Epoxy resin composition with bio-based granular material

Abstract

The present invention relates to epoxy resin compositions comprising a resin component containing at least one epoxy liquid resin, a hardener component containing at least one amine hardener, and at least one bio-based granular material with a particle size ≤ 200 µm and a lignin content of at least 10 wt.%, wherein the bio-based granular material is part of the resin and / or the hardener component and the content of bio-based granular material, in relation to the total epoxy resin composition, is 1 to 40 wt.%, preferably 2 to 30 wt.%, in particular 5 to 25 wt.%. The bio-based granular material can be well mixed into the resin and / or hardener component and well re-dispersed after storage. It enables visually high-value coatings with a defect-free and smooth surface.

Description

[0001] EPOXY RESIN COMPOSITION WITH BIOBASED GRANULES

[0002] Technical area

[0003] The invention relates to the field of cold-curing epoxy resin compositions for floor coatings.

[0004] State of the art

[0005] Epoxy resin-based floor coating products are widely used in the construction industry. They consist of liquid resin and hardener components that are mixed prior to application and then cure at ambient temperatures to form a solid coating.

[0006] Many floor coating products contain inorganic fillers, depending on the intended application and technical requirements. However, for certain applications, products that are largely free of inorganic fillers are desired. Alternatives to traditional fillers that meet the requirements for floor coating products are therefore of great interest.

[0007] DE 10 2008 026 266 A1 describes molded bodies for use as floor or soundproofing elements, which are produced by bonding ground granules from olive stones with reactive adhesives based on polyurethanes or epoxy resins.

[0008] WO 2015 / 018466 describes adhesives for fastening technology, which may contain so-called biogenic fillers.

[0009] Alkylated amines such as N-benzyl-1,2-ethanediamine are known as hardeners for epoxy resins, for example, from WO 2017 / 037069. They enable low-emission epoxy resin coatings with attractive surfaces.

[0010] Description of the invention

[0011] The object of the present invention is to provide an epoxy resin composition suitable for floor coating purposes, which contains additives that mix well and can be easily redispersed after storage, enabling optically high-quality coatings with a flawless and smooth surface. This object is achieved with the epoxy resin composition as described in claim 1. The bio-based granules contained in the composition, with a lignin content of at least 10 wt. %, have surprisingly little tendency to settle and remain excellently redispersible even after prolonged storage and transport of the components. After curing, the composition displays a remarkably smooth, optically flawless surface. In contrast, bio-based granules with no or too low lignin content are not redispersible or can only be redispersed with great difficulty after storage, which is disadvantageous for their applicability.Particularly surprising is that compositions containing at least one amine of formula (I) in the amine hardener exhibit particularly good flow behavior of the mixed components. The bio-based granules, in combination with the amine of formula (I), enable particularly low viscosity and, in addition, particularly rapid curing in cold conditions, making the corresponding coatings particularly easy to process and quickly accessible even in cold ambient conditions.

[0012] Of particular interest are compositions according to the invention that are largely free of inorganic fillers, with the bio-based granules being considered part of the organic binder. Such a composition, also referred to as "unfilled," has a reduced content of petroleum-based binders and thinners and is therefore particularly sustainable.

[0013] The epoxy resin composition enables particularly sustainable floor coating systems that can be stored well before use, are easy to apply and ensure technically high-quality and long-lasting protection with a visually appealing appearance.

[0014] 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.

[0015] Ways to implement the invention

[0016] The invention relates to an epoxy resin composition comprising

[0017] - a resin component containing at least one epoxy liquid resin,

[0018] - a hardener component containing at least one amine hardener, and

[0019] - at least one bio-based granulate with a particle size of < 200 μm and a lignin content of at least 10 wt.%, preferably at least 15 wt.%, wherein the bio-based granulate is part of the resin and / or hardener component and the content of bio-based granulate, based on the total epoxy resin composition, is 1 to 40 wt.%, preferably 2 to 30 wt.%, in particular 5 to 25 wt.%. "Liquid epoxy resin" refers to a technical polyepoxide with a glass transition temperature below 25°C.

[0020] A “primary amino group” is an amino group that is bonded to a single organic residue and carries two hydrogen atoms; a “secondary amino group” is an amino group that is bonded to two organic residues, which may also together be part of a ring, and carries one hydrogen atom; and a “tertiary amino group” is an amino group that is bonded to three organic residues, which may also be part of one or more rings in twos or threes, and does not carry a hydrogen atom.

[0021] The hydrogen atoms of primary and secondary amino groups are called “amine hydrogen”.

[0022] Substance names beginning with “poly”, such as polyamine, polyol or polyepoxide, refer to substances that formally contain two or more of the functional groups mentioned in their name per molecule.

[0023] In this document, "olive kernel" refers specifically to the residue from olive kernel shells after pressing or extracting the oil from the olives. Likewise, "cashew shells" refers specifically to the remaining shell fragments of cashew nuts after pressing or extracting the cashew shell oil from the hard shells.

[0024] A “thinner” is a substance that is soluble in an epoxy resin and reduces its viscosity, but is not chemically bound into the epoxy polymer during curing.

[0025] The term “molecular weight” refers to the molar mass (in grams per mole) of a molecule. The term “average molecular weight” refers to the number average M n a polydisperse mixture of oligomeric or polymeric molecules, which is usually determined by gel permeation chromatography (GPC) against polystyrene as a standard.

[0026] “Room temperature” is defined as 23°C.

[0027] The resin component and the hardener component of the epoxy resin composition are preferably stored separately from each other prior to application. The resin component and the hardener component of the epoxy resin composition are thus preferably stored separately from each other. The separate components can be stored for a period of several months up to a year or longer without losing their applicability.

[0028] The bio-based granulate with a lignin content of at least 10 wt.% has a particle size of <200 pm, preferably <100 pm. The particle size is preferably determined by sieve analysis as described in ASTM C136 / C136M-2014. A particle size of more than 200 pm is disadvantageous in that it results in coatings whose surface texture exhibits clearly visible unevenness. This is evident, for example, in Table 1 when comparing composition Z-1 with Z-2 (Ref.) and Z-3 (Ref.).

[0029] The epoxy resin composition contains 1 to 40 wt.%, preferably 2 to 30 wt.%, in particular 5 to 25 wt.%, of bio-based granules.

[0030] A bio-based granulate content of more than 40 wt.% based on the total weight of the epoxy resin composition is disadvantageous in that it no longer ensures sufficient dispersibility of the epoxy resin composition. This is evident, for example, in Table 1 when comparing compositions Z-1 and Z-6 to Z-8 with Z-9 (Ref.).

[0031] The preferred ranges mentioned are advantageous in that they allow good dispersibility of the epoxy resin composition as well as a high proportion of bio-based granules to be achieved.

[0032] Preferably, the bio-based granulate has a moisture content of less than 15 wt.%, preferably less than 12 wt.%. Such granulate is particularly easy to mix into the respective component and ensures trouble-free curing of the composition.

[0033] Suitable as bio-based granules are all types of shredded wood with a lignin content of at least 10% by weight.

[0034] Preferred bio-based granules are waste products from agricultural products, especially foodstuffs such as gels, nuts, or seeds, where inedible components in the form of shells, husks, or kernels of lignified material with a lignin content of at least 10 wt. These are processed for the inventive use and ground to the desired particle size or particle distribution and, if necessary, further treated, in particular dried or sieved.

[0035] Particularly preferably, the bio-based granulate with a lignin content of at least 10 wt.% is selected from the group consisting of ground olive kernels, coconut shells, almond shells, walnut shells, pecan shells, Brazil nut shells, hazelnut shells, macadamia nut shells, cashew nut shells, pistachio shells, cocoa fruit shells, apricot kernel shells, peach kernel shells and plum kernel shells.

[0036] The most preferred bio-based granulate is olive pit granulate. This granulate is available in high quantities and of good quality and enables epoxy resin compositions with particularly good redispersibility after storage of the components and particularly good processability at cold temperatures, especially 12 °C.

[0037] A suitable olive pit granulate is preferably obtained from olive pit shell fragments from the extraction of olive oil, which are dried, ground, and sieved. The olive pit granulate preferably has a lignin content of at least 15 wt.% and an oil content of less than 3 wt.%, preferably less than 1 wt.%, particularly preferably less than 0.5 wt.%. The olive pit granulate preferably has a Mohs hardness of 3 to 4.

[0038] Surprisingly, it was found that the addition of comparable amounts of bio-based granules with a low lignin content or without lignin, such as rice husks with a particle size of 1 to 30 μm, leads to a viscosity that is almost twice as high. In particular, the resin components produced therewith could not be redispersed after storage and settling of the rice husks. When using the granules according to the invention with a lignin content of at least 10 wt. %, preferably at least 15 wt. %, redispersion after storage and settling of the granules was, however, possible without any problems. This can be seen, for example, in Table 1 when comparing compositions Z-1 and Z-6 to Z-8 with Z-4 (Ref.) and Z-5 (Ref.). The bio-based granule is preferably a constituent of the resin component. The resin component preferably has a bio-based granule content of 2 to 45 wt. based on the total resin component.-%, particularly preferably 4 to 35 wt.%, in particular 6 to 30 wt.%.

[0039] The resin component of the epoxy resin composition contains at least one epoxy liquid resin.

[0040] A suitable epoxy liquid 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.

[0041] Suitable liquid epoxy resins are, in particular, aromatic epoxy resins, especially the glycidyl ethers of:

[0042] - Bisphenol A, bisphenol F, or bisphenol A / F, where A is acetone and F is formaldehyde, which served as starting materials for the production of these bisphenols. In the case of bisphenol F, positional isomers may also be present, in particular those derived from 2,4'- or 2,2'-hydroxyphenylmethane;

[0043] - Dihydroxybenzene derivatives such as resorcinol, hydroquinone or pyrocatechol;

[0044] - 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 orParaformaldehyde or acetaldehyde or crotonaldehyde or isobutyraldehyde or 2-ethylhexanal or benzaldehyde or furfural;.

[0045] - aromatic amines, such as aniline, toluidine, 4-aminophenol, 4,4'-methylenediphenyldiamine, 4,4'-methylenediphenyldi-(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).

[0046] Other suitable epoxy liquid resins are aliphatic or cycloaliphatic polyepoxides, in particular

[0047] - Glycidyl ethers of saturated or unsaturated, branched or unbranched, cyclic or open-chain di-, tri- or tetrafunctional C2 to C50 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;

[0048] - hydrogenated bisphenol A, F or A / F liquid resins, or the glycidylation products of hydrogenated bisphenol A, F or A / F;

[0049] - an N-glycidyl derivative of amides or heterocyclic nitrogen bases, such as triglycidyl cyanurate or triglycidyl isocyanurate, or reaction products of epichlorohydrin with hydantoin;

[0050] - Epoxy resins from the oxidation of olefins, such as in particular vinylcyclohexene, dicyclopentadiene, cyclohexadiene, cyclododecadiene, cyclododecatriene, isoprene, 1,5-hexadiene, butadiene, polybutadiene or divinylbenzene.

[0051] Also suitable are liquid epoxy resins which are at least partially based on renewable raw materials, such as in particular diglycidyl ether of vanillin alcohol, diglycidyl ether of isosorbide or triglycidyl ether of glycerol, as well as bisphenol A diglycidyl ether of bio-based epichlorohydrin.

[0052] The liquid epoxy resin is, in particular, an aromatic liquid resin based on a bisphenol or novolak, especially with an average epoxy equivalent weight in the range of 156 to 210 g / eq. A bisphenol A diglycidyl ether and / or bisphenol F diglycidyl ether is particularly suitable, as commercially available, for example, as Araldite® GY 250, Araldite® PY 304, Araldite® GY 282 (from Huntsman), DER™ 331 or DER™ 330 (from Dow), or Epon™ Resin 828 (from Hexion). Such liquid resins have a low viscosity for an epoxy resin and enable rapid curing and high hardness.

[0053] Particularly preferred is a bisphenol A diglycidyl ether obtained from the reaction of bisphenol A with bio-based epichlorohydrin. This enables particularly sustainable epoxy resin compositions.

[0054] Also particularly suitable are phenol-formaldehyde novolak glycidyl ethers, in particular with an average functionality in the range of 2.3 to 4, preferably 2.5 to 3. They may contain proportions of other epoxy resins, in particular bisphenol A diglycidyl ether or bisphenol F diglycidyl ether.

[0055] Diglycidyl ethers of vanillin alcohol or triglycidyl ethers of glycerol, especially diglycidyl ethers of vanillin alcohol, are also particularly suitable. This enables particularly sustainable epoxy resin compositions.

[0056] The resin component preferably additionally contains at least one reactive diluent containing epoxy groups, in particular 1 to 15% by weight, preferably 1.5 to 10% by weight, in particular 2 to 8% by weight, of reactive diluent containing epoxy groups, based on the total weight of the epoxy resin composition.

[0057] Preferred reactive diluents containing epoxy groups are butanediol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane di- or triglycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, guaiacol glycidyl ether, 4-methoxyphenyl glycidyl ether, pn-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, 4-nonylphenyl glycidyl ether, 4-dodecylphenyl glycidyl ether, vanillin glycidyl ether, cardanol glycidyl ether, benzyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, hexyl glycidyl ether, 2-ethylhexyl glycidyl ether or glycidyl ethers of natural alcohols such as in particular Cs to Cw or C12 to C14 or C13 to Cis alkyl glycidyl ethers.

[0058] Glycidyl ethers of natural alcohols, especially C12 to C14 alkyl glycidyl ethers, are particularly preferred. These produce particularly easy-to-process epoxy resin compositions.

[0059] If necessary, the resin component also contains portions of solid epoxy resin. The hardener component of the epoxy resin composition contains at least one amine hardener.

[0060] Suitable amine hardeners are in particular aliphatic, cycloaliphatic or arylaliphatic di- or triamines with at least 3 amine hydrogens, such as in particular

[0061] - primary di- or triamines, 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 (C11-neodiamine), 1,6-hexanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,2(4),4-trimethylhexamethylenediamine (TMD), 1,7-heptanediamine,

[0062] 1.8-Octandiamin, 1 ,9-Nonandiamin, 1 ,10-Decandiamin, 1 ,11-Undecandiamin, 1 ,12- Dodecandiamin, 1 ,2-, 1 ,3- oder 1 ,4-Diaminocyclohexan, Bis(4-aminocyclohexyl)- methan, Bis(4-amino-3-methylcyclohexyl)methan, Bis(4-amino-3-ethylcyclo- hexyl)methan, Bis(4-amino-3,5-dimethylcyclohexyl)methan, Bis(4-amino-3-ethyl-5- methylcyclohexyl)methan, 1-Amino-3-aminomethyl-3,5,5-trimethylcyclohexan (Isophorondiamin oder lPDA), 1 ,3-Bis(aminomethyl)cyclohexan, 1 ,4- Bis(aminomethyl)cyclohexan, 2(4)-Methyl-1 ,3-diaminocyclohexan, 2, 5(2,6)- Bis(aminomethyl)bicyclo[2.2.1]heptan (NBDA), 3(4),8(9)-Bis(amino- methyl)tricyclo[5.2.1 .0 2 ’ 6 ]decan, 1 ,4-Diamino-2,2,6-trimethylcyclohexan (TMCDA),

[0063] 1 .8-Menthandiamin, 3,9-Bis(3-aminopropyl)-2,4,8, 10-tetraoxaspiro[5.5]undecan, 1 ,3- Bis(aminomethyl)benzol (MXDA) oder 1 ,4-Bis(aminomethyl)benzol,

[0064] - Aliphatic primary di- or triamines containing ether groups, in particular 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)polytetrahydrofurans or other polytetrahydrofurandiamines, or polyoxyalkylenedi- or triamines, in particular Jeffamine® D-230, D-400, D-2000, EDR-104, EDR-148, EDR-176, T-403, T-3000 or Jeffamine® T-5000 (all from Huntsman), or equivalent amines from BASF or Nitroil;

[0065] - polyamines containing secondary amino groups, such as in particular 2-aminoethylpiperazine, 3-dimethylaminopropylamine (DMAPA), 3-(3-(dimethylamino)propylamino)propylamine (DMAPAPA), bis(hexamethylene)triamine (BHMT), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA) or higher homologues of linear polyethyleneamines, 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-ethylpropyl)-2-methyl-1,5-pentanediamine, N,N'-bis(3-amino-1-ethylpropyl)-2-methyl-1,5-pentanediamine, products from the reductive alkylation of primary polyamines with aldehydes or ketones, in particular N-benzyl-1,2-ethanediamine, N-furfuryl-1,2-ethanediamine, N-tetrahydrofurfuryl-1,2-ethanediamine, N-benzyl-1,2-propanediamine, N-benzyl-1,3-bis(aminomethyl)benzene, N-2-ethylhexyl-1,3-bis(aminomethyl)benzene, N-benzyldiethylenetriamine, N,N'-dibenzyldiethylenetriamine, N-benzyltriethylenetetramine, N,N'-dibenzyltriethylenetetramine, N"-benzyl-N,N'-bis(3-aminopropyl)ethylenediamine, N",N"'-dibenzyl-N,N'-bis(3-aminopropyl)ethylenediamine, or partially styrenated polyamines such as styrenated MXDA containing N-phenylethyl-1,3-bis(aminomethyl)benzene (available as Gaskamine® 240 from Mitsubishi Gas Chemical); and,

[0066] - amine-functional adducts of the above-mentioned or other polyamines with epoxides or epoxy resins, in particular amine-functional adducts with aromatic diepoxides.

[0067] The amine hardener preferably contains at least one aliphatic, cycloaliphatic or arylaliphatic di- or triamine with at least 3 amine hydrogens, in particular selected from the group consisting of 2-butyl-2-ethyl-1,5-pentanediamine (C11 - neodiamine), 2,2(4),4-trimethylhexamethylenediamine (TMD), 1,2-diaminocyclohexane, bis(4-aminocyclohexyl)methane, isophoronediamine (IPDA), 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 2(4)-methyl-1,3-diaminocyclohexane, 2,5(2,6)-bis(aminomethyl)bicyclo[2.2.1]heptane (NBDA), 1,3-bis(aminomethyl)benzene (MXDA), polyoxypropylenediamines with medium molecular weight M n from 200 to 500 g / mol, polyoxypropylenetriamines with medium molecular weight M nfrom 300 to 500 g / mol, 3-(3-(dimethylamino)propylamino)propylamine (DMAPAPA), bis(hexamethylene)triamine (BHMT), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), N,N'-bis(3-aminopropyl)ethylenediamine (N4-amine), N-benzyl-1,2-ethanediamine, N-furfuryl-1,2-ethanediamine, N-tetrahydrofurfuryl-1,2-ethanediamine, N-benzyl-1,3-bis(aminomethyl)benzene, and amine-functional adducts of these amines with aromatic diepoxides. The amine hardener preferably contains isophoronediamine (IPDA). This amine enables a high glass transition temperature and low tendency to yellowing.

[0068] The amine hardener also preferably contains 1,3-bis(aminomethyl)benzene (MXDA). This amine enables particularly rapid curing.

[0069] The amine hardener also preferably contains 1,3-bis(aminomethyl)cyclohexane. This amine enables rapid curing and a particularly low tendency to yellowing.

[0070] In a particularly preferred embodiment of the invention, the amine hardener contains at least one amine of the formula (I),

[0071] NH2-A— NH— CH2-Y (I) where

[0072] A represents a divalent alkylene or cycloalkylene radical having 2 to 8 C atoms, and

[0073] Y represents an optionally substituted phenyl radical having 6 to 12 C atoms, furfuryl or a naphthyl radical, where the two nitrogen atoms to which the radical A is bonded are separated from each other by at least two C atoms.

[0074] The amine of formula (I) enables a particularly low viscosity of the freshly mixed composition even at low application quantities and thus a particularly easy processability and application, especially on flat surfaces, and in addition a particularly rapid curing in the cold, which enables a particularly rapid walkability in cold ambient conditions.

[0075] Preferably, A in formula (I) is 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, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 4(2)-methyl-1,3-cyclohexylene, 1 ,3-cyclohexylene-bis(methylene) and 1,4-cyclohexylene-bis(methylene), in particular 1,2-ethylene, 1,2-propylene, 2-methyl-1,5-pentylene and 1,3-cyclohexylene-bis(methylene).

[0076] Most preferably, A is 1,2-ethylene. Preferably, Y in formula (I) is selected from the group consisting of phenyl, 4-methylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 4-dimethylaminophenyl, furfuryl, and 1-naphthyl.

[0077] Y particularly preferably represents phenyl or furfuryl, in particular phenyl.

[0078] Most preferably, in formula (I), A is 1,2-ethylene and Y is phenyl. The amine of formula (I) is thus most preferably N-benzyl-1,2-ethanediamine.

[0079] Preferably, the amine hardener contains, in addition to at least one amine of the formula (I), at least one further amine having two primary amino groups, in particular selected from the group consisting of isophoronediamine, 1,3-bis(aminomethyl)benzene, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 2,2(4),4-trimethylhexamethylenediamine, bis(4-aminocyclohexyl)methane, 2(4)-methyl-1,3-diaminocyclohexane and 2,5(2,6)-bis(aminomethyl)bi cy cl o[2.2.1]heptane.

[0080] Preferred among these are isophoronediamine, 1,3-bis(aminomethyl)benzene and / or 1,3-bis(aminomethyl)cyclohexane.

[0081] The amine hardener preferably contains so much amine of formula (I) that 3 to 40%, particularly preferably 5 to 30%, in particular 6 to 20%, of all amine hydrogens in the epoxy resin composition originate from the amine of formula (I).

[0082] The amine of formula (I) is, in particular, a reaction product from the reductive alkylation of a superstoichiometric amount of the amine of formula H2N-A-NH2 with the aldehyde of formula Y-CHO and hydrogen, in particular after removal of the excess amine of formula H2N-A-NH2. In addition to the amine of formula (I), such a reaction product may contain the corresponding dialkylated amine of formula Y-CH2-NH-A-NH-CH2-Y, in particular in an amount of 10 to 30 wt.% based on the sum of the amine of formula (I) and the corresponding dialkylated amine.

[0083] N-benzyl-1,2-ethanediamine can thus be used in particular as a mixture containing 10 to 30 wt.% N,N'-dibenzyl-1,2-ethanediamine based on the sum of N-benzyl-1,2-ethanediamine and N,N'-dibenzyl-1,2-ethanediamine. The hardener component of the epoxy resin composition preferably further contains at least one tertiary amine of the formula where R is a

[0084] Alkylene group having 1 to 20 C atoms, which is optionally substituted and optionally has heteroatoms, and n stands for a value of 1 to 3, preferably in an amount of 0.25 to 5 wt.%, in particular 0.5 to 3 wt.%, based on the total weight of the epoxy resin composition.

[0085] Preferably, R is methylene and n is 2 or, in particular, 3.

[0086] Such a tertiary amine acts in particular as an accelerator during curing.

[0087] Preferably, the tertiary amine is selected from the group consisting of 2-(dimethylaminomethyl)phenol, 2,6-bis(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol and 2,4,6-tris(((3-(dimethylamino)propyl)amino)methyl)phenol, in particular 2,4,6-tris(((3-(dimethylamino)propyl)amino)methyl)phenol and 2,4,6-tris(dimethylaminomethyl)phenol.

[0088] The most preferred amine is 2,4,6-tris(dimethylaminomethyl)phenol. This tertiary amine is commercially available, for example, as Ancamine® K54 from Evonik.

[0089] The epoxy resin composition may also contain other components.

[0090] Preferably, the epoxy resin composition further contains at least one thinner, which is present in particular only in a small amount.

[0091] The epoxy resin composition preferably contains, based on the total epoxy resin composition, less than 20% by weight, in particular less than 15% by weight, preferably less than 10% by weight, of diluent having a boiling point at atmospheric pressure of at least 180°C, in particular at least 200°C.

[0092] Suitable thinners are in particular 2-phenoxyethanol, 2-benzyloxyethanol,

[0093] 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-butylyl ether, propylene glycol butyl ether, propylene glycol phenyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol di-n-butyl ether, diphenylmethane, diisopropylnaphthalene, petroleum fractions such as Solvesso® types (from Exxon), alkylphenols such as tert.Butylphenol, nonylphenol, dodecylphenol, cardanol (from cashew shell oil, containing as main component 3-(8,11,14-pentadecatrienyl)phenol), styrenated phenol, biphenols, aromatic hydrocarbon resins, in particular types containing phenol groups, alkoxylated phenol, in particular ethoxylated or propoxylated phenol, in particular 2-phenoxyethanol, isopropyl biphenyls, adipates, sebacates, phthalates, benzoates, organic phosphoric or sulfonic acid esters or sulfonamides.

[0094] Preferred diluents are selected from the list consisting of benzyl alcohol, 2-phenoxyethanol, cardanol, styrenated phenol, diisopropylnaphthalene, isopropylbiphenylene, and phenol-containing aromatic hydrocarbon resins. Benzyl alcohol and / or diisopropylnaphthalene are particularly preferred.

[0095] The epoxy resin composition may contain at least one additional filler. Suitable additional fillers include, in particular, inorganic fillers such as ground or precipitated calcium carbonate, 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), titanium dioxide, iron oxides, molecular sieves, aluminum oxide, aluminum hydroxide, magnesium hydroxide, silica, cement, gypsum, or fly ash, as well as other fillers such as carbon black, graphite, metal powders such as aluminum, copper, iron, zinc, silver, or steel, PVC powder, or hollow spheres.

[0096] Preferred inorganic fillers are selected from the list consisting of calcium carbonate, barite, quartz flour, quartz sand, titanium dioxide and iron oxides.

[0097] In a preferred embodiment of the invention, the epoxy resin composition contains little or no inorganic fillers. In particular, the epoxy resin composition has an inorganic filler content of less than 5 wt.%, preferably less than 2 wt.%, in particular less than 1 wt.%, based on the total epoxy resin composition. In such an epoxy resin composition, also referred to as "unfilled," the content of petroleum-based binders and thinners is particularly low, making the composition particularly sustainable and, in particular, significantly smaller in its carbon footprint than conventional unfilled epoxy resin compositions.

[0098] The epoxy resin composition may contain other auxiliary substances and additives, in particular the following:

[0099] - other amines, in particular monoamines such as benzylamine or furfurylamine, polyamidoamines, Mannich bases or aromatic polyamines such as 4,4'-diaminodiphenylmethane, 2,4(6)-toluenediamine or 3,5-diethyl-2,4(6)-toluenediamine;

[0100] - 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;

[0101] - other accelerators, in particular acids such as salicylic acid or p-toluenesulphonic acid, nitrates such as calcium nitrate, phenols, in particular bisphenols, phenol resins such as phenol-formaldehyde resins, also called novolaks, or phosphites such as di- or triphenyl phosphites;

[0102] - 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;

[0103] - fibres, in particular glass fibres, carbon fibres, metal fibres, ceramic fibres or plastic fibres such as polyamide fibres or polyethylene fibres;

[0104] - Nanofillers, especially carbon nanotubes;

[0105] - dyes or pigments;

[0106] - solvents;

[0107] - Rheology modifiers, in particular thickeners or anti-settling agents; - Adhesion improvers, in particular organoalkoxysilanes;

[0108] - flame-retardant substances, in particular the fillers already mentioned: aluminium hydroxide or magnesium hydroxide, antimony trioxide, antimony pentoxide, boric acid (B(OH)s), zinc borate, zinc phosphate, melamine borate, melamine cyanurate, ammonium polyphosphate, melamine phosphate, melamine pyrophosphate, polybrominated diphenyl oxides or diphenyl ethers, phosphates such as in particular diphenyl cresyl phosphate, resorcinol bis(diphenyl phosphate), resorcinol diphosphate oligomer, tetraphenylresorcinol diphosphite, ethylenediamine diphosphate, bisphenol A bis(diphenyl phosphate), tris(chloroethyl)phosphate, tris(chloropropyl)phosphate,

[0109] Tris(dichloroisopropyl)phosphate, tris[3-bromo-2,2-bis(bromomethyl)propyl]phosphate, tetrabromobisphenol A, bis(2,3-dibromopropyl ether) of bisphenol A, brominated epoxy resins, ethylenebis(tetrabromophthalimide), ethylenebis(dibromonorbornanedicarboximide), 1,2-bis(tribromophenoxy)ethane, tris(2,3-dibromopropyl)isocyanurate, tribromophenol, hexabromocyclododecane, bis(hexachlorocyclopentadieno)cyclooctane or chlorinated paraffins; or

[0110] - Additives such as wetting agents, flow agents, defoamers, deaerators, stabilizers against oxidation, heat, light or UV radiation or biocides.

[0111] Other components of the epoxy resin composition can be included in the resin and / or hardener components. Components reactive with amine groups are preferably included in the resin component, while substances reactive with epoxy groups are preferably included in the hardener component.

[0112] In a preferred embodiment of the invention, the epoxy resin composition contains at least one surface-active additive selected from defoamers and deaerators, in particular in an amount of 0.01 to 1 wt.%, preferably 0.02 to 0.5 wt.%, based on the total epoxy resin composition. Such a composition is particularly suitable as a floor coating and allows for surface application in the liquid state, forming a more attractive surface, particularly without defects caused by air bubbles, such as craters or so-called pinholes.

[0113] The epoxy resin composition preferably contains only a low content of solvents with a boiling point at atmospheric pressure of less than 180°C, preferably less than 1 wt.%, in particular less than 0.5 wt.%, based on the total epoxy resin composition. Such a largely solvent-free composition causes hardly any VOC emissions.

[0114] The epoxy resin composition preferably contains less than 5% water by weight. Such a non-water-based epoxy resin composition is particularly versatile and particularly water-resistant.

[0115] To apply the epoxy resin composition, the resin and hardener components are mixed together shortly before or during application.

[0116] The mixing ratio is preferably selected such that the ratio of the number of groups reactive toward epoxy groups, particularly amine hydrogens, to the number of epoxy groups is in the range of 0.5 to 1.5, particularly 0.7 to 1.2. In parts by weight, the mixing ratio between the resin and hardener components is typically in the range of approximately 1:1 to 20:1.

[0117] The components are mixed using a suitable process; this can be done continuously or batchwise. Mixing is preferably carried out at ambient temperature, which is typically in the range of 5 to 45°C, preferably 10 to 35°C.

[0118] With the mixing of the components, curing begins through a chemical reaction. The amine hydrogens present in the epoxy resin composition, and any other groups reactive toward epoxy groups, react with the epoxy groups, causing their ring opening (addition reaction). As a result of this reaction, the composition polymerizes and thus cures.

[0119] Curing typically occurs at ambient temperature, particularly in the range of 5 to 45°C, preferably 10 to 35°C, and typically lasts for a few hours to days.

[0120] The invention further relates to a cured composition obtained from the curing of the epoxy resin composition after mixing the components. The epoxy resin composition is preferably applied to at least one substrate, with the following being particularly suitable:

[0121] - Glass, glass ceramics, concrete, mortar, cement screed, fiber cement, brick, tile, plaster or natural stones such as granite or marble;

[0122] - asphalt or bitumen;

[0123] - Repair or levelling compounds based on PCC (polymer-modified cement mortar) or ECO (epoxy resin-modified cement mortar);

[0124] - Metals or alloys such as aluminum, iron, steel or non-ferrous metals, or surface-treated metals or alloys such as galvanized or chrome-plated metals;

[0125] - Leather, textiles, paper, wood, wood materials bonded with resins, for example phenolic, melamine or epoxy resins, resin-textile composites or other so-called polymer composites;

[0126] - plastics, in particular rigid or flexible PVC, ABS, SAN, polycarbonate (PC), polyamide (PA), polyester, polystyrene, PMMA, epoxy resins, phenolic resins, PUR, POM, TPO, PE, PP, EPM or EPDM, the plastics optionally being surface-treated by means of plasma, corona or flames;

[0127] - Fiber-reinforced plastics, such as carbon fiber-reinforced plastics (CFRP), glass fiber-reinforced plastics (GRP) or sheet molding compounds (SMC);

[0128] - insulating foams, in particular made of EPS, XPS, PUR, PIR, rock wool, glass wool or foamed glass (foam glass);

[0129] - coated substrates, in particular painted tiles, painted concrete, powder-coated metals or alloys or painted sheets;

[0130] - Coatings, paints or varnishes, in particular coated floors, which are covered with another layer of floor covering.

[0131] If necessary, the substrates can be pretreated before applying the epoxy resin composition.

[0132] The described epoxy resin composition is preferably used as a covering, coating, leveling, sealing or primer, in particular as a component of a floor covering, in particular for offices, industrial halls, gymnasiums, cold rooms, balconies, terraces, parking decks or bridges.

[0133] For such use, the epoxy resin composition is applied, in particular, as a self-leveling or slightly thixotropic coating to predominantly flat surfaces. It preferably has a liquid consistency with low viscosity and good flow properties. Five minutes after mixing the components, it preferably has a viscosity at 20 °C of 200 to 4,000 mPa s, particularly preferably 300 to 2,000 mPa s, in particular 400 to 1,000 mPa s, determined using a plate-to-plate viscometer with a plate diameter of 50 mm, a plate-to-plate distance of 0.5 mm, and a shear rate of 100 s. 1 .

[0134] In a preferred embodiment of the invention, the epoxy resin composition has a viscosity at 12 °C of less than 2,800 mPa s, preferably less than 2,400 mPa s, in particular less than 2,300 mPa s, 5 minutes after mixing the components, determined by means of a plate-plate viscometer with a plate diameter of 50 mm, a plate-plate distance of 0.5 mm and a shear rate of 100 s -1 , wherein, based on the total epoxy resin composition, in particular less than 10 wt.% of thinner having a boiling point at atmospheric pressure of at least 180°C and in particular less than 5 wt.% of reactive diluents containing epoxy groups are contained. Such a composition is particularly low in emissions and can be applied excellently even under cool ambient conditions, in particular even in thin layers in the range of 0.1 to 1 mm. The epoxy resin composition preferably contains at least one amine of formula (I) in the amine hardener, as described above.

[0135] The mixed composition is applied to a substrate within the processing time, preferably as a thin film with a layer thickness of typically about 50 μm to about 5 mm, preferably 0.1 to 3 mm, typically at ambient temperature, in particular in the range of about 5 to 45°C, preferably 10 to 35°C. Application is carried out in particular by pouring onto the substrate to be coated and then uniformly spreading it with, for example, a brush, roller, squeegee, or notched trowel. Application can also be carried out by spraying.

[0136] The use of the epoxy resin composition results in an article comprising the cured composition.

[0137] A further subject of the invention is a method for coating comprising the steps of a) mixing the components of the described epoxy resin composition, b) applying the mixed composition to at least one substrate, in particular a floor, in particular in a layer thickness in the range of 0.1 to 3 mm, c) allowing the applied coating to cure under ambient conditions, in particular at a temperature in the range of 5 to 45°C.

[0138] Mixing in step a) can be carried out continuously or batchwise. Batchwise mixing in an open vessel using a stirrer is preferred until a macroscopically homogeneous liquid is obtained.

[0139] Application in step b) is preferably carried out by pouring the mixture onto the substrate and then spreading it evenly, particularly using a brush, roller, squeegee, or notched trowel. Care must be taken to ensure that the application takes place within the time period within which the mixed composition has a viscosity suitable for application; a low viscosity facilitates application. This time period suitable for processing is also referred to as the "processing time."

[0140] Particularly suitable substrates are those already mentioned, with the substrate preferably being in the form of soil. Preferred substrates are concrete, mortar, cement screed, fiber cement, brick, tile, gypsum, natural stone, asphalt, bitumen, PCC (polymer-modified cement mortar), ECO (epoxy resin-modified cement mortar), wood, resin-bonded wood materials, resin-textile composites, plastics, fiber-reinforced plastics, varnished tiles, painted concrete, or coated floors of all kinds.

[0141] Steps a), b) and c) are preferably all carried out at ambient temperatures, in particular at 5 to 45 °C, particularly preferably at 5 to 30 °C.

[0142] The epoxy resin composition is in particular a component of a floor covering comprising

[0143] - if necessary, a leveling layer,

[0144] - if necessary, a primer,

[0145] - if necessary, a waterproofing layer, - one or more layers of a base layer, which may be sprinkled with quartz sand,

[0146] - and if necessary a sealant (top coat).

[0147] The epoxy resin composition according to the invention can represent the adhesion primer and / or the leveling layer and / or the waterproofing layer and / or the base layer and / or the sealant of the floor covering. Other layers not corresponding to the epoxy resin composition according to the invention can also be epoxy resin compositions, or another material, in particular a polyurethane or polyurea coating, or bitumen or asphalt.

[0148] In a preferred embodiment of the invention, the epoxy resin composition according to the invention is used as a component of a floor protection system in which the epoxy resin composition according to the invention constitutes the base layer and / or the sealant. The base layer is preferably sprinkled with quartz sand. Such a floor protection system is used in particular in industrial halls, warehouses, cold storage rooms, or cellars, or on balconies, terraces, parking decks, or bridges.

[0149] In a further preferred embodiment of the invention, the epoxy resin composition is used as a component of a soil protection system in which the epoxy resin composition according to the invention forms a waterproofing layer covered with bitumen and then asphalt. The waterproofing layer is preferably sprinkled with quartz sand. Such a soil protection system is used particularly on bridges. The epoxy resin composition according to the invention protects the underlying bridge structure from moisture penetration and thus from corrosion.

[0150] A further subject matter of the invention is a soil protection system comprising i) at least one layer of the epoxy resin composition according to the invention in a layer thickness of 0.1 to 3 mm, ii) quartz sand which has been scattered in and / or on, in particular on, the epoxy resin composition i), iii) optionally at least one further layer of the epoxy resin composition according to the invention, which is applied in particular in a layer thickness of 0.1 to 1 mm to the sand-strewn layer, iv) optionally at least one layer of bitumen which is applied to the epoxy resin composition i) or iii), and v) optionally at least one layer of asphalt which is applied to the bitumen layer.

[0151] In the event that layers iv) and v) are not part of the soil protection system, layer iii) is preferably present and forms the sealing and thus the top layer or surface of the soil protection system.

[0152] In the event that layers iv) and v) are part of the soil protection system, the soil protection system is preferably applied to a bridge, and the epoxy resin composition according to the invention serves as a sealant that protects the underlying bridge structure from water penetration and thus from corrosion. Layer iii) is preferably also present, and layer iv) is thus applied to the epoxy resin composition iii).

[0153] The floor protection system is particularly sustainable, easy to apply, and provides technically high-quality, long-lasting protection with a visually appealing appearance. The content of petroleum-based binders and thinners, and thus the carbon footprint, is particularly low.

[0154] Examples

[0155] The following are exemplary embodiments intended to further illustrate the described invention. Of course, the invention is not limited to these described exemplary embodiments.

[0156] A “standard climate” is defined as a temperature of 23±1°C and a relative humidity of 50±5%.

[0157] “EEW” stands for epoxy equivalent weight.

[0158] “AHEW” stands for the amine hydrogen equivalent weight.

[0159] Substances used: Epoxy liquid resin 1 Bisphenol A diglycidyl ether, EEW approx. 187 g / Eq (Araldit® GY-250, from Huntsman)

[0160] Epoxy liquid resin 2 1:1 mixture of bisphenol A diglycidyl ether and bisphenol F diglycidyl ether, EEW approx. 177 g / Eq (Epikote® Resin 05447, from Hexion)

[0161] Reactive diluent monoglycidyl ether of Ci2-14 alcohols, EEW approx. 294 g / Eq (Grilonit® Epoxide 8, from Ems Chemie)

[0162] Diisopropylnaphthalene Ruetasolv® DI (from Rütgers)

[0163] Vent BYK-054 (from BYK)

[0164] Benzyl alcohol (from Valtris)

[0165] IPDA isophoronediamine, AHEW 42.6 g / Eq (Vestamin® IPD, from Evonik)

[0166] TEPA tetraethylenepentamine, AHEW approx. 30 g / eq (technical, from Huntsman)

[0167] N-Benzyl-1,2-ethanediamine AHEW 50.1 g / Eq, prepared as described below

[0168] MXDA 1,3-Bis(aminomethyl)benzene, AHEW 34 g / Eq (from Mitsubishi Gas Chemical)

[0169] Polyetherdiamine Polyoxypropylenediamine, AHEW 60 g / mol (Jeffamine® D-230, from Huntsman)

[0170] Ancamine® K54 2,4,6-Tris(dimethylaminomethyl)phenol (from Evonik)

[0171] Olive kernels < 100 pm Olive kernels from olive oil production, dried, ground, particle size < 100 pm, lignin content > 20 wt.% (from Micronizados Vegetales SL)

[0172] Olive kernels 300-600 pm Olive kernels from the extraction of olive oil, dried, ground, particle size 300-600 pm (from Micronizados Vegetales SL)

[0173] Olive kernels 600-800 pm Olive kernels from the extraction of olive oil, dried, ground, particle size 600-800 pm (from Micronizados Vegetales SL)

[0174] Pecan shells < 200 pm ground shells of pecan nuts, particle size < 200 pm, lignin content > 25 wt.% (from Composition Materials Co.)

[0175] Walnut shells < 200 pm ground walnut shells, particle size < 200 pm, lignin content > 15 wt.% (from Composition Materials Co.) Rice hulls 1-30 pm ground rice hulls, lignin content < 5 wt.% (from Composition Materials Co.)

[0176] Quartz flour < 70 pm Dorsilit® 10,000 (from Dorfner)

[0177] Preparation of N-benzyl-1,2-ethanediamine:

[0178] 180.3 g (3 mol) of 1,2-ethanediamine were initially charged at room temperature, mixed with a solution of 106.0 g (1 mol) of benzaldehyde in 1200 ml of isopropanol, and stirred for 2 hours. The mixture was then hydrogenated at 80°C, 80 bar hydrogen pressure, and a flow rate of 5 ml / min on a continuously operating hydrogenation apparatus with a Pd / C fixed-bed catalyst. The hydrogenated solution was concentrated on a rotary evaporator at 65°C, removing unreacted 1,2-ethanediamine, water, and isopropanol. The resulting reaction mixture was purified by distillation at 80°C under vacuum. A colorless liquid was obtained with an N-benzyl-1,2-ethanediamine content of > 97%, determined by GC.

[0179] Production of epoxy resin compositions:

[0180] Compositions Z-1 to Z-9:

[0181] To prepare the compositions, the ingredients of the resin component listed in Table 1 were mixed in the specified amounts (in parts by weight) using a dissolver and stored in a sealed container.

[0182] The ingredients of the hardener component listed in Table 1 were mixed using a magnetic stirrer and stored in a sealed container.

[0183] The compositions designated "(Ref.)" are non-inventive compositions and serve as a comparison.

[0184] Dispersibility:

[0185] The dispersibility of the granules used was assessed during the preparation of the resin component using a dissolver. A uniform distribution of the ingredients after a short mixing time was rated "+". A uniform distribution of the ingredients only achieved after a longer mixing time was rated "+ / -". If a uniform distribution of the ingredients could not be achieved, this was rated "-". The results are shown in Table 1. Viscosity of the resin component:

[0186] One hour after mixing the ingredients of the resin component, the viscosity of the resin component was measured at 23°C on a thermostatted plate-plate viscometer MCR 102E (Anton Paar) (plate diameter 50 mm, plate-plate distance 0.5 mm, shear rate 100 s -1 ). The results are shown in Table 1.

[0187] Redispersibility:

[0188] The resin components were mixed as described using a dissolver. 1 kg of the mixed resin component was then stored in a sealed container on a vibrating table at 45°C for 14 days. The resulting sediment in the resin component was then stirred again using the dissolver. If the sediment could be evenly distributed throughout the resin component after a short mixing time, the redispersibility was rated "+". If, however, even distribution could not be achieved after a short mixing time, the redispersibility was rated "-". The results are shown in Table 1.

[0189] For the following tests, the resin and hardener components were mixed in the weight ratio specified in Table 1 using a drill mixer.

[0190] Surface texture:

[0191] The freshly mixed composition was applied in an amount of 0.5 g / m 2 applied to a concrete slab using a roller and stored for 7 days in standard climate.

[0192] The surface quality was then assessed visually. No visible unevenness on the surface of the board was rated "+," while unevenness clearly visible to the eye was rated "-." The results are shown in Table 1.

[0193] Mixed viscosity:

[0194] Five minutes after mixing the resin and hardener components, the viscosity was determined at 23°C using a thermostatted MCR 102E plate-to-plate viscometer (Anton Paar) (plate diameter 50 mm, plate-to-plate spacing 0.5 mm, shear rate 100 s-1). The inventive compositions Z-1 and Z-6 to Z-8 all had a viscosity in the range of 0.4 to 2 Pa s.

[0195]

[0196] Table 1 : Composition and properties of Z-1 to Z-9 "nb" stands for "not determined"

[0197]

[0198] Table 1 : (Continued)

[0199] Compositions Z-10 to Z-15: The compositions were prepared according to the ingredients of the resin component and the hardener component listed in Table 2 as described for composition Z-1.

[0200] The dispersibility and redispersibility of the resin component were determined as described for composition Z-1.

[0201] For the following tests, the resin and hardener components were mixed using a drill mixer in the weight ratio specified in Table 2. The mixed viscosity was determined 5 minutes after mixing the resin and hardener components at 12°C or 20°C using a thermostatted plate-to-plate viscometer (plate diameter 50 mm, plate-to-plate distance 0.5 mm, shear rate 100 s-1).

[0202] The surface quality was tested as described for composition Z-1.

[0203] The Shore D hardness was determined according to DIN 53505 on two cylindrical test specimens (diameter 20 mm, thickness 5 mm), one of which was stored at 8°C and one at 23°C and the hardness was measured after the specified time in each case.

[0204] The results are shown in Table 2.

[0205] The compositions designated "(Ref.)" are non-inventive compositions and serve as a comparison.

[0206] From Table 2 it can be seen that a composition with a hardener containing N-benzyl-1,2-ethanediamine and a bio-based granulate according to the invention has a surprisingly low viscosity, in particular at 12 °C (Z-10 compared to Z-11), whereas with corresponding compositions with N-benzyl-1,2-ethanediamine in the hardener and quartz powder instead of the bio-based granulate this viscosity advantage does not exist (Z-12 (Ref.) compared to Z-13 (Ref.)).

[0207]

[0208] Table 2: Composition and properties of Z-10 to Z-15 "nb" stands for "not determined"

Claims

Patent claims:

1. Epoxy resin composition comprising - a resin component containing at least one epoxy liquid resin, - a hardener component containing at least one amine hardener, and - at least one bio-based granulate having a particle size of < 200 pm and a lignin content of at least 10 wt.%, preferably at least 15 wt.%, wherein the bio-based granulate is part of the resin and / or the hardener component and the content of bio-based granulate, based on the total epoxy resin composition, is 1 to 40 wt.%, preferably 2 to 30 wt.%, in particular 5 to 25 wt.%.

2. Composition according to claim 1, characterized in that the resin component and the hardener component are present separately from one another.

3. Composition according to one of the preceding claims, characterized in that the bio-based granules have a moisture content of less than 15% by weight, preferably less than 12% by weight.

4. Composition according to one of the preceding claims, characterized in that the bio-based granulate is selected from the group consisting of ground olive kernels, coconut shells, almond shells, walnut shells, pecan shells, Brazil nut shells, hazelnut shells, macadamia nut shells, cashew nut shells, pistachio shells, cocoa fruit shells, apricot kernel shells, peach kernel shells and plum kernel shells. 5 Composition according to one of the preceding claims, characterized in that the bio-based granulate is a granulate of olive kernels.

6. Composition according to one of the preceding claims, characterized in that the amine hardener contains at least one aliphatic, cycloaliphatic or arylaliphatic di- or triamine with at least 3 amine hydrogens, in particular selected from the list consisting of 2-butyl-2-ethyl-1,5-pentanediamine, 2,2(4),4-trimethylhexamethylenediamine, 1,2- Diaminocyclohexane, bis(4-aminocyclohexyl)methane, isophoronediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 2(4)-methyl-1,3-diaminocyclohexane, 2,5(2,6)-bis(aminomethyl)bicyclo[2.2.1]heptane, 1,3-bis(aminomethyl)benzene, polyoxypropylenediamines with medium molecular weight M n from 200 to 500 g / mol, polyoxypropylenetriamines with medium molecular weight M nfrom 300 to 500 g / mol, 3-(3-(dimethylamino)propylamino)propylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N,N'-bis(3-aminopropyl)ethylenediamine, N-benzyl-1,2-ethanediamine, N-furfuryl-1,2-ethanediamine, N-tetrahydrofurfuryl-1,2-ethanediamine, N-benzyl-1,3-bis(aminomethyl)benzene, and amine-functional adducts of these amines with aromatic diepoxides. Composition according to one of the preceding claims, characterized in that the amine curing agent contains at least one amine of the formula (I), NH2-A— NH— CH2-Y (l) where A represents a divalent alkylene or cycloalkylene radical having 2 to 8 C atoms, and Y represents an optionally substituted phenyl radical having 6 to 12 C atoms, furfuryl or a naphthyl radical, where the two nitrogen atoms to which the radical A is bonded are separated from one another by at least two C atoms. Composition according to claim 7, characterized in that the amine hardener, in addition to at least one amine of the formula (I), contains at least one further amine having two primary amino groups, in particular selected from the group consisting of isophoronediamine, 1,3-bis(aminomethyl)benzene, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 2,2(4),4-trimethylhexamethylenediamine, bis(4-aminocyclohexyl)methane, 2(4)-methyl-1,3-diaminocyclohexane and 2,5(2,6)-bis(aminomethyl)bicyclo[2.2.1]heptane. Composition according to one of claims 7 or 8, characterized in that the amine hardener contains such an amount of amine of the formula (I) that 3 to 40%, preferably 5 to 30%, in particular 6 to 20%, of all amine hydrogens in the epoxy resin composition originate from the amine of formula (I).

10. Composition according to one of the preceding claims, characterized in that, based on the total epoxy resin composition, less than 20% by weight, in particular less than 15% by weight, preferably less than 10% by weight, of diluents having a boiling point at atmospheric pressure of at least 180 °C, in particular at least 200 °C, are present, preferably selected from the list consisting of benzyl alcohol, 2-phenoxyethanol, cardanol, styrenated phenol, diisopropylnaphthalene, isopropylbiphenyls and phenol-containing aromatic hydrocarbon resins.

11. Composition according to one of the preceding claims, characterized in that, based on the total epoxy resin composition, the content of inorganic fillers is less than 5% by weight, preferably less than 2% by weight, in particular less than 1% by weight.

12. Composition according to one of the preceding claims, characterized in that at least one surface-active additive selected from defoamers and deaerators is present, in particular in an amount based on the total epoxy resin composition of 0.01 to 1 wt.%, preferably 0.02 to 0.5 wt.%.

13. Cured composition obtained from the curing of the epoxy resin composition according to one of claims 1 to 12 after mixing the components.

14. Use of the composition according to any one of claims 1 to 12 as a covering, coating, levelling, sealing or primer, in particular as a component of a floor covering.

15. Method for coating comprising the steps of a) mixing the components of the epoxy resin composition according to any one of claims 1 to 12, b) applying the mixed composition to at least one substrate, in particular a floor, in particular in a layer thickness in the range of 0.1 to 3 mm, c) allowing the applied coating to cure under ambient conditions, in particular at a temperature in the range of 5 to 45°C, particularly preferably at 5 to 30°C. Soil protection system, comprising i) at least one layer of the epoxy resin composition according to one of claims 1 to 12 in a layer thickness of 0.1 to 3 mm, ii) quartz sand which has been scattered in and / or onto, in particular onto, the epoxy resin composition i), iii) optionally at least one further layer of the epoxy resin composition according to one of claims 1 to 12, which in particular in a layer thickness of 0.1 to 1 mm is applied to the sand-strewn layer, iv) optionally at least one layer of bitumen which is applied to the epoxy resin composition iii), and v) optionally at least one layer of asphalt which is applied to the bitumen layer.

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