ACCELERATOR FOR THE CURING OF EPOXY RESINS WITH ALKYLATED AMINES

Technical area

The invention relates to the field of accelerators for epoxy resin compositions and their use, in particular as coatings.

State of the art

Epoxy resin-based coatings are widely used in construction. They consist of liquid resin and hardener components, which are mixed before application and then harden at ambient temperatures in the range of about 5 to 35 ° C to form a high-strength and durable material. Such epoxy resin coatings have a tendency to surface defects such as cloudiness, stains, roughness or stickiness, which is also known as "blushing". Blushing is caused by the salt formation of the amines contained in the hardener component with carbon dioxide (CO2) from the air and occurs particularly at high humidity and low temperatures.

The viscosity of an epoxy resin composition is reduced by means of thinners so that it can be applied easily and the substrate surfaces are well wetted. At the same time, thinners also reduce the susceptibility to blushing. The usual thinners, such as benzyl alcohol, are volatile compounds (VOC or SVOC) which are not built into the polymer matrix during curing and can therefore lead to emissions. For low-emission products, which are increasingly in demand by consumers, thinners can therefore only be used in small quantities or not at all.

To reduce blushing and as reactive thinners, alkylated amines can be used in the hardener component, as in EP 2,151, 461, EP

2,943,464, WO 2016/023839, EP 3,138,863 or EP 3,144,335.

However, alkylated amines lead to slower curing. The accelerators known for cold-curing epoxy resin compositions such as 2,4,6-tris (dimethylaminomethyl) phenol or acids such as salicylic acid can be used to accelerate the process. This means that the curing speed is still unsatisfactory, especially at cold temperatures, within the first 24 hours.

In EP 0,471, 988, EP 0,697,426 and EP 1, 319,677 calcium nitrate is described as an accelerator for the curing of epoxy resins with amines. However, neither cold temperatures nor alkylated amines are used.

Presentation of the invention

The object of the present invention is to provide low-emission epoxy resin coatings with good processability, which cure quickly and without blushing-related surface defects even in cold and damp conditions and thereby result in mechanically high-quality coatings with a low tendency to yellow.

This object is achieved with the composition containing calcium nitrate, at least one epoxy resin and at least one amine of the formula (I), as described in claim 1. The use of calcium nitrate as an accelerator for alkylated amines such as N-benzyl-1,2-ethanediamine has not yet been described. Surprisingly, calcium nitrate enables particularly rapid hardening in damp and cold conditions within the first 24 hours, which is particularly demanding for amines of the formula (I) with alkylated amino groups. A coating can therefore be walked on after a short time, typically within the first 24 hours after application, and can be processed further, for example overcoated or sealed. In addition, aesthetically beautiful surfaces with a high gloss are created even in cold and damp conditions.

The composition described enables low-emission epoxy resin products with good processability and long pot life, which cure quickly and can soon be walked on, especially in cold and damp conditions, and result in mechanically high-quality materials with a high surface quality and little tendency to yellow. Such epoxy resin products are particularly suitable as coatings, especially for floors.

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 of Carrying Out the Invention

The invention relates to a composition containing calcium nitrate, at least one epoxy resin and at least one amine of the formula (I),

(H 2 N) m -A- (NH-Y) n (I)

in which

m for 0 or 1, n for 1 or 2 and (m + n) for 2,

A stands for an alkylene radical with 2 to 10 carbon atoms, optionally containing nitrogen atoms or cyclic or aromatic fractions, and

Y stands for an alkyl, cycloalkyl or aralkyl radical having 1 to 20 carbon atoms.

A “primary amino group” is an amino group that is bound to a single organic radical and bears two hydrogen atoms; a “secondary amino group” is an amino group which is bonded to two organic radicals, which can also be part of a ring together, and which bears a hydrogen atom; and the term “tertiary amino group” denotes an amino group that is bonded to three organic radicals, two or three of which can be part of one or more rings, and which does not carry a hydrogen atom.

The hydrogen atoms of primary and secondary amino groups are referred to as “amine hydrogen”.

The “amine hydrogen equivalent weight” is the mass of an amine or an amine-containing composition that contains one molar equivalent of amine hydrogen.

Substance names beginning with “poly” such as polyamine or polyepoxide denote substances that formally contain two or more of the functional groups per molecule that appear in their name.

A “thinner” is a substance that is soluble in an epoxy resin and lowers its viscosity, which is not chemically incorporated into the epoxy resin polymer during curing.

“Molecular weight” is the molar mass (in grams per mole) of a molecule. The number average M n of a polydisperse mixture of oligomeric or polymeric molecules, which is usually determined by means of gel permeation chromatography (GPC) against polystyrene as the standard, is referred to as the “average molecular weight” .

The “pot life” refers to the processing time of an epoxy resin composition, ie the maximum possible time span between the mixing of the components and the application of the mixed composition in which it is in a sufficiently flowable state and can wet the substrate surfaces.

The “open time” of an adhesive is the maximum possible time span between the application of the adhesive and the joining of the parts to be bonded for a force-fit connection.

A temperature of 23 ° C is referred to as “room temperature”.

Calcium nitrate Ca (NO3) 2 can be present or used in the composition in anhydrous form or as tetrahydrate. Calcium nitrate is also known as the calcium salt of nitric acid or calcium nitrate. It acts in the composition as an accelerator during the curing of the epoxy resin with the amine of the formula (I).

Calcium nitrate is preferably used in the form of a solution that is liquid at room temperature.

In particular, calcium nitrate is used as a solution in water or an alcohol. Suitable alcohols are, in particular methanol, ethanol, the isomeric propanols or butanols, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monolbutylether, propylene glycol monophenyl ether, dipropylene glycol, dipropylene glycol monomethyl ether.

Calcium nitrate is particularly preferably used as a solution in water or ethanol.

Most preferably, calcium nitrate is present as an aqueous solution or is used as an aqueous solution.

The calcium nitrate solution preferably has a concentration in the range from 10 to 80% by weight, depending on the solubility in the solvent used.

An aqueous solution of calcium nitrate preferably has a concentration in the range from 30 to 70% by weight, in particular 40 to 70% by weight.

The composition preferably contains such an amount of calcium nitrate that 0.1 to 20, preferably 0.2 to 10, particularly preferably 0.3 to 7, in particular 0.5 to 5, parts by weight of calcium nitrate are present per 100 parts by weight of all amines with primary and / or secondary amino groups present.

Calcium nitrate can be present as a single accelerator or used in combination with other accelerators commonly used in epoxy resin compositions.

A liquid epoxy resin or a mixture containing two or more liquid epoxy resins is particularly suitable as the epoxy resin.

A technical polyepoxide with a glass transition temperature below 25 ° C is called "liquid epoxy resin".

A suitable liquid epoxy resin is obtained in a known manner, in particular from the oxidation of the corresponding olefins or from the reaction of epichlorohydrin with the corresponding polyols, polyphenols or amines.

Suitable liquid epoxy resins are in particular aromatic epoxy resins, in particular the glycidyl ethers of:

Bisphenol-A, bisphenol-F or bisphenol-A / F, where A stands for acetone and F for formaldehyde, which were used as starting materials for the production of these bisphenols. In the case of bisphenol-F, positional isomers can also be present, in particular derived of 2,4'- or 2,2'-hydroxyphenyl methane.

- Dihydroxybenzene derivatives such as resorcinol, hydroquinone or pyrocatechol;

- other 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, tris (4-hydroxyphenyl) methane, 1, 1, 2,2-tetrakis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) ether or bis (4-hydroxyphenyl) sulfone;

- Novolaks, which are in particular condensation products of phenol or cresols 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-phenylene-bis (1-methylethylidene)] bisaniline (bisaniline-M).

Further suitable liquid epoxy resins are aliphatic or cycloaliphatic

Polyepoxides, in particular

Glycidyl ethers of saturated or unsaturated, branched or unbranched, cyclic or open-chain di-, tri- or tetrafunctional C2 to C3o alcohols, in particular ethylene glycol, propylene glycol, butylene glycol, hexanediol, octanediol, polypropylene glycols, dimethylolcyclohexylene glycol, dimethylolcyclohexylene 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 flydantoin.

- Epoxy resins from the oxidation of olefins, such as in particular vinylcylohexene, dicyclopentadiene, cyclohexadiene, cyclododecadiene, cyclododecatriene,

Isoprene, 1,5-flexadiene, butadiene, polybutadiene or divinylbenzene.

A liquid resin based on a bisphenol, in particular a bisphenol A diglycidyl ether and / or bisphenol F diglycidyl ether, such as are commercially available, for example from Olin, Huntsman or Momentive, is preferred as the epoxy resin. These liquid resins have a low viscosity for epoxy resins and, when cured, they have good coating properties. They can contain proportions of solid bisphenol A resin or novolak glycidyl ethers.

The composition also contains at least one amine of the formula (I).

A is preferably a divalent radical selected from the group consisting of 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene, 1,3-butylene, 2-methyl-1 , 2-propylene, 1,3-pentylene, 1,5-pentylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene, 2-methyl-1,5-pentylene, 1,7-heptylene , 1, 8-octylene, 2,5-dimethyl-1, 6-hexylene, 1, 9-nonylene, 2.2 (4), 4-trimethyl-1, 6-hexylene, 1, 10-decylene, 1, 11 -undecylene, 2-butyl-2-ethyl-1,5-pentylene, 1,2-dodecylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, (1,5 , 5-trimethylcyclohexan-1-yl) methane-1, 3, 4 (2) -methyl-1, 3-cyclohexylene, 1, 3-cyclohexylene-bis (methylene), 1, 4-cyclohexylene-bis- (methylene) , 1,3-phenylene-bis (methylene), 1,4-phenylene-bis (methylene), 3-aza-1,5-pentylene, 3,6-diaza-1,8-octylene, 3,6,9 -Triaza-1, 11 -undecylene, 3-aza-1, 6-hexylene and 3,7-diaza-1, 9-nonylene.These amines of the formula (I) are particularly easily available industrially.

Of these, 1,2-ethylene, 1,2-propylene, 2-methyl-1,5-pentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, (1,5, 5-trimethylcyclohexan-1-yl) methane-1, 3, 4 (2) -methyl-1, 3-cyclohexylene, 1, 3-cyclohexylene-bis (methylene),

1,4-Cyclohexylenebis (methylene), 1,3-phenylenebis (methylene), 1,4-phenylenebis (methylene), 3-aza-1,5-pentylen, 3,6-diaza-1 , 8-octylene, 3,6,9-triaza-1, 11-undecylene, 3-aza-1, 6-hexylene or 3, 7-diaza-1, 9-nonylene.

The radical A is particularly preferably free of nitrogen atoms. Such a composition is particularly not sensitive to blushing effects.

In particular, A stands for a divalent radical selected from the group consisting of 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene, 1,3-butylene, 2-methyl-1, 2-propylene, 1,3-pentylene, 1,5-pentylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene, 2-methyl-1,5-pentylene, 1,7-heptylene, 1, 8-octylene, 2,5-dimethyl-1, 6-hexylene, 1, 9-nonylene, 2, 2 (4), 4-trimethyl-1, 6-hexylene, 1, 10-decylene, 1, 11 -Undecylene, 2-butyl-2-ethyl-1, 5-pentylene, 1, 12-dodecylene, 1, 2-cyclohexylene, 1, 3-cyclohexylene, 1, 4-cyclohexylene, (1, 5,5-trimethylcyclohexane 1 -yl) methane-1, 3, 4 (2) -methyl-1, 3-cyclohexylene, 1, 3-cyclohexylene-bis (methylene), 1, 4-cyclohexylene-bis (methylene), 1, 3-phenylene -bis (methylene) and 1,4-phenylene-bis (methylene).

A very particularly preferably represents 1,2-ethylene, 1,2-propylene, 1,3-cyclohexylenebis (methylene) or 1,3-phenylenebis (methylene). These amines of the formula (I) have a comparatively low viscosity and enable coatings with particularly attractive surfaces.

1,2-Ethylene is particularly preferred. These amines of the formula (I) have a particularly low viscosity, are particularly readily available and enable particularly rapid curing.

1,2-Propylene is also particularly preferred. These amines of the formula (I) have a particularly low viscosity and enable particularly beautiful surfaces.

Y is preferably hexyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl or an optionally substituted 1-phenylethyl, 2-phenylethyl,

Benzyl, naphthylmethyl, cyclohexylmethyl or 2-cyclohexylethyl radical.

Y is particularly preferably a radical selected from 2-ethylhexyl, 2-phenylethyl, benzyl, 1-naphthylmethyl and cyclohexylmethyl. These amines of the formula (I) have a comparatively low viscosity and enable particularly beautiful surfaces.

Y very particularly preferably represents benzyl. These amines of the formula (I) enable particularly rapid curing and particularly beautiful surfaces.

The amine of the formula (I) is preferably selected from the group consisting of N-benzyl-1,2-ethanediamine, N, N'-dibenzyl-1,2-ethanediamine, N- (1-naphthylmethyl) -1,2-ethanediamine, N-Cyclohexylmethyl-1,2-ethanediamine, N-benzyl-1,2-propanediamine, N, N'-dibenzyl-1,2-propanediamine, 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, N- (2-phenylethyl) - 1.3-bis (aminomethyl) benzene (part of styrenated 1, 3-bis (aminomethyl) benzene, available as gas fireplaces ® 240 from Mitsubishi gas Chemical), N -Benzyldi-ethylenetriamine, N-benzyltriethylenetetramine, N 1 , N 4 -dibenzyltriethylenetetramine, N-benzyltetraethylene pentamine, N 1, N 5 -dibenzyltetraethylene pentamine, N'-benzyl-N- (3-aminopropyl) ethylenediamine, N "-benzyl-N, N'-bis (3-aminopropyl) ethylenediamine and N", N "'- dibenzyl-N, N '-bis (3-aminopropyl) ethylenediamine.

Amines of the formula (I) in which m and n are each 1 are preferred. These amines of the formula (I) enable particularly rapid curing. Such an amine of the formula (I) may also contain a certain proportion of dialkylated amine, that is to say an amine of the formula (I) in which m is 0 and n is 2. The weight ratio between monoalkylated (n and m each stand for 1) and dialkylated amine (n stands for 2) is preferably at least 50/50, in particular at least 65/35.

Particularly preferred amine of the formula (I) is N-benzyl-1,2-ethanediamine or N-benzyl-1,2-propanediamine.

N-Benzyl-1,2-ethanediamine optionally contains proportions of N, N'-dibenzyl-1,2-ethanediamine. N-Benzyl-1,2-propanediamine optionally contains proportions of N, N'-dibenzyl-1,2-propanediamine.

Most preferred amine of the formula (I) is N-benzyl-1,2-ethanediamine. If necessary, this contains up to 35% by weight of N, N'-dibenzyl-1,2-ethanediamine, based on the sum of the two amines. This enables particularly rapid curing.

The amine of the formula (I) is preferably used as a component of a reaction mixture from the partial alkylation of at least one amine of the formula A (NFh) 2 with at least one alkylating agent.

The alkylation is preferably a reductive alkylation, an aldehyde or ketone and hydrogen being used as the alkylating agent.

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

When using molecular hydrogen, the reductive alkylation is preferably carried out in a pressure apparatus at a hydrogen pressure of 5 to 150 bar, in particular 10 to 100 bar. This can be done in a batch process or preferably in a continuous process.

The reductive alkylation is preferably carried out at a temperature in the range from 40 to 120.degree. C., in particular 60 to 100.degree.

In the case of small volatile diamines, such as in particular 1,2-ethanediamine or 1,2-propanediamine, this is preferably used in a stoichiometric excess compared to the aldehyde or ketone and not converted

set diamine is at least partially removed from the reaction mixture, in particular by means of stripping. If desired, the reaction mixture can then be purified further, in particular in that the monoalkylated amine is at least partially freed from the dialkylated amine by means of distillation.

The amine of the formula (I) is preferably present in such an amount that 0.1 to 1.2, preferably 0.2 to 1, in particular 0.2 to 0.8, mol of amine hydrogen from amines of the formula (I) are present per mole of epoxide groups. In the event that less than 1 mol of amine hydrogens from amines of the formula (I) are present per mole of epoxide groups, further amines which are reactive towards epoxide groups are preferably present.

Neither the epoxy resin nor the amine of the formula (I), the hardening of which is accelerated by calcium nitrate, are preferably present as an emulsion in water. In particular, the reaction mixture comprising at least one epoxy resin, at least one amine of the formula (I) and calcium nitrate is not water-based. The reaction mixture preferably contains less than 5% by weight, particularly preferably less than 1% by weight, of water. Such a reaction mixture enables very hydrophobic and stable materials.

In addition to calcium nitrate, at least one epoxy resin and at least one amine of the formula (I), the composition preferably also contains at least one further component selected from further accelerators, reactive thinners, further amines, thinners and fillers.

The epoxy resin composition preferably comprises

- A Flarz component containing the epoxy resin and optionally at least one reactive thinner and

- A Flärter component containing the amine of the formula (I) and optionally other amines,

where calcium nitrate, further accelerators and / or thinners can be present as part of the Flarz and / or Flärter component or as part of a further component.

Preferred further accelerators are 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 aforementioned 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-diazabi-cyclo [5.4.

2.4.6-Tris (dimethylaminomethyl) phenol or polymers of phenol, formaldehyde and N, N-dimethyl-1,3-propanediamine, phosphites such as, in particular, di- or triphenyl phosphites, or compounds containing mercapto groups.

Acids, tertiary amines or Mannich bases containing tertiary amino groups are preferred as accelerators. Salicylic acid or is particularly preferred

2.4.6-tris (dimethylaminomethyl) phenol.

The composition preferably contains 2,4,6-tris (dimethylaminomethyl) phenol, preferably in a weight ratio of calcium nitrate to 2,4,6-tris (dimethylaminomethyl) phenol in the range from 0.1 / 1 to 5/1, in particular 0.2 / 1 to 2/1.

Such a combination enables epoxy resin compositions which cure quickly to a particularly high final hardness in warm and cold ambient conditions.

As reactive diluents are preferably epoxy-containing reactive diluents, in particular butanediol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane-pandi- or triglycidlyether, phenyl glycidyl ether, cresyl glycidyl ether, glycidyl ether guaiacol, 4-methoxyphenyl glycidyl ether, p-butylphenyl, p-tert.Butylphenylglycidylether, 4-nonylphenyl glycidyl ether, 4-Dodecylphenylglyci dyl ether, cardanol glycidyl ether, benzyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, hexyl glycidyl ether, 2-ethylhexyl glycidyl ether, or glycidyl ethers of natural alcohols such as, in particular, C 8 to C 10 or C 12 to C 1 -C 5 alkyl ethers or C 13 to C 13 alkyl ethers.

Preferred further amines are aliphatic, cycloaliphatic or arylaliphatic polyamines with at least 2, in particular at least 3, amine hydrogens, such as in particular 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 -neodiamine), 1,6-hexanediamine, 2,5-dimethyl-1, 6-hexanediamine, 2,2 (4), 4-trimethyl-1,6-hexanediamine (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, 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 [5.2.1.02 6 ] decane, 1, 4-diamino-2,2,6-trimethylcyclohexane (TMCDA), 1, 8-menthane diamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.5 ] undecane, 1,3-bis (aminomethyl) benzene (MXDA), 1,4-bis (aminomethyl) benzene, bis (2-aminoethyl) ether, 3,6-dioxaoctane-1,8-diamine, 4,7- Dioxadecane-1, 10-diamine, 4,7-Dioxadecane-2,9-diamine, 4,9-Dioxadodecane-1, 12-diamine, 5,8-Dioxadodecane-3,10-diamine, 4,7, 10-trioxatridecane-1,13-diamine or higher oligomers of these diamines, bis (3-aminopropyl) polytetrahydrofuran or other polytetrahydrofuran diamines, cycloaliphatic ether group-containing diamines from the propoxylation and subsequent amination of 1,4-dimethylolcyclohexane, available in particular as Jeffamine ® RFD-270 (from Huntsman), or polyoxyalkylene di- or triamines, especially 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 corresponding amines from BASF or Nitroil, 2-aminoethylpiperazine, 3-dimethylaminopropylannine (DMAPA), 3- (3- (dimethylamino) propylamino) propylamine (DMAPAPA), bis (6-aminohexyl ) amine (BHMT), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylene pentamine (TEPA), pentaethylene hexamine (PEHA) or higher homologues of linear polyethylene amines, 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-diamino-nobutane, N5- (3- Aminopropyl) -2-methyl-1,5-pentanediamine, N3- (3-aminopentyl) -1,3-pentanediamine, N5- (3-amino-1-ethylpropyl) -2-methyl-1,5-pentanediamine, N , N'-bis (3-amino-1-ethylpropyl) -2-methyl-1, 5-pentanediamine, adducts of the above-mentioned or other polyamines with epoxides or epoxy resins,in particular adducts with diepoxides or monoepoxides, or polyamidoamines, in particular reaction products of a mono- or polybasic carboxylic acid or its ester or anhydride, in particular a dimer fatty acid, with an aliphatic, cycloaliphatic or aromatic polyamine used in stoichiometric excess, in particular a polyalkyleneamine such as as DETA or TETA, or Mannich bases, especially phenalkamines, that is, reaction products of phenols, especially cardanol, with aldehydes, especially formaldehyde, and polyamines.cycloaliphatic or aromatic polyamine, in particular a polyalkylene amine such as DETA or TETA, or Mannich bases, in particular phenalkamines, that is, reaction products of phenols, in particular cardanol, with aldehydes, in particular formaldehyde, and polyamines.cycloaliphatic or aromatic polyamine, in particular a polyalkylene amine such as DETA or TETA, or Mannich bases, in particular phenalkamines, that is, reaction products of phenols, in particular cardanol, with aldehydes, in particular formaldehyde, and polyamines.

The composition preferably contains at least one further amine selected from the group consisting of 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, polyoxypropylenediamines with an average molecular weight M n in the range from 200 to 500 g / mol, DMAPAPA, BHMT, DETA, TETA, TEPA, PEHA, DPTA, N3-amine, N4-amine, adducts of these or other polyamines with mono- or diepoxides and Mannich bases.

Of these, TMD, 1,3-bis (aminomethyl) cyclohexane, IPDA, MXDA, BHMT, DETA, TETA, TEPA, PEHA, DPTA, N3-amine, N4-amine or adducts thereof with mono- or diepoxides, in particular adducts thereof, are preferred with bisphenol-A or bis-phenol-F diglycidyl ether. The use of such an amine can enable a particularly high hardness or a particularly high glass transition temperature.

Of these, DMAPAPA is also preferred, in particular for use in epoxy resin adhesives. In this way, particularly high strengths and adhesive forces are obtained.

Of these, an adduct of MPMD or 1,2-propanediamine with cresyl glycidyl ether, in particular ortho-cresyl glycidyl ether, is also preferred. The adductation is preferably carried out with an excess of MPMD or 1,2-propanediamine compared to the cresyl glycidyl ether and the non-adducted amine is removed by distillation after the reaction.

The composition can preferably contain a combination of two or more of the further amines mentioned.

IPDA is particularly preferred as a further amine. This amine is widely available and enables epoxy resin products with high hardness and high glass transition temperature.

TETA or TEPA or N4-amine are also particularly preferred as a further amine. These amines are widely available, inexpensive and enable epoxy resin products with particularly rapid curing, high hardness and high glass transition temperature.

The composition can preferably also contain a combination of two or more such further amines.

Such further amines are preferably used in such an amount that 0.1 to 10, preferably 0.2 to 5, mol of amine hydrogen from further amines are present per mole of amine hydrogen from amines of the formula (I).

Particularly suitable thinners are 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 diethylene glycol , Ethylenglykoldiphenylether, 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-butylylether, propylene glycol butyl ether, propylene glycol phenyl ether, dipropylene glycol, Dipro-pylenglykolmonomethylether, dipropylene glycol dimethyl ether, dipropylene glycol di-n-butyl ether, diphenyl ether, diisopropyl naphthalene, petroleum fractions such as Solvesso ®Types (from Exxon), alkylphenols such as tert-butylphenol, nonylphenol, dodecylphenol, cardanol (made from cashew shell oil, containing 3- (8,1,1,14-pentadecatrienyl) phenol as the main component), styrenated phenol, bisphe -nols, aromatic hydrocarbon resins, especially types containing phenol groups, alkoxylated phenol, especially ethoxylated or propoxylated phenol, especially 2-phenoxyethanol, adipates, sebacates, phthalates, benzoates, organic phosphoric or sulfonic acid esters or sulfonamides.

Thinners with a boiling point of more than 200 ° C. are preferred.

The thinner is preferably selected from the group consisting of benzyl alcohol, styrenated phenol, ethoxylated phenol, aromatic hydrocarbon resins containing phenol groups, in particular the Novares ® types LS 500, LX 200, LA 300 or LA 700 (from Rütgers), diisopropylnaphthalene and Cardanol. Benzyl alcohol is particularly preferred.

Thinners containing phenolic groups also act as accelerators.

The composition preferably contains only a small amount of diluents. It preferably contains less than 25% by weight, particularly preferably less than 15% by weight, in particular less than 10% by weight,

Thinner. This enables low-emission or emission-free epoxy resin products.

Suitable fillers are in particular ground or precipitated calcium carbonate, which is optionally coated with fatty acids, especially stearates, barite (barite), talc, quartz powder, quartz sand, silicon carbide, iron mica, dolomite, wollastonite, kaolin, mica (potassium-aluminum -Silicate), molecular sieve, aluminum oxide, aluminum hydroxide, magnesium hydroxide, silicic acid, cement, gypsum, fly ash, soot, graphite, metal powder such as aluminum, copper, iron, zinc, silver or steel, PVC powder or hollow spheres.

Calcium carbonate, quartz powder and quartz sand are preferred.

If necessary, the composition contains further auxiliaries and additives, in particular the following:

Reactive diluents, in particular the previously mentioned or epoxidized soybean oil or linseed oil, compounds containing acetoacetate groups, in particular acetoacetylated polyols, butyrolactone, carbonates, aldehydes, isocyanates or silicones containing reactive groups;

- solvents;

- Other 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- and / or -2,6-tolylenediamine, 3,5-diethyl-2,4- and / or -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 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 or sulfonamide-modified melamines;

- 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, iron oxides or chromium (III) oxide;

- Rheology mod ifizierer, in particular thickeners or anti-settling agents;

- Adhesion improvers, in particular organoalkoxysilanes;

1,2-bis (tribromophenoxy) ethane, tris (2,3-dibromopropyl) isocyanurate, tribromophenol, hexabromocyclododecane, bis (hexachlorocyclopentadieno) cyclooctane or chloroparaffins; or

- Additives, in particular dispersed paraffin wax, film-forming aids, wetting agents, leveling agents, defoamers, deaerators, stabilizers against oxidation, heat, light or UV radiation or biocides.

The composition preferably contains further auxiliaries and additives, in particular pigments, wetting agents, leveling agents and / or defoamers.

In the composition, the ratio of the number of groups reactive toward epoxy groups to the number of epoxy groups is preferably in the range from 0.5 to 1.5, in particular 0.7 to 1.2.

The primary and secondary amino groups present in the composition and any further groups reactive toward epoxide groups which may be present react with the epoxide groups by opening their rings (addition reaction). As a result of primarily this reaction, the composition polymerizes and thereby hardens.

The resin and hardener components of the composition are stored in separate containers. Other components of the

Compositions can be present as a constituent of the resin or hardener component, further constituents reactive toward epoxy groups preferably being a constituent of the hardener component. It is also possible that further constituents are present as separate, further components.

A suitable container for storing the resin or hardener component is in particular a barrel, hobbock, bag, bucket, can, cartridge or tube. The components can be stored, which means that they can be stored for several months, up to a year or longer before they are used, without their respective properties changing to an extent relevant to their use. To use the epoxy resin composition, the components are mixed with one another shortly before or during application. The mixing ratio between the resin and hardener components is preferably chosen so that the epoxy-reactive groups of the hardener component are in a suitable ratio to the epoxy groups of the resin component, as described above.

The components are mixed using a suitable process; it can be carried out continuously or batchwise. If the mixing does not take place immediately before application, it must be ensured that there is not too much time between mixing the components and application and that the application takes place within the pot life. Mixing takes place in particular at ambient temperature, which is typically in the range from about 5 to 40.degree.

When the two components are mixed, hardening begins through a chemical reaction, as described above. Curing typically takes place at a temperature in the range from 0 to 150 ° C. It is preferably carried out at ambient temperature and typically extends over a few days to weeks. The duration depends, among other things, on the temperature, the reactivity of the constituents and their stoichiometry and the presence of accelerators.

The composition is applied to at least one substrate, the following being particularly suitable:

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

- Repair or leveling compounds based on PCC (polymer-modified

Cement mortar) or ECC (epoxy resin modified cement mortar);

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

- asphalt or bitumen;

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

- Plastics such as hard and soft PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxy resins, phenolic resins, PUR, POM, TPO, PE, PP, EPM or EPDM, each untreated or surface-treated, for example by means of plasma , Corona or flames;

- Fiber-reinforced plastics, such as carbon-fiber-reinforced plastics (CFRP), glass-fiber-reinforced plastics (GFRP) and sheet molding compounds (SMC);

- Insulating foams, in particular made of EPS, XPS, PUR, PIR, rock wool, glass wool or foamed glass (foam glass);

- Coated or lacquered substrates, in particular lacquered tiles, gestri chener concrete, powder-coated metals or alloys or lacquered sheets;

- Coatings, paints or varnishes, in particular coated floors, which are covered with a further floor covering layer.

If necessary, the substrates can be pretreated before application, in particular by physical and / or chemical cleaning processes or the application of an activator or a primer.

The curing of the composition described becomes a

cured composition obtained.

The composition described can advantageously be used as a coating, primer, adhesive, sealant, potting compound, casting resin or as a matrix for fiber composite materials (composites) such as in particular CFRP or GFRP. The term coating also includes primers, paints, varnishes and seals.

The composition is preferred as a coating or adhesive

used.

The composition described is particularly preferably used as a coating. Coating is understood to mean all types of coverings applied over a large area, in particular floor coverings, paints, varnishes, seals, primers, primers or protective coatings, in particular also those for heavy corrosion protection.

The composition is particularly suitable as a floor covering or floor coating for interiors such as offices, industrial halls, gyms 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 surface sealing of wooden structures, vehicles, loading areas, tanks, silos, shafts, pipelines, pipelines, machines or steel structures, e.g. ships, piers,

Offshore platforms, lock gates, hydropower plants, river structures,

Swimming pools, wind turbines, bridges, chimneys, cranes or sheet pile walls, or as a primer, adhesive coating, corrosion protection primer or for making surfaces water-repellent.

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

For use as a coating, the composition advantageously has a liquid consistency with low viscosity and good flow properties. The mixed composition is typically applied flatly as a thin film with a layer thickness of about 50 mm to about 5 mm on a substrate within the pot life, typically at ambient temperature. The application takes place in particular by pouring it onto the substrate to be coated and then uniformly distributing it with the aid of, for example, a squeegee or a notched trowel. The application can also take place with a brush or roller or as a spray application, for example as a corrosion protection coating on steel. The curing process typically produces largely homogeneous, glossy and non-sticky films of high hardness

Another object of the invention is a method for coating comprising the steps

(i) mixing the components of the composition described,

(ii) applying the blended composition to a substrate within the pot life,

followed by curing the blended composition.

A further coating can be applied to the completely or partially cured composition, this further layer likewise being an epoxy resin composition, but also a different material, in particular a polyurethane or polyurea coating.

The composition described is also particularly preferably used as an adhesive. When used as an adhesive, it typically has a pasty consistency with structurally viscous properties after the components have been mixed. During application, the mixed adhesive is applied to at least one of the substrates to be bonded within the pot life and the two substrates are bonded together within the open time of the adhesive.

The mixed adhesive is applied or applied in particular by means of a brush, roller, spatula, squeegee, trowel, or from a tube, cartridge or metering device.

The adhesive is particularly suitable for use in the construction industry, in particular for the reinforcement of structures using steel lamellas or lamellas made of carbon fiber-reinforced composite plastics (CFRP), for structures that contain glued precast concrete parts, in particular bridges or concrete towers For example for wind turbines, shafts, pipelines or

Tunnels, or for constructions, which bonded natural stones, ceramic

Elements or parts made of fiber cement, steel, cast iron, aluminum, wood or polyester contain, for anchoring dowels or steel rods in

Drilled holes, for fixing railings, parapets or door frames, for repairs such as filling edges, holes or joints in concrete repairs, or for sticking films made of polyvinyl chloride (PVC), flexible polyolefin (Combiflex ® ) or adhesive modified chlorosulfonated polyethylene (Hypalon ® ) on concrete or steel.

Further areas of application relate to structural bonding in the construction or manufacturing industry, in particular as an adhesive mortar, assembly adhesive, reinforcement adhesive such as in particular for bonding lamellas made of CFRP or steel to concrete, masonry or wood, as an element adhesive for, for example, bridge elements, sandwich element adhesive, facade element adhesive, reinforcement adhesive, bodywork adhesive or half-shell adhesive for rotor blades of wind turbines.

Such an epoxy resin adhesive is also suitable for filling cavities such as cracks, crevices or boreholes, whereby the adhesive is filled or injected into the cavity and, after curing, fills it and connects the flanks of the cavity with one another in a non-positive manner or glued.

Another object of the invention is a method for gluing comprising the steps

(i) mixing the components of the composition described,

(ii) applying the mixed composition within the pot life,

- either on at least one of the substrates to be bonded and joining the substrates to form a bond within the open time,

- or in a cavity or gap between several substrates and, if necessary, inserting an anchor into the cavity or gap within the open time,

followed by curing the blended composition.

A reinforcing iron, a threaded rod or a bolt is particularly referred to as an “anchor”. Such is in particular glued or anchored in a wall, wall, ceiling or foundation in such a way that part of it is non-positively glued and part of it protrudes and can be structurally loaded.

Similar or different substrates can be bonded.

From the application and curing of the composition described or from the method of coating or the method of gluing, an article is obtained which is coated or glued with the composition. This article can be a building or a part of it, in particular a building construction or civil engineering, an office, an industrial hall, a gym, a cold room, a silo, a bridge, a roof, a stairwell, a balcony, a Terrace or a parking deck, or it can be an industrial good or a consumer good, in particular a pier, an offshore platform, a lock gate, a crane, a sheet pile wall, a pipeline or a rotor blade of a wind turbine, or a means of transport such as in particular an automobile, a truck, a rail vehicle, a ship, an airplane or a helicopter,

The invention thus further provides an article obtained from the described method for coating or from the described method for gluing.

The composition described is distinguished by advantageous properties. It is simple and easy to process, especially as a coating, hardens quickly and can soon be walked on and / or worked on, especially in cold and damp conditions. In particular, mechanically high-quality coatings with a beautiful surface and a low tendency to yellowing are created.

Examples

In the following, exemplary embodiments are listed which are intended to explain the described invention in more detail. It goes without saying that the invention is not restricted to the exemplary embodiments described.

“AHEW” stands for the amine hydrogen equivalent weight.

"EEW" stands for the epoxy equivalent weight.

A temperature of 23 + 1 ° C and a relative humidity of 50 + 5% are referred to as “standard climate” (“NK”).

Description of the measurement methods:

The viscosity was measured on a thermostated cone-plate viscometer Rheotec RC30 (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 HCIO4 in acetic acid against crystal violet).

Substances and abbreviations used:

Sikafloor ® -264N (A) Sikafloor ® -264N component A (RAL 5005), filled pigmented resin component of an epoxy resin floor coating, EEW 450 g / Eq (from Sika)

B-EDA N-Benzyl-1,2-ethanediamine, prepared as described below, AHEW 50.1 g / eq

B-PDA N-benzyl-1,2-propanediamine, prepared as described below, AHEW 54.8 g / eq

TETA triethylenetetramine, AHEW approx. 28 g / eq (technical, from

Huntsman)

Adduct-1 adduct from 1,2-propylenediamine and technical o-cresyl glycidyl ether, prepared as described below AHEW 90 g / eq

Jeffamine ® D-230 polyoxypropylenediamine with average molecular weight approx. 240 g / mol, AHEW 60 g / Eq (from Huntsman)

Ca nitrate solution 50% by weight calcium nitrate tetrahydrate in water

Ancamine ® K54 2,4,6-Tris (dimethylaminomethyl) phenol (from Air Products)

N-Benzyl-1,2-ethanediamine (B-EDA):

180.3 g (3 mol) of 1,2-ethylenediamine were placed in a round bottom flask under a nitrogen atmosphere at room temperature. A solution of 106.0 g (1 mol) of benzaldehyde in 1200 ml of isopropanol was slowly added dropwise with thorough stirring and the mixture was stirred for a further 2 hours. The reaction mixture was then hydrogenated at a hydrogen pressure of 80 bar, a temperature of 80 ° C. and a flow rate of 5 ml / min in a continuously operating hydrogenation apparatus with a Pd / C fixed bed catalyst. To check the reaction was checked by IR-Spektros copy if the Iminbande at about 1665 cm 1disappeared. The hydrogenated solution was then concentrated on a rotary evaporator at 65 ° C., unreacted 1,2-ethylenediamine, water and isopropanol being removed. The reaction mixture obtained in this way was a clear, slightly yellowish liquid with an amine number of 678 mg KOH / g. 50 g of this were distilled at 80 ° C. under vacuum, 31.3 g of distillate being collected at a steam temperature of 60 to 65 ° C. and 0.06 mbar. A colorless liquid was obtained with a viscosity of 8.3 mPa s at 20 ° C., an amine number of 750 mg KOH / g and a purity of> 97% determined by GC.

N-Benzyl-1,2-propanediamine (B-PDA):

444.8 g (6 mol) of 1,2-propanediamine were placed in a round bottom flask under a nitrogen atmosphere at room temperature. A solution of 212.2 g (2 mol) of benzaldehyde in 500 ml of isopropanol was slowly added dropwise with thorough stirring and the mixture was stirred for a further 2 hours. The reaction mixture was then hydrogenated at a hydrogen pressure of 90 bar, a temperature of 85 ° C. and a flow rate of 5 ml / min in a continuously operating hydrogenation apparatus with a Pd / C fixed bed catalyst. To monitor the reaction, it was checked by means of IR spectroscopy whether the imine band at approx. 1665 cm 1 had disappeared. The hydrogenated solution was then concentrated on a rotary evaporator at 65 ° C., with

unreacted 1,2-propanediamine, isopropanol and water were removed. A clear, slightly yellowish liquid was obtained. 300 g of this were distilled at 80 ° C. under vacuum, with 237.5 g of distillate being collected at a steam temperature of 60 to 65 ° C. and 0.08 mbar. A colorless liquid with an amine number of 682 mg KOFI / g was obtained, which, according to 1 FI-NMR, is a mixture of N 1 -benzyl-1,2-propanediamine and N 2 -benzyl-1,2-propanediamine in a ratio of approx. 2/1 and had a GC purity of> 97%.

Adduct-1:

There were 04.15 kg 1, provided 2-propanediamine under a nitrogen atmosphere, warmed to 70 ° C and then slowly with vigorous stirring to 2.93 kg of Araldite ® offset DY-K (o-cresyl glycidyl ether technically, of Fluntsman), the Tem-perature of the reaction mixture Was 70 to 80 ° C. After 1 hour at 80 ° C., the reaction mixture was cooled and the volatile constituents were removed by distillation using a thin-film evaporator (0.5-1 mbar, jacket temperature 115 ° C.).

Production of epoxy resin compositions:

Examples 1 to 17:

For each example, the ingredients of the Flärter component stated in Tables 1 to 3 were mixed in the stated amounts (in parts by weight) by means of a centrifugal mixer (SpeedMixer ™ DAC 150, FlackTek Inc.) and stored in the absence of moisture.

As Flarz component was Sikafloor ® -264N Comp. A (blue) (Sika) used in the given in Tables 1 to 3 amount (parts by weight).

The two components of each composition were then processed into a homogeneous liquid using the centrifugal mixer and this was immediately tested as follows:

Ten minutes after the mixing, the viscosity was measured at 20 ° C

("Viscosity (10 ')").

To determine the Shore D hardness according to DIN 53505, two cylindrical test specimens (diameter 20 mm, thickness 5 mm) were produced. One was stored in a normal climate and the hardness measured after 1 day and after 2 days (1d

NK) or (2d NK), the other was stored at 8 ° C and 80% relative humidity and the hardness was measured after 1 day and after 2 days in a cold state (1d 8 80%) or (2d 8780% ).

A first film was drawn onto a glass plate in a layer thickness of 500 mΐti and this was stored or cured in a standard climate. The king's hardness (König pendulum hardness, measured in accordance with DIN EN ISO 1522) was determined on this film after 1 day (“King's hardness (1d NK)”), after 2 days (“King's hardness (2d NK)”), after 4 days (“King's hardness (4d NK) ”), after 7 days (“ King's hardness (7d NK) ”) and after 14 days (“ King's hardness (14d NK) ”). After 14 days, the aspect of the film was assessed (referred to as “Aspect (NK)” in the table). A film with a glossy, non-sticky surface without structure was described as “beautiful”. Any type of drawing or pattern on the surface is referred to as “structure”. A film with a non-sticky surface without structure and with reduced gloss was referred to as “matt”.

A second film was drawn onto a glass plate in a layer thickness of 500 mΐti and this was stored or cured immediately after application for 7 days at 8 ° C. and 80% relative humidity and then for 2 weeks in a standard climate. 24 hours after application, a polypropylene bottle lid was placed on the film, under which a damp sponge was placed. After a further 24 hours, the sponge and the lid were removed and placed in a new location on the film, where they were removed again and repositioned after 24 hours, a total of 4 times. The aspect of this film was then assessed (labeled “Aspect (8780%)” in the tables) in the same way as described for the aspect (NK). The number and type of visible marks that were created in the film by the damp sponge or the attached lid were also given. The number of white discolored spots was stated as “blushing”. The “ring” was given as the thickness of any ring-shaped impression caused by the first lid, placed on it 24 hours after application, sinking in. Such a ring-shaped imprint indicates that the coating cannot yet be walked on. On the films cured in this way, the Such a ring-shaped imprint indicates that the coating cannot yet be walked on. On the films cured in this way, the Such a ring-shaped imprint indicates that the coating cannot yet be walked on. On the films cured in this way, the

King's hardness determined, in each case after 7 days at 8 ° C and 80% relative humidity ("Königsh. (7d 8 80%)"), then after a further 2 days in the NK ("Königsh. (+ 2d NK)") or 7 days in the NK ("Königsh. (+ 7d NK)") or 14d in the NK ("Königsh. (+ 14d NK)").

The change in color after exposure was also determined in a weathering tester as a measure of the yellowing. For this purpose, a further film was applied to a glass plate in a layer thickness of 500 mΐti and this was stored or cured in a standard climate for 2 weeks and then in a weathering tester of the type Q-Sun Xenon Xe-1 with an optical filter Q-SUN Daylight- Q and a xenon lamp with a light intensity of 0.51 W / m 2 at 340 nm at a temperature of 65 ° C for 72 hours (Q-Sun (72h)). The color difference DE of the film exposed in this way was then compared to the corresponding non-exposed film using an NH310 colorimeter from Shenzen 3NFI Technology Co. LTD, equipped with silicone

Photoelectric Diode Detector, Light Source A, Color Space Measurement

Interface CIE L * a * b * C * H * , determined. DE values ​​up to 5 indicate a slight yellowing.

The results are given in Tables 1-3.

The examples labeled “(Ref.)” Are comparative examples.

Table 1: Composition and properties of Examples 1 to 6.

1 resolved in B-EDA

Table 2: Composition and properties of Examples 7 to 12.

Table 3: Composition and properties of Examples 13 to 17.

"Nm" stands for "not measurable" (too soft)

Patent claims:

1. Composition containing calcium nitrate, at least one epoxy resin and at least one amine of the formula (I),

(H 2 N) m -A- (NH-Y) n (I)

in which

m for 0 or 1, n for 1 or 2 and (m + n) for 2,

A stands for an alkylene radical with 2 to 10 carbon atoms, optionally containing nitrogen atoms or cyclic or aromatic fractions, and

Y stands for an alkyl, cycloalkyl or aralkyl radical having 1 to 20 carbon atoms.

2. Composition according to claim 1, characterized in that

Calcium nitrate is present as an aqueous solution.

3. Composition according to one of claims 1 or 2, characterized in that per 100 parts by weight of all amines present with primary and / or secondary amino groups 0.1 to 20, preferably 0.2 to 10, particularly preferably 0.3 to 7, in particular 0.5 to 5, parts by weight of calcium nitrate are present.

4. Composition according to one of claims 1 to 3, characterized in that A stands for 1,2-ethylene, 1,2-propylene, 1,3-cyclohexylenebis (methylene) or 1,3-phenylenebis ( methylene).

5. Composition according to one of claims 1 to 4, characterized in that Y stands for a radical selected from 2-ethylhexyl, 2-phenylethyl, benzyl, 1-naphthylmethyl and cyclohexylmethyl.

6. Composition according to one of claims 1 to 5, characterized in that m and n each stand for 1.

7. Composition according to one of claims 1 to 6, characterized in that the amine of the formula (I) is N-benzyl-1,2-ethanediamine or N-benzyl-1,2-propanediamine.

8. Composition according to one of claims 1 to 7, characterized in that 0.1 to 1.2, preferably 0.2 to 1, in particular 0.2 to 0.8, mol of amine hydrogen from amines of the formula (I) are present per mole of epoxide groups.

9. Composition according to one of claims 1 to 8, characterized in that it additionally contains at least one further component selected from further accelerators, reactive thinners, further amines, thinners and fillers.

10. Composition according to one of claims 1 to 9, characterized in that it contains 2,4,6-tris (dimethylaminomethyl) phenol.

11. Composition according to one of claims 1 to 10, characterized in that it contains at least one further amine selected from the group consisting of 2,2 (4), 4-trimethyl-1, 6-hexanediamine, 1, 2-, 1,3- or 1,4-diamino cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 1-amino-3-aminomethyl -3,5,5-trimethyl-cyclohexane, 2 (4) -methyl-1, 3-diaminocyclohexane, 1,3-bis (aminomethyl) benzene, polyoxypropylenediamines with an average molecular weight M n in the range from 200 to 500 g / mol, 3- (3- (dimethylamino) propylamino) propylamine, bis (6-aminohexyl) amine, diethylenetriamine, triethylenetetramine, tetraethylene pentamine, pentaethylene hexamine, dipropylenetriamine, N- (2-aminoethyl) -1, Contains 3-propanediamine, N, N'-bis (3-aminopropyl) ethylenediamine, adducts of these or other polyamines with mono- or diepoxides and Mannich bases.

12. Composition according to one of claims 1 to 11, characterized in that it contains at least one thinner selected from the group consisting of benzyl alcohol, styrenated phenol, ethoxylated phenol, aromatic hydrocarbon resins containing phenol groups, diisopropylnaphthalene and cardanol.

13. A method for coating comprising the steps

(i) mixing the components of the composition according to any one of claims 1 to 12,

(ii) applying the blended composition to a substrate

within the pot life,

followed by curing the blended composition.

14. A method for gluing comprising the steps

(i) mixing the components of the composition according to any one of claims 1 to 12,

(ii) applying the mixed composition within the pot life,

- either on at least one of the substrates to be bonded and joining the substrates to form a bond within the open time,

- or in a cavity or gap between several substrates and, if necessary, inserting an anchor into the cavity or gap within the open time,

followed by curing the blended composition.

15. Article obtained from the method according to one of claims 13 or 14.