polyoxyalkylene or triols and are available, for example under the name Jeffamine ^® (from Huntsman), under the name polyetheramine (from BASF) or under the name PC Amines (from Nitroil). Particularly suitable polyoxyalkylene or -triami- ne are 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, or the corresponding amines by BASF or Nitroil;

secondary amino-containing polyamines having two primary aliphatic amino groups, in particular 3- (2-aminoethyl) aminopropylamine bis (hexamethylene) triamine (BHMT), diethylenetriamine (DETA), triethylenetetamine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA) or higher homologs of linear polyethyleneamines such as polyethylenepolyamine having 5 to 7 ethylenepolyamines (HEPA), products of the multiple cyanoethylation or cyanobutylation and subsequent hydrogenation of primary di- and polyamines having at least two primary amino groups, such as dipropylenetriamine ( DPTA), N- (2-aminoethyl) -1,3-propanediamine (N3-amine), N, N'-bis (3-aminopropyl) ethylenediamine (N4-amine), N, N'-bis (3 -aminopropyl) -1,4-diaminobutane, N5- (3-aminopropyl) -2-methyl-1,5-pentanediamine, N3- (3-aminopentyl) -1,3-pentanediamine N5- (3-amino-) 1-ethyl-propyl) -2-methyl-1,5-pentanediamine or N, N'-bis (3-amino-1-ethyl-propyl) -2-methyl-1,5-pentanediamine;

aliphatic, cycloaliphatic or arylaliphatic primary triamines, in particular 4-aminomethyl-1, 8-octanediamine, 1, 3,5-tris (aminomethyl) benzene, 1, 3,5-tris (aminomethyl) cyclohexane, tris (2-aminoethyl) amine Tris (2-amino-propyl) amine or tris (3-aminopropyl) amine;

aromatic polyamines, in particular m- and p-phenylenediamine, 4,4'-, 2,4 'and / or 2,2'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA) diisocyanate, 2,4- and / or 2,6-toluene diamine, mixtures of 3,5-dimethylthio-2,4- and -2,6-toluene diamine (available as Ethacure 300 from Albermarle ^®), mixtures of 3,5-diethyl -2,4- and -2,6-toluenediamine (DETDA), 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane (M-DEA),

3,3 ', 5,5'-tetraethyl-2,2'-dichloro-4,4'-diaminodiphenylmethane (M-CDEA), 3,3'-diisopropyl-5,5'-dimethyl-4,4'- diaminodiphenylmethane (M-MIPA), 3,3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane (M-DIPA), 4,4'-diamino diphenylsulfone (DDS), 4-amino-N- ( 4-aminophenyl) benzenesulfonamide, 5,5'- Methylendianthranilsäure, dimethyl (5,5'-ethylendianthranilatil), 1, 3-propylene-bis (4-aminobenzoate), 1, 4-butylene-bis (4-aminobenzoate), polytetramethylene oxide bis (4-aminobenzoat ) (available (as Versalink ^® from Air Products), 1, 2- (bis (2-aminophenylthio) ethane, 2-methylpropyl 4-chloro-3,5-diaminobenzoate), or tert-butyl 4-chloro-3, 5-diaminobenzoate);

Polyamidoamines, in particular reaction products of a mono- or polybasic carboxylic acid, or their esters or anhydrides, in particular a dinner fatty acid, with an aliphatic, cycloaliphatic or aromatic polyamine used in stoichiometric excess, in particular a polyalkyleneamine such as DETA or TETA, especially those commercially available polyamidoamines Versamid ^® 100, 125, 140 or 150 (from Cognis), Aradur ^® 223, 250 or 848 (from Huntsman), Euretek ^® 3607 or 530 (from Huntsman) or Beckopox ^® EH 651, EH 654, EH 655, EH 661 or EH 663 (from Cytec);

Called phenalkamines, and Mannich bases, in particular reaction products of a Mannich reaction of phenols, in particular Carda- nol, with aldehydes, especially formaldehyde, in particular the commercially available phenalkamines Cardolite ^® NC-541, NC-557, NC-558, NC 566, Lite 2001 Lite 2002, NX-4943, NX-5607 or NX-5608 (from Cardolite®) Aradur ^® 3440, 3441, 3442 or 3460 (Huntsman) or Beckopox® ^® EH 614, EH 621, EH 624, EH 628 or EH 629 (from Cytec);

Adducts of 1,2-ethylenediamine or 1,2-propylenediamine with reactive diluents having epoxide groups, in particular monoglycidyl ethers of phenols, mono- or diglycidyl ethers of aliphatic or cycloaliphatic alcohols, diols or glycols, in particular phenyl glycidyl ether, cresyl glycidyl ethers, guaiacol glycidyl ethers, 4-methoxyphenyl glycidyl ethers, 4-n-butyl-phenylglycidyl ether, 4-tert-butylphenylglycidyl ether, 4-nonylphenylglycidyl ether, 4-dodecylphenylglycidyl ether, cardanolglycidyl ether, benzylglycidyl ether, allylglycidyl ether, butylglycidyl ether, hexylglycidyl ether, 2-ethylhexylglycidyl ether, fatty alcohol glycidyl ether, in particular Cs - to C-io-alkyl glycidyl ether or Ci2- to Ci ₄ alkyl glycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, 1, 4-Cyclohexandimethanoldiglycidylether or diglycidyl ethers of polyethylene or polypropylene glycols; - As well as higher molecular weight by-products from the previously described preparation of the amine of formula (I), in particular in the form of multiply adducted diamines, as previously described. Preferred as a further amine are polyamines having one or two secondary amino groups, in particular N-benzyl-1,2-propanediamine, N-benzyl-1,3-bis (aminomethyl) benzene, N-2-ethylhexyl-1,3-bis (aminomethyl) benzene or styrenated MXDA. Such amines give particularly low-viscosity hardeners that allow epoxy resin compositions with particularly rapid curing and beautiful surface.

Also preferred as a further amine are primary diamines, in particular MPMD, TMD, H ₁₂ -MDA, IPDA, 2- or 4-methyl-1,3-diaminocyclohexane or mixtures thereof, 1,3-bis (aminomethyl) cyclohexane, 1,4 Bis (aminomethyl) cyclohexane, NBDA or MXDA. Such amines give particularly low viscosity hardeners.

As another amine Further preferred are ether groups-containing aliphatic primary di- or triamines, in particular polyoxyalkylene or triamines having an average molecular weight in the range of 200 to 500 g / mol, especially Jeffamine ^® D-230 or Jeffamine ^® T-403 (both from Huntsman), or cycloaliphatic diamines containing ether groups of the propoxylation and subsequent amination of 1, 4-dimethylolcyclohexane, especially Jeffamine ^® RFD-270 (from Huntsman). Such amines give particularly low viscosity hardeners.

As another amine Also preferred are adducts of 1, 2-ethylene diamine or 1, 2-propylene diamine with epoxide having reactive, especially with cresyl glycidyl ether or C ₂ - to C ₁₄ -Alkylglycidylether or 1, 4-butanediol diglycidyl ether, or 1, 6-hexanediol diglycidyl ether.

Very particularly preferred as a further amine is N-benzyl-1,2-propanediamine. This amine gives very particular low viscosity hardeners, which are particularly easy-to-process epoxy resin products with fast curing and a beautiful surface.

The hardener according to the invention contains preferably 1 to 80% by weight, preferably 2 to 70% by weight, particularly preferably 5 to 60% by weight, in particular 10 to 50% by weight, of amine of the formula (I). Such hardeners are characterized by a low viscosity and allow epoxy resin coatings with high curing speed, high hardness and beautiful surfaces.

A particularly preferred hardener for epoxy resins contains

 at least one amine of the formula (I),

 N-benzyl-1,2-propanediamine, and

 optionally at least one further amine and / or an accelerator.

 In this case, the amine of the formula (I), N-benzyl-1,2-propanediamine and the further amine are present in an amount such that all of the amine hydrogens of the hardener

 5 to 60% of the amine of the formula (I),

 20 to 80% of N-benzyl-1,2-propanediamine, and

 0 to 40% originate from at least one further amine.

Such a curing agent has a low viscosity and, in particular, cures quickly and largely without blushing effects to give cured films of high gloss and high hardness.

The hardener is preferably substantially free of amines having a molecular weight below 120 g / mol, in particular below 150 g / mol. The hardener preferably contains less than 2% by weight, in particular less than 1% by weight, of amines having a molecular weight of less than 120 g / mol, in particular less than 150 g / mol.

Such a curing agent is toxicologically and odorally particularly advantageous and allows low-emission coatings with particularly beautiful surfaces. The hardener may further contain at least one diluent, 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 mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, propylene glycol butyl ether, propylene glycol phenyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol di-n-butyl ether, N-methylpyrrolidone, diphenylmethane, diisopropylnaphthalene, petroleum fractions such as Solvesso ^® grades (from Exxon), alkylphenols such as tert-butylphenol, nonylphenol, dodecylphenol and 8.1 1,14-pentadecatrienylphenol (Card anol, from cashew nut oil, obtainable, for example, as car dolite NC-700 from Cardolite Corp., USA), styrenated phenol, bisphenols, aromatic hydrocarbon resins, in particular phenol group-containing types, alkoxylated phenol, in particular ethoxylated or propoxylated phenol, in particular 2- Phenoxyethanol, adipate, sebacate, phthalates, benzoates, organic phosphoric or sulphonic acid esters or sulphonamides. Benzyl alcohol, dodecyl phenol, tert-butylphenol, styrenated phenol, ethoxylated phenol, or phenol group-containing aromatic hydrocarbon resins, in particular the Novares LS 500 ^® types, LX 200, LA 300 or LA 700 are preferred (from Rutgers).

Preferably, the hardener contains no or only a small content of thinners. The hardener preferably contains a maximum of 5% by weight of thinner.

The hardener may contain further substances which are reactive toward epoxide groups, for example monoamines such as hexylamine or benzylamine, or compounds containing mercapto groups, in particular the following: - liquid mercaptan-terminated polysulfide polymers, known under the trade name Thiokol ^® (from Morton Thiokol, for example, available from SPI Supplies, or by Toray Fine Chemicals), in particular the types of LP-3, LP-33, LP-980, LP 23, LP-55, LP-56, LP-12, LP-31, LP-32 or LP-2; and also known under the brand name Thioplast ^® (ex Akzo Nobel), in particular the types of G 10, G 1 12 G 131, G 1, G 12, G 21, G 22, G 44 or G 4;

 Mercaptan-terminated polyoxyalkylene ethers, obtainable, for example, by reaction of polyoxyalkylene di- or triols with either epichlorohydrin or with an alkylene oxide, followed by sodium hydrogen sulfide;

- mercaptan-terminated compounds in the form of polyoxyalkylene derivatives known under the trademark Capcure ^® (from Cognis), in particular the types WR-8, LÖF or 3-800;

 Polyesters of thiocarboxylic acids, for example pentaerythritol tetramer capoacetate, trimethylolpropane trimercaptoacetate, glycol dimercaptoacetate, pentaerythritol tetra- (3-mercaptopropionate), trimethylolpropane tri (3-mercaptopropionate) or glycoldi- (3-mercaptopropionate), or esterification products of polyoxyalkylene diols or triols, ethoxylated Trimethylolpropane or polyester diols with thiocarboxylic acids such as thioglycolic acid or 2- or 3-mercaptopropionic acid; or

 - Other mercapto-containing compounds, such as in particular 2,4,6-trimercapto-1, 3,5-triazine, 2,2 '- (ethylenedioxy) -diethanthiol (triethylene glycol dimercaptan) or ethanedithiol.

Another object of the invention is an epoxy resin composition comprising

 a resin component containing at least one epoxy resin and

 a hardener component containing at least one amine of the formula (I) as described above.

The resin and hardener components are typically present in separate containers and only become available immediately before application mixed together so that their reactive groups come into contact with each other and the composition hardens.

 The hardener component is preferably non-aqueous and preferably contains less than 5% by weight, more preferably less than 2% by weight, in particular less than 1% by weight, of water.

 The hardener component preferably comprises a hardener containing at least one amine of the formula (I) and at least one further amine and / or at least one accelerator, as described above. As epoxy resin customary technical epoxy resins are suitable. These are obtained in a known manner, for example from the oxidation of the corresponding olefins or from the reaction of epichlorohydrin with the corresponding polyols, polyphenols or amines.

 So-called polyepoxide flux resins, hereinafter referred to as "liquid resin", which have a glass transition temperature below 25 ° C., are particularly suitable as epoxy resin.

 Also possible as an epoxy resin are so-called solid resins, which have a glass transition temperature above 25 ° C and can be comminuted at 25 ° C pourable powders.

Suitable epoxy resins are in particular aromatic epoxy resins, in particular the glycidylation products of:

 - Bisphenol-A, bisphenol-F or bisphenol-A / F, where A is acetone and F is formaldehyde, which were used as starting materials for the preparation of these bisphenols. In the case of bisphenol-F, positional isomers may also be present, especially derived from 2,4'- or 2,2'-hydroxyphenylmethane.

- Dihydroxybenzene derivatives such as resorcinol, hydroquinone or pyrocatechol;

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'-dihydroxydiphenyl (DOD), 4,4'-dihydroxybenzophenone, bis (2-hydroxynaphth-1-yl) methane, bis (4-hydroxynaphth-1-yl) methane, 1, 5 Dihydroxynaphthalene, ths (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) ether or bis (4-hydroxyphenyl) sulfone;

 Condensation products of phenols with formaldehyde obtained under acidic conditions, such as phenol novolaks or cresol novolaks, also called bisphenol F novolaks;

 aromatic amines such as aniline, toluidine, 4-aminophenol, 4,4'-methylenediphenyldiamine, 4,4'-methylenediphenyl-di (N-methyl) amine, 4,4 '- [1,4-phenylene bis ( 1-methylethylidene)] bisaniline (bisaniline-P) or 4,4 '- [1,3-phenylene-bis (1-methylethylidene)] bisaniline (bisaniline-M).

Other suitable epoxy resins are aliphatic or cydoaliphatic poly epoxides, in particular

 Glycidyl ethers of saturated or unsaturated, branched or unbranched, cyclic or open-chain di-, tri- or tetrafunctional C 2 - to C 30 -alcohols, in particular ethylene glycol, propylene glycol, butylene glycol, hexanediol, octanediol, polypropylene glycols, dimethylolcyclohexane, neopentyl glycol, dibromoneopentyl glycol, Castor oil, trimethylolpropane, trimethylolethane, pentaerythrol, sorbitol or glycerol, or alkoxylated glycerol or alkoxylated trimethylolpropane;

 a hydrogenated bisphenol A, F or A / F liquid resin, or the glycidylation products of hydrogenated bisphenol A, F or A F;

an N-glycidyl derivative of amides or heterocyclic nitrogen bases, such as triglycidyl cyanurate or triglycidyl isocyanurate, or reaction products of epichlorohydrin with hydantoin. - Epoxy resins from the oxidation of olefins, in particular vinylcyclohexene, dicyclopentadiene, cyclohexadiene, cyclododecadiene, cyclododeca-, isoprene, 1, 5-hexadiene, butadiene, polybutadiene or divinylbenzene. Preferred as the epoxy resin in the resin component is a bisphenol-based liquid resin, particularly a diglycidyl ether of bisphenol-A, bisphenol-F or bisphenol-A / F, as commercially available from Dow, Huntsman or Momentive, for example. These liquid resins have a low viscosity for epoxy resins and, when cured, good properties as a coating. They may contain portions of bisphenol A solid resin or bisphenol F novolacs.

The resin component may contain a reactive diluent, in particular a reactive diluent having at least one epoxide group. Suitable reactive diluents are, in particular, the glycidyl ethers of monohydric or polyhydric phenols or aliphatic or cycloaliphatic alcohols, in particular the polyglycidyl ethers of diols or polyols already mentioned, or furthermore phenylglycidyl ether, cresyl glycidyl ether, benzylglycidyl ether, p-n-butylphenyl glycidyl ether, p-tert .Butylphenylglycidylether, nonyl phenyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, hexyl glycidyl ether, 2-ethylhexyl glycidyl ether, or glycidyl ethers of natural alcohols, such as in particular Cs-C-io-alkyl glycidyl ethers, or C12 to Ci ₄ -Alkylglycidylether. The addition of a reactive diluent to the epoxy resin causes a reduction of the viscosity, and / or a reduction of the glass transition temperature and / or the mechanical values.

Optionally, the epoxy resin composition contains further constituents, in particular auxiliaries and additives commonly used in epoxy resin compositions, for example the following:

- Solvents, thinners, film-forming aids or extenders, in particular the diluents already mentioned;

Reactive diluents, in particular epoxide-containing reactive diluents, as mentioned above, epoxidized soybean oil or linseed oil, Acetoacetate-containing compounds, in particular acetoacetylated polyols, butyrolactone, carbonates, aldehydes, and also isocyanates or silicones having reactive groups;

 Polymers, in particular polyamides, polysulfides, polyvinylformal (PVF), polyvinyl butyral (PVB), polyurethanes (PUR), polymers with carboxyl groups, polyamides, butadiene-acrylonitrile copolymers, styrene-acrylonitrile copolymers, butadiene-styrene copolymers , Homo- or copolymers of unsaturated monomers, in particular from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate or alkyl (meth) acrylates, in particular chlorosulfonated polyethylenes or fluorine-containing polymers, sulfonamide-modified melamines or purified montan waxes;

 inorganic or organic fillers, in particular ground or precipitated calcium carbonates, which are optionally coated with fatty acids, in particular stearates, barytes, talcs, quartz flour, quartz sand, iron mica, dolomites, wollastonites, kaolins, mica (potassium aluminum silicate) , Molecular sieves, aluminum oxides, aluminum hydroxides, magnesium hydroxide, silicas, cements, gypsum, flyash, soot, graphite, metal powders such as aluminum, copper, iron, zinc, silver or steel, PVC powder or hollow spheres;

- Fibers, in particular glass fibers, carbon fibers, metal fibers, ceramic fibers or plastic fibers such as polyamide fibers or polyethylene fibers;

 Pigments, in particular titanium dioxide and / or iron oxides;

 - the aforementioned accelerators;

 Rheology modifiers, in particular thickeners or anti-settling agents;

- adhesion promoters, in particular organoalkoxysilanes;

 - stabilizers against oxidation, heat, light or UV radiation;

flame-retarding substances, in particular aluminum hydroxide (ATH), magnesium dihydroxide (MDH), antimony trioxide, antimony pentoxide, boric acid (B (OH) ₃ ), zinc borate, zinc phosphate, melamine borate, melamine cyanurate, ammonium polyphosphate, melamine phosphate, melamine pyrophosphate, polybrominated diphenyl oxides or diphenyl ethers, phosphates in particular diphenylcresyl phosphate, resorcinol bis (diphenylphosphate), resorcinol diphosphate oligomer, tetraphenylresorcinol diphosphite, ethylenediamine diphosphate or Bisphenol A bis (diphenyl phosphate), tris (chloroethyl) phosphate, tris (chloropropyl) phosphate or tris (dichloroisopropyl) phosphate, tris [3-bromo-2,2-bis (bromomethyl) propyl] phosphate, tetrabromo- Bisphenol A, bis (2,3-dibromo propyl 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;

 - surface-active substances, in particular wetting agents, leveling agents, deaerators or defoamers;

 - Biocides, such as algicides, fungicides or fungal growth inhibiting substances.

The epoxy resin composition preferably comprises further auxiliaries and additives, in particular wetting agents, leveling agents, defoamers, stabilizers, pigments and / or accelerators, in particular salicylic acid and / or 2,4,6-tris (dimethylaminomethyl) phenol.

 Preferably, the epoxy resin composition contains no or only a small content of thinners, preferably at most 5% by weight, in particular at most 2% by weight.

In the epoxy resin composition, the ratio of the number of epoxy-reactive groups to the number of epoxy groups is preferably in the range of 0.5 to 1 .5, especially 0.7 to 1 .2.

When mixing the resin and the hardener component, the amine hydrogens present in the epoxy resin composition and, if appropriate, further epoxy-reactive groups react with the epoxide groups under their ring opening (addition reaction). As a result of these reactions, the composition polymerizes and eventually cures. It is known to the person skilled in the art that primary amino groups are difunctional with respect to epoxide groups and a primary amino group thus counts as two epoxide-reactive groups. The two components of the epoxy resin composition are each stored in a separate container. Further constituents of the epoxy resin composition may be present as constituent of the resin component or of the hardener component, other epoxide-reactive further constituents preferably being a constituent of the hardener component. A suitable container for storing the resin or hardener component is in particular a barrel, a hobbock, a bag, a bucket, a can, a cartridge or a tube. The components are storable, which means that they can be stored for several months to a year or more before being used, without changing their respective properties to a degree that is relevant to their use. To apply the epoxy resin composition, the resin and hardener components are mixed together shortly before or during application. The mixing ratio between the two components is preferably selected so that the epoxy groups reactive groups of the curing agent component are in a suitable ratio to the epoxy groups of the resin component, as previously described. In parts by weight, the mixing ratio between the resin component and the hardener component is usually in the range of 1:10 to 10: 1.

The mixing of the two components takes place by means of a suitable method; it can be continuous or batchwise. If mixing occurs before application, care must be taken that there is not too much time between blending the components and the application, as this can lead to disturbances, such as a slow or incomplete build-up of adhesion to the substrate. The mixing takes place in particular at ambient temperature, which is typically in the range of about 5 to 50 ° C, preferably at about 10 to 30 ° C.

With the mixing of the two components, the curing begins by chemical reaction, as previously described. Curing takes place especially at ambient temperature. It typically lasts for a few days to weeks until it is largely completed under the given conditions. The duration depends, among other things, on the temperature, the reactivity of the constituents and their stoichiometry and the presence of accelerators.

A further subject of the invention is therefore also a cured composition obtained from the curing of an epoxy resin composition as described in the present document.

The application of the epoxy resin composition takes place on at least one substrate, the following being particularly suitable:

- glass, glass ceramic, concrete, mortar, brick, brick, plaster or natural stones such as granite or marble;

 - metals or alloys such as aluminum, iron, steel or non-ferrous metals, or surface-refined metals or alloys such as galvanized or chromium-plated metals;

- Leather, textiles, paper, wood, with resins, for example phenolic, melamine or epoxy resins, bonded wood-based materials, resin-textile composites or other so-called polymer composites;

 Plastics, in particular hard or soft PVC, ABS, polycarbonate (PC), polyamide (PA), polyester, PMMA, epoxy resins, PUR, POM, PO, PE, PP, EPM or EPDM, the plastics optionally being replaced by plasma, Corona or flames are surface treated;

 - Fiber reinforced plastics such as Carbon Fiber Reinforced Plastics (CFRP), Glass Fiber Reinforced Plastics (GRP) or Sheet Molding Compounds (SMC);

coated substrates, such as powder-coated metals or alloys;

- paints or varnishes.

The substrates may be pretreated if necessary prior to application of the epoxy resin composition. Such pretreatments include, in particular, physical and / or chemical cleaning methods, for example grinding, sandblasting, shot peening, brushing and / or blowing off, as well as further treatment with cleaners or solvents or the application of an adhesion promoter, a primer solution or a primer. The described epoxy resin composition can advantageously be used as a fiber composite matrix for fiber composite materials (composites), in particular CFRP or GFRP, or as potting compound, sealant, adhesive, coating, coating, paint, varnish, sealant, primer or primer.

It can be used in particular as potting compound, for example as electrical potting compound, or as adhesive, in particular as car body adhesive, sandwich element adhesive, half-shell adhesive for wind turbine rotor blades, bridge element adhesive or anchoring adhesive.

In particular, it is also usable as a coating, coating, painting, lacquer, sealant, primer or primer for construction and industrial applications, in particular as a floor covering or floor coating for interiors such as offices, industrial halls, gymnasiums or cold rooms, or outdoors for balconies, terraces, parking decks , Bridges or roofs, as a protective coating for concrete, cement, metals, plastics or wood, for example for the surface sealing of wooden constructions, vehicles, loading areas, tanks, silos, shafts, pipelines, pipelines, machines or steel constructions, such as ships, piers, Offshore platforms, floodgates, hydroelectric power plants, river structures, swimming pools, wind turbines, bridges, fireplaces, cranes or sheet piling.

In particular, it is furthermore usable as a primer, adhesive coating, anticorrosive primer or for the hydrophobization of surfaces.

On the completely or partially cured epoxy resin composition, in particular when it is used as a coating, coating or coating, it is possible to apply a further coating, a further coating, or a further coating, wherein this further coating may likewise be an epoxy resin composition but also a different material, in particular a polyurethane or polyurea coating.

Particularly advantageously, the described epoxy resin composition is used as a coating. A further subject of the invention is accordingly a coating containing an epoxy resin composition as described above.

 Coating of all types of surface-applied coatings is understood as coating, in particular paints, varnishes, sealants, primers or primers, as described above, or floor coverings or protective coatings, especially those for heavy corrosion protection.

The described epoxy resin composition is particularly advantageously used in low-emission coatings with eco-labels, for example according to Emicode (EC1 Plus), AgBB, DIBt, Der Blaue Engel, AFSSET, RTS (M1) and US Green Building Council (LEED).

As a coating, the epoxy resin composition is advantageously used in a process for coating, wherein it has a liquid consistency with low viscosity and good flow properties and is applied in particular as a self-leveling or thixotropic coating on predominantly flat surfaces or as a paint. Preferably, the epoxy resin composition in this application, immediately after mixing the resin and the hardener component has a viscosity, measured at 20 ° C, in the range of 300 to 4Ό00 mPa s, preferably in the range of 300 to 2Ό00 mPa s, especially preferably in the range of 300 to 1 '500 mPa s, on. The blended composition is applied flat over the processing time as a thin film having a layer thickness of typically about 50 μm to about 5 mm onto a substrate, typically at ambient temperature. The application is carried out in particular by pouring onto the substrate to be coated and subsequent uniform distribution using, for example, a doctor blade or a dental trowel. The application can also be done with a brush or roller or as a spray application, for example as a corrosion protection coating on steel.

Curing typically produces largely clear, glossy and non-tacky films of high hardness, which have good adhesion to a wide variety of substrates. The application of the epoxy resin composition results in an article comprising the cured composition from the cure of the described epoxy resin composition. The cured composition is present in particular in the form of a coating.

The described epoxy resin composition is characterized by advantageous properties. It is low viscous and odorless and hardens quickly and largely without blushing effects, even at low levels or without the use of thinners, and especially without the use of volatile, odorous amines. In the areal use as a coating, clear, non-sticky films of high hardness and high surface quality are formed, which hardly yellow under the influence of light. With the epoxy resin composition described in particular low-emission epoxy resin products are available, which meet the conditions for many eco-labels and at the same time meet high standards of occupational safety, processing and performance characteristics.

Another object of the invention is an amine of the formula (I), welh in wel-

m is 0 to 1,

 X is 1, 2-propylene, and

Y is a radical of the formula where R is a

Hydrogen radical or methyl radical is.

Preferably, m stands on the average for a value of less than 0.2.

 With particular preference, m stands on average for a value in the range from 0 to 0.18, in particular 0 to 0.15.

 This amine is especially suitable for use in a curing agent for epoxy resins, as previously described.

It has the already mentioned advantageous properties. Examples

 Inn Below are exemplary embodiments which are intended to explain the described invention in more detail. Of course, the invention is not limited to these described embodiments.

 "AHEW" stands for the amine hydrogen equivalent weight.

 "EEW" stands for the epoxy equivalent weight.

 The term "Nornnklinna" refers to a temperature of 23 + 1 ° C and a relative humidity of 50 + 5%. "NK" stands for "standard climate".

Description of the measuring methods:

Infrared (FT-IR) spectra were measured as neat films on a Perkin-Elmer FT-IR 1600 instrument equipped with a horizontal ZnSe crystal ATR measuring unit; the absorption bands are given in wavenumbers (cm ^-1 ) (measurement window: 4000-650 cm ^-1 ).

The viscosity was measured on a thermostatted Rheotec RC30 cone-plate viscometer (cone diameter 50 mm, cone angle 1 °, cone tip-plate distance 0.05 mm, shear rate 10 s ^-1 ).

The amine number was determined by titration (with 0.1 N HClO ₄ in acetic acid against crystal violet).

Used substances:

Araldite ^® GY 250: Bisphenol A diglycidyl ether, EEW about 187.5 g / eq (of

 Huntsman)

Araldite ^® DY-E: monoglycidyl ether of C ₂ - to C ₄ -alcohols, EEW approx. 290 g / Eq (from Huntsman)

Erisys RDGE ^®-H: resorcinol diglycidyl ether, EEW about 1 18.5 g / Eq (from

 Emerald Performance Materials)

N-Benzyl-1, 2-pro reaction mixture, prepared as described in the following pandiamin ben, AHEW about 54.75 g / eq N-Benzyl-1, 2-propanediamine:

In a round-bottomed flask, 444.8 g (6 mol) of 1,2-propanediamine were initially introduced under nitrogen atmosphere at room temperature. With good stirring, a solution of 212.2 g (2 mol) of benzaldehyde in 1 '500 ml of isopropanol was slowly added dropwise and stirred for 2 hours. The reaction mixture was then hydrogenated at a hydrogen pressure of 90 bar, a temperature of 85 ° C and a flow of 5 ml / min on a continuous hydrogenation apparatus with Pd / C fixed bed catalyst. The reaction was checked by IR spectroscopy to see if the imine band had disappeared at about 1665 cm ^{-1 and then} the hydrogenated solution was concentrated on a rotary evaporator at 65 ° C., removing unreacted 1,2-propanediamine and isopropanol of which 300 g were distilled under reduced pressure at 80 ° C., collecting 237.5 g of distillate at a vapor temperature of 60 to 63 ° C. and 0.08 to 0.09 bar to obtain a colorless liquid having a viscosity of 8.5 mPa s at 20 ° C and an amine value of 682 mg KOH / g, which according to ¹ H-NMR, a mixture of N ¹ -benzyl-1, 2-propandiamin and N ² -benzyl-1, 2-propanediamine in the ratio of approx . 2/1 which, according to GC-FID, had a purity of> 97%.

Preparation of amines of the formula (I):

Amine 1:

148.3 g (2 mol) of 1,2-propylenediamine were initially introduced under a nitrogen atmosphere and heated to 80.degree. With good stirring, a solution of 37.4 g (0.1 mol) Araldite ^® GY-250 was added dropwise in 500 ml of warm (50 ° C) isopropanol slowly, keeping the temperature of the reaction mixture was maintained by cooling between 70 and 85 ° C. The reaction mixture was then left for 2 hours at 80 ° C and then the volatile constituents (isopropanol and excess 1, 2-propylenediamine) removed by distillation. There was obtained a clear, slightly yellowish, highly viscous liquid having a viscosity at 60 ° C of 86.9 Pa s and an amine value of 420.9 mg KOH / g. FT-IR: 2960, 2923, 2868, 1606, 1581, 1508, 1455, 1295, 1245, 1 181, 1034, 825.

Amine 2:

148.3 g (2 mol) of 1,2-propylenediamine were initially introduced under a nitrogen atmosphere and heated to 80.degree. With good stirring, a solution of 23.7 g (0.1 mol) Erisys RDGE ^®-H was added dropwise in 350 ml of warm (50 ° C) isopropanol slowly, keeping the temperature of the reaction mixture was maintained by cooling between 70 and 85 ° C. The reaction mixture was then left at 80 ° C. for 2 hours and then the volatiles (isopropanol and excess 1, 2-propylenediamine) were removed by distillation. A clear, slightly yellowish liquid having a viscosity at 60 ° C. of 13.2 Pa s and an amine number of 553.5 mg KOH / g was obtained.

FT-IR: 2955, 2921, 2869, 1589, 1490, 1450, 1286, 1263, 1 181, 1 145, 1039, 831, 760, 686.

Amine 3:

120.2 g (2 mol) of 1,2-ethylenediamine were initially introduced under a nitrogen atmosphere and heated to 80.degree. With good stirring, a solution of 37.4 g (0.1 mol) Araldite ^® GY-250 was added dropwise in 500 ml of warm (50 ° C) isopropanol slowly, keeping the temperature of the reaction mixture was maintained by cooling between 70 and 85 ° C. The reaction mixture was then left for 2 hours at 80 ° C and then the volatiles (isopropanol and excess 1, 2-ethylenediamine) removed by distillation. A clear, slightly yellowish, highly viscous liquid having a viscosity at 60 ° C. of 60.0 Pa.s (shear rate 5 s ^-1 ) and an amine number of 440.5 mg KOH / g was obtained.

Preparation of an amine as a comparison:

Amine 4:

148.3 g (2 mol) of 1,3-propylenediamine were initially introduced under a nitrogen atmosphere and heated to 80.degree. With good stirring, a solution of 37.4 g (0.1 mol) Araldite ^® GY-250 in 500 ml was slowly warm (50 ° C) isopropanol was added dropwise, wherein the temperature of the reaction mixture was maintained by cooling between 70 and 85 ° C. The reaction mixture was then left for 2 hours at 80 ° C and then the volatiles (isopropanol and excess 1, 3-propylenediamine) removed by distillation. A clear, slightly yellowish, highly viscous liquid having a viscosity at 60 ° C. of 30.5 Pa.s (shear rate 5 s ^-1 ) and an amine value of 417.6 mg KOH / g was obtained.

Preparation of hardeners and epoxy resin compositions

For each example, the ingredients of the hardener component shown in Table 1 were mixed in the indicated amounts (in parts by weight) by means of a centrifugal mixer (Speed Mixer ™ DAC 150, FlackTek Inc.) and stored with exclusion of moisture.

 Likewise, the ingredients of the resin component shown in Table 1 were processed and stored.

 Subsequently, the two components of each composition were processed by means of the centrifugal mixer to a homogeneous liquid and this immediately tested as follows:

 Ten minutes after mixing, the viscosity was determined at 20 ° C ("viscosity (10 ')").

 A first film was coated in a layer thickness of 500 μηη on a glass plate and this stored or cured under standard conditions. On this film the king's hardness (pendulum hardness according to King, measured according to DIN EN ISO 1522) after 1 day ("Königshärte (1 d NK)"), after 2 days ("Königshärte (2d NK)"), after 4 days (" King Hardness (4d NK) ") after 7 days (" Royal Hardness (7d NK) ") and after 14 days (" Royal Hardness (14d NK) ") After 14 days, the aspect of the film was evaluated (in the table with" Aspect (NK) "). "Beautiful" was a film that was clear and had a glossy and non-sticky surface without any texture, meaning any kind of drawing or pattern on the surface.

A second film was applied in a layer thickness of 500 μηη on a glass plate and this immediately after the application for 7 days 8 ° C and 80% relative humidity and then stored for 3 weeks in NK, or cured. Twenty-four hours after application, a polypropylene bottle cap was placed on the film, under which a moist sponge was placed. After another 24 hours, the sponge and lid were removed and placed in a new location on the film, where it was removed and repositioned after 24 hours, a total of 4 times. Next, the aspect of this film was evaluated (in the tables, "Aspect (8780%)") in the same manner as described for the aspect (NK), indicating the number of marks in the film On the thus hardened films, the king hardness was again determined, in each case after 7 days at 8 ° C and 80% relative humidity ("Königshärte (7d 8 80%)"), then after another 2 Days in NK ("Königshärte (+ 2d NK)"), 7 days in NK ("Königshärte (+ 7d NK)") and after 14d in NK ("Königshärte (+ 14d NK)").

The results are given in Table 1.

Example Ex-1 Ex-2 Ex-3 Ex-4 Ex-5 Ref-1 Ref-2

Resin Comp .:

Araldite ^® GY-250 167.2 167.2 167.2 167.2 167.2 167.2 167.2

Araldite ^® DY-E 31 .8 31 .8 31 .8 31 .8 31 .8 31 .8 31 .8

Hardener Comp .:

 Amine 1 51 .3 30.8 - - - - -

Amine 2 - - 32.1 - - - -

Amine 3 - - - 49.7 39.8 - -

Amine 4 - - - - - 51 .3 41 .0

N-benzyl-1, 2

25.6 37.3 27.4 24.9 35.9 25.6 31 .5 propandiamine

 Viscosity (10 ')

 5.0 1 .5 3.4 10.6 5.0 1 1 .1 4.7 [Pa-s]

 King's hardness [s]

 (1d NK) 81 77 95 83 89 83 129 (2d NK) 126 132 127 84 132 105 163 (4d NK) 155 165 132 120 173 147 191 (7d NK) 172 166 157 147 194 183 204 (14d NK) 179 181 nb 209 209 208 210 light, lightweight, light weight

Aspect (NK) beautiful beautiful

 Sign. Sign. Sign. Sign.

King's hardness [s]

 (7d 8 80%) 12 19 8 1 1 18 7 1 1 (+ 2d NK) 13 36 13 13 28 21 1 1 (+ 7d NK) 15 38 n.b. 20 60 27 38 (+ 14d NK) 17 50 n.b. 25 143 50 73

Aspect (8780%) slightly slightly slightly cloudy, cloudy, cloudy, cloudy, cloudy cloudy matt uneven uneven uneven uneven number brands 4 ¹ 2 2 1 1 1 1

Table 1: Composition and properties of Ex-1 to Ex-5 and Ref-1 and Ref-2. "nb" stands for "not determined""drawing." stands for "drawing" ¹ weak

Claims

 claims:

1 . Use of an amine of the formula (I) in a curing agent for epoxy resins,

 (I)

 in which

 m is 0 to 3,

 X is 1, 2-ethylene or 1, 2-propylene, and

 Y represents a mononuclear or polynuclear aromatic hydrocarbon radical.

Use according to claim 1, characterized in that the hardener is a non-aqueous hardener.

Use according to one of claims 1 or 2, characterized in that X is 1, 2-propylene.

Use according to any one of claims 1 to 3, characterized in that Y represents an aromatic hydrocarbon radical.

selects from the group consisting of and where R is a hydrogen radical or methyl radical. Use according to one of claims 1 to 4, characterized in that m is 0 to 1, X is 1, 2-propylene and Y is a radical of

formula stand. 6. Use of a reaction product from the reaction of at least one diamine selected from 1, 2-ethylenediamine and 1, 2-propylenediamine with at least one Di lycidylether of formula (II)

containing at least one amine of formula (I) as described in any one of claims 1 to 5 in a curing agent for epoxy resins. Use according to claim 6, characterized in that the

Ratio between the number of primary amino groups and the number of epoxide groups is at least 2.5: 1 and excess diamine is removed by distillation after the reaction. Use according to one of claims 6 or 7, characterized in that the reaction product contains less than 1% by weight of 1, 2-ethylenediamine and / or 1, 2-propylenediamine. 9. hardener for epoxy resins containing at least one amine of formula (I) as described in any of claims 1 to 5 and at least one further amine and / or at least one accelerator.

10. Hardener according to claim 9, characterized in that the further amine comprises N-benzyl-1,2-propanediamine.

1 1. Hardener according to one of claims 9 or 10, characterized in that 1 to 80% by weight of amine of the formula (I) is contained.

Epoxy resin composition comprising

 a resin component containing at least one epoxy resin and

- A curing agent component containing at least one amine of the formula (I) as described in any one of claims 1 to 5.

A coating containing an epoxy resin composition as described in claim 12.

14. Cured composition obtained from the curing of an epoxy resin composition according to one of claims 12 or 13.

Amine of the formula (I),

 (I)

 in which

 m is 0 to 1,

 X is 1, 2-propylene

Y is a radical of the formula where R is a hydrogen radical or methyl radical.