Adhesive for bonding membranes made of soft PVC

Abstract

The invention relates to the use of an epoxy resin adhesive for bonding a membrane made of soft PVC to a further substrate, wherein the curing-agent component of the adhesive comprises at least one amine A1 having at least one dimethylamino group and at least one amine hydrogen, and at least one further amine A2 having at least three amine hydrogens, and the curing-agent component comprises, based on the total of all the liquid or dissolved constituents contained in the curing-agent component, an amine A1 content of 10 to 45 wt.%. The use according to the invention allows bonding of untreated membranes made of soft PVC to form a stable, water-resistant adhesive bond and is particularly suitable for sealing tunnels, foundations and roofs.

Description

[0001] ADHESIVE FOR BONDING SOFT PVC MEMBRANES

[0002] Technical area

[0003] The invention relates to the bonding of waterproofing membranes made of soft PVC with epoxy resin-based adhesives.

[0004] State of the art

[0005] Plastic membranes for waterproofing foundations, drainage systems, underground shafts, tunnels, or roofs are often made of soft PVC. To create a waterproof surface, membranes are laid out in overlapping sheets and then bonded together using a suitable process. Soft PVC membranes are usually laid in sheets and typically welded to join the sheets. The underlying membrane is heated with hot air until the PVC melts, and then pressed onto the upper membrane so that the two membranes are joined with a weld seam after cooling. To create a watertight surface, double seams are usually welded, which can be checked for leaks using compressed air. This process is quite complex and not possible with certain coated membranes. As an alternative to welding, membranes can also be glued.In tunnel construction or when sealing foundations, the membranes are also bonded to the structure, typically to a concrete or mortar substrate. However, bonding soft PVC membranes with state-of-the-art adhesives is unsatisfactory, as these adhere only weakly to soft PVC and / or detach over time.

[0006] The epoxy resin adhesives used in construction for a wide variety of applications are generally permanently resistant to moisture and develop high adhesive strengths on a wide variety of substrates, such as concrete, mortar, steel, or fiberglass or carbon fiber-reinforced composite materials. However, they typically exhibit insufficient adhesion to untreated soft PVC.

[0007] To achieve good adhesion with epoxy resin adhesives, PVC membranes can be pretreated with an adhesion-promoting coating, or specially coated membrane strips can be used, which can be bonded with epoxy resin adhesives. Such specially coated membrane strips are welded to the PVC membrane to enable bonding of the membrane to the substrate. However, this process is very complex, and it would therefore be advantageous to have adhesives that enable permanent and moisture-resistant bonding of non-specially pretreated soft PVC membranes.

[0008] The use of dimethylamino group-containing amines such as 3-(3-dimethylaminopropylamino)propylamine as co-hardeners for epoxy resins to achieve high compressive strengths is known from the prior art, for example from EP 3,336,120.

[0009] Description of the invention

[0010] The object of the present invention is therefore to provide an adhesive for bonding membranes made of soft PVC, which enables a long-lasting, resilient adhesive bond with high resistance to the influence of heat and moisture, even without complex pretreatment or coating of the membrane.

[0011] Surprisingly, this object is achieved by using an adhesive according to claim 1. The epoxy resin adhesive used comprises a hardener component containing at least one amine A1 having at least one dimethylamino group and at least one amine hydrogen, and at least one further amine A2 having at least three amine hydrogens, wherein the content of amines A1 is 10 to 45% by weight, preferably 15 to 40% by weight, based on the sum of all liquid or dissolved constituents contained in the hardener component. Surprisingly, such a combination of amines enables good adhesion to untreated membranes made of soft PVC while simultaneously providing high resistance of the bond to the effects of moisture. Corresponding adhesives with a lower content of amine A1 show insufficient or no adhesion to soft PVC, whereas adhesives with a higher content of amine A1 result in bonds with insufficient water resistance.Furthermore, it has been shown that amines with dimethylamino groups, which are free of amine hydrogens, also result in bonds with insufficient water resistance.

[0012] In a particularly preferred embodiment of the invention, a combination of at least one amine A2-1 with an amine hydrogen equivalent weight of at least 80 g / eq, preferably at least 90 g / eq, and one amine A2-2 with two primary amino groups and four amine hydrogens is used as amine A2. Such a hardener enables low-emission adhesives with a high filler content and very good adhesion to soft PVC, which are particularly suitable for bonding soft PVC to concrete or mortar surfaces. Combinations of 3-(3-dimethylaminopropylamino)propylamine as amine A1, isophoronediamine as amine A2-2, and at least one amine selected from phenalkamines, phenalkamides, and amine-functional adducts of N-benzyl-1,2-ethanediamine with polyepoxides as amine A2-1 are particularly suitable.

[0013] The inventive use enables the bonding of soft PVC membranes to a variety of substrates, in particular to concrete or mortar, as is common, for example, in tunnel construction. In particular, even non-specially coated waterproofing membranes made of soft PVC can be bonded directly and permanently to concrete, mortar, or other substrate surfaces without further pretreatment. Furthermore, the inventive use enables the bonding of soft PVC membranes to one another and the bonding of soft PVC membranes to other membranes, for example those made of polyolefin, in particular surface-modified polyethylene. The resulting adhesive bond is stable and resistant to heat and moisture. In particular, the adhesive bond has a peel strength of at least 1 N / mm, preferably at least 1.5 N / mm, after storage for 28 days at 70°C and 100% relative humidity.

[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. Ways of carrying out the invention

[0015] The invention relates to the use of an adhesive for bonding a membrane made of soft PVC to another substrate, characterized in that the adhesive

[0016] - a resin component containing at least one epoxy resin and

[0017] - containing a hardener component

[0018] (a) at least one amine A1 having at least one dimethylamino group and at least one amine hydrogen, and

[0019] (b) at least one further amine A2 having at least three amine hydrogens which is free from dimethylamino groups, wherein the hardener component has a content of amines A1 of 10 to 45% by weight, based on the sum of all liquid or dissolved constituents contained in the hardener component.

[0020] A “membrane” is a flexible plastic film that is typically used to seal underground structures, tunnels, or roofs.

[0021] “Soft PVC” is a flexible, plasticized plastic made of polyvinyl chloride.

[0022] Z CH3

[0023] --N

[0024] A “dimethylamino group” is an amino group of the formula ^ H 3.

[0025] The hydrogen atoms of primary and secondary amine groups are called “amine hydrogen”.

[0026] The "amine hydrogen equivalent weight" is the mass of an amine or amine-containing compound containing one molar equivalent of amine hydrogen. It is expressed in the unit "g / eq."

[0027] The "sum of all liquid or dissolved components contained in the hardener component" refers to the hardener component after deducting any solids it may contain, especially fillers. 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 a hydrogen atom; and a "tertiary amino group" is an amino group that is bonded to three organic residues, two or three of which may also be part of one or more rings, and does not carry a hydrogen atom.

[0028] The "epoxide equivalent weight" is the mass of an epoxy-containing compound or composition that contains one molar equivalent of epoxy groups. It is expressed in the unit "g / eq."

[0029] Substance names beginning with “poly”, such as polyamine or polyepoxide, refer to substances that formally contain two or more of the functional groups mentioned in their name per molecule.

[0030] A “thinner” is a substance that is soluble in an epoxy resin and reduces its viscosity, but which is not chemically bound into the epoxy resin polymer during curing.

[0031] The “pot life” of an adhesive is the maximum period of time from mixing the components and applying the adhesive during which the mixed adhesive is in a sufficiently flowable state and can wet the substrate surfaces well.

[0032] The “open time” of an adhesive is the maximum possible time period between the application of the adhesive and the joining of the parts to be bonded for a force-locking connection.

[0033] 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.

[0034] “Room temperature” is defined as a temperature of 23 °C.

[0035] All industry standards and norms mentioned in this document refer to the versions valid at the time of filing the initial application, unless otherwise stated. Percentages by weight (wt%) refer to the mass fraction of a component of a composition relative to the total composition, unless otherwise stated. The terms "mass" and "weight" are used synonymously in this document.

[0036] The resin and hardener components of the adhesive are stored separately in separate containers and are only mixed together shortly before or during application.

[0037] A suitable epoxy resin is obtained in a known manner, in particular from the oxidation of olefins or from the reaction of epichlorohydrin with polyols, polyphenols or amines.

[0038] Aromatic epoxy resins are preferred, in particular the glycidyl ethers of:

[0039] - Bisphenol-A, bisphenol-F, or bisphenol-A / F, where A stands for acetone and F for 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 derived from 2,4'- or 2,2'-hydroxyphenylmethane.

[0040] - Dihydroxybenzene derivatives such as resorcinol, hydroquinone or pyrocatechol,

[0041] - weiteren Bisphenolen oder Polyphenolen wie Bis(4-hydroxy-3-methylphenyl)- methan, 2,2-Bis(4-hydroxy-3-methylphenyl)propan (Bisphenol-C), Bis(3,5- dimethyl-4-hydroxyphenyl)methan, 2,2-Bis(3,5-dimethyl-4-hydroxyphenyl)pro- pan, 2,2-Bis(3,5-dibromo-4-hydroxyphenyl)propan, 2,2-Bis(4-hydroxy-3-tert.bu- tylphenyl)propan, 2,2-Bis(4-hydroxyphenyl)butan (Bisphenol-B), 3,3-Bis(4- hydroxyphenyl)pentan, 3,4-Bis(4-hydroxyphenyl)hexan, 4,4-Bis(4-hydroxy- phenyl)heptan, 2,4-Bis(4-hydroxyphenyl)-2-methylbutan, 2,4-Bis(3,5-dimethyl-4- hydroxyphenyl)-2-methylbutan, 1 ,1-Bis(4-hydroxyphenyl)cyclohexan (Bisphe- nol-Z), 1 ,1-Bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexan (Bisphenol-TMC),

[0042] 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,

[0043] - 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,

[0044] - aromatic amines, such as aniline, toluidine, 4-aminophenol, 4,4'-methylenediphenyldiamine, 4,4'-methylenediphenyldi-(N-methyl)amine, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline (bisaniline-P) or 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline (bisaniline-M).

[0045] Other suitable epoxy resins are aliphatic or cycloaliphatic polyepoxides, in particular

[0046] - 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;

[0047] - a hydrogenated bisphenol-A, -F or -A / F liquid resin, or the glycidylation products of hydrogenated bisphenol-A, -F or -A / F;

[0048] - an N-glycidyl derivative of amides or heterocyclic nitrogen bases, such as triglycidyl cyanurate or triglycidyl isocyanurate, or reaction products of epichlorohydrin with hydantoin.

[0049] - Epoxy resins from the oxidation of olefins, such as in particular vinylcyclohexene, dicyclopentadiene, cyclohexadiene, cyclododecadiene, cyclododecatriene, isoprene, 1,5-hexadiene, butadiene, polybutadiene or divinylbenzene.

[0050] Other suitable epoxy resins are those resulting from the reaction of bio-based hydroxy-functional raw materials with epichlorohydrin, in particular vanillin-based epoxy resins such as diglycidyl ethers of vanillin alcohol, or glycerol-based epoxy resins.

[0051] Preferably, the epoxy resin is a liquid resin or a mixture containing two or more epoxy liquid resins.

[0052] An “epoxy liquid resin” is a technical polyepoxide with a glass transition temperature below 25°C.

[0053] If necessary, the resin component also contains portions of solid epoxy resin.

[0054] The resin component particularly preferably contains at least one aromatic liquid epoxy resin, in particular a bisphenol A diglycidyl ether, a bisphenol F diglycidyl ether, or a phenol-formaldehyde novolak glycidyl ether, with the phenol-formaldehyde novolak glycidyl ether preferably having an average functionality in the range of 2.3 to 4, preferably 2.5 to 3. These epoxy resins are very hydrophobic and have a low viscosity for an epoxy resin. They enable good processability, rapid curing, and high adhesive strengths.

[0055] The aromatic epoxy liquid resin preferably has an average epoxy equivalent weight of 150 to 250 g / eq.

[0056] The resin component preferably additionally contains at least one reactive diluent containing epoxy groups.

[0057] Particularly suitable for this purpose are 1,4-butanediol diglycidyl ether, 1,6-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, 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 C10 or C12 to C14 or C13 to C15 alkyl glycidyl ether. Preferred reactive diluents are 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, p-tert-butylphenyl glycidyl ether, cardanol glycidyl ether or Cs to Cw or C12 to C14 or C13 to C18 alkyl glycidyl ether.

[0058] 1,4-Butanediol diglycidyl ether and / or 1,6-hexanediol diglycidyl ether are particularly preferred. Such an adhesive enables particularly high adhesive strengths with soft PVC membranes while maintaining good water resistance.

[0059] The weight ratio between aromatic epoxy liquid resins and reactive diluents containing epoxy groups is preferably in the range from 60 / 40 to 95 / 5, in particular 70 / 30 to 95 / 10.

[0060] The hardener component contains at least one amine A1 with at least one dimethylamino group and at least one amine hydrogen. Such an amine enables particularly good adhesion to soft PVC and is incorporated into the polymer network during the curing of the adhesive.

[0061] The amine A1 is preferably selected from the group consisting of 2-dimethylaminoethylamine, 3-dimethylaminopropylamine (DMAPA), 4-dimethylaminobutylamine, 6-dimethylaminohexylamine, 2-(2-dimethylaminoethylamino)ethylamine, 2-(3-dimethylaminopropylamino)ethylamine, 3-(2-Dimethylaminoethylamino)propylamine, 3-(3-Dimethylaminopropylamino)propylamine (DMAPAPA), N-(3-Dimethylaminopropyl)-1,3-bis(aminomethyl)benzene, N-(3-Dimethylaminopropyl)-1,4-bis-(aminomethyl)benzene, 2,4,6-Tris(4-dimethylamino-2-azabutyl)phenol, bis(2-dimethylaminoethyl)amine, bis(3-dimethylaminopropyl)amine and bis(6-dimethylaminohexyl)amine.

[0062] The amine A1 preferably contains at least two amine hydrogens, in particular at least three amine hydrogens.

[0063] The most preferred amine A1 is 3-(3-dimethylaminopropylamino)propylamine (DMAPAPA). It is low-odor, toxicologically advantageous, commercially readily available, and enables very high bond strengths with good water resistance. Another preferred amine A1 is 3-dimethylaminopropylamine (DMAPA). It has a particularly high concentration of dimethylamino groups and is commercially readily available.

[0064] Another preferred amine A1 is N-(3-dimethylaminopropyl)-1,3-bis(aminomethyl)benzene. It is particularly low-odor, obtainable from the reductive alkylation of 3-dimethylaminopropylamine with 3-cyanobenzaldehyde, and enables particularly high adhesive strengths with good water resistance of the bond.

[0065] The adhesive preferably contains an amount of Amine A1 such that the hardener component has an Amine A1 content of 15 to 40% by weight, based on the sum of all liquid or dissolved components contained in the hardener component. Any fillers contained in the hardener component are therefore not included. Such an amount of Amine A1 enables a particularly advantageous combination of high adhesive strength and good water resistance of the bond.

[0066] Furthermore, the adhesive preferably contains an amount of amine A1 such that the number of amine hydrogen equivalents from amines A1, based on the total number of amine hydrogen equivalents in the hardener component, is in the range of 20 to 60%, preferably 25 to 55%. Such an amount of amine A1 enables a particularly advantageous combination of high adhesive strength and good water resistance of the bond.

[0067] The hardener component contains at least one additional amine A2 with at least three amine hydrogens, which is free of dimethylamino groups. Such an amine enables high bond strength with good resistance to moisture.

[0068] Suitable as amine A2 are commercially available polyamines with aliphatically bound amino groups, as they are usually used for curing epoxy resins. Preferably, the amine A2 is selected from the group consisting of 1,5-diamino-2-methylpentane (MPMD), 1,6-hexanediamine, 2,2(4),4-trimethyl-1,6-hexanediamine (TMD), 2-butyl-2-ethyl-1,5-pentanediamine (C11-neodiamine), isophoronediamine (IPDA), 1,3-bis(aminomethyl)benzene (MXDA), 1,4-bis(aminomethyl)benzene, 2,5-bis(aminomethyl)furan, 2,5-bis(aminomethyl)tetrahydrofuran, 1,3-bis(aminomethyl)cyclohexane (BAC), 1,4-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, 1,2-diaminocyclohexane (DACH), 1 ,3-diaminocyclohexane, 1,4-diaminocyclohexane, 2(4)-methyl-1,3-diaminocyclohexane (MCDA), 2,5(2,6)-bis-(aminomethyl)bicyclo[2.2.1]heptane (NBDA), N-benzyl-1,2-ethanediamine, N-furfuryl-1,2-ethanediamine, N-tetrahydrofurfuryl-1,2-ethanediamine, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), dipropylenetriamine (DPTA), N-(2-aminoethyl)-1,3-propanediamine (N3-amine), N,N'-bis(3-aminopropyl)ethylenediamine (N4-amine), bis(1,6-hexylene)triamine (BHMT), phenalkamines, phenalkamides, polyamidoamines, amine-functional adducts of the mentioned amines with epoxides, and combinations of two or more of these amines.

[0069] Particularly suitable phenalkamines are reaction products of cardanol with formaldehyde and polyamines. Phenalkamines that also contain amide groups are particularly suitable as phenalkamides. Particularly suitable polyamidoamines are reaction products of dimer fatty acids with polyalkyleneamines, such as DETA, TETA, or TEPA.

[0070] Particularly preferred are IPDA, MXDA, BAC, DACH, MCDA, N-benzyl-1,2-ethanediamine, amine-functional adducts of N-benzyl-1,2-ethanediamine with polyepoxides, DETA, TETA, TEPA, DPTA, N3-amine, N4-amine, phenalkamines, phenalkamides and combinations of two or more of these amines.

[0071] IPDA is particularly preferred.

[0072] Also particularly preferred is N-benzyl-1,2-ethanediamine.

[0073] Also particularly preferred are amine-functional adducts of N-benzyl-1,2-ethanediamine with at least one polyepoxide, in particular an aromatic epoxy liquid resin. These adducts are particularly low-viscosity, can be produced in high concentrations without solvents or thinners, and enable high water resistance of the bond.

[0074] Also particularly preferred are phenalkamines or phenalkamides, in particular solvent-free phenalkamines or phenalkamides as marketed commercially by Cardolite, in particular phenalkamides such as Cardolite® LITE 3025, LITE 3040 or LITE 3060 (all from Cardolite).

[0075] In a preferred embodiment, the hardener component contains, as amine A2, at least one amine A2-1 with an amine hydrogen equivalent weight of at least 80 g / eq, preferably at least 90 g / eq. Such an amine enables adhesives with high filler content and low diluent content. Particularly suitable as amine A2-1 is a phenalkamine or phenalkamide or an amine-functional adduct of N-benzyl-1,2-ethanediamine with at least one polyepoxide, in particular an aromatic epoxy liquid resin. These amines are hydrophobic, comparatively low-viscosity, and enable low-emission adhesives with high moisture resistance.

[0076] In a particularly preferred embodiment, the hardener component contains as amine A2 a combination of at least one amine A2-1 as described above and at least one amine A2-2 with two primary amino groups and four amine hydrogens.

[0077] Preferably, the amine A2-2 is selected from IPDA, MXDA, BAC, DACH and MCDA, with IPDA being most preferred.

[0078] In the most preferred embodiment, the hardener component contains a combination of 3-(3-dimethylaminopropylamino)propylamine (DMAPAPA), isophoronediamine (IPDA) and at least one amine selected from phenalkamines, phenalkamides and amine-functional adducts of N-benzyl-1,2-ethanediamine with at least one aromatic epoxy liquid resin.

[0079] The preferred amines and amounts enable adhesives with particularly high adhesive strengths and high resistance to moisture. The adhesive preferably contains other ingredients, which are present as part of the resin and / or hardener component and / or as another separate component. Components reactive toward amine hydrogens are preferably present as part of the resin component. Components reactive toward epoxy groups are preferably present as part of the hardener component.

[0080] The adhesive preferably contains at least one further ingredient selected from thinners, fillers, accelerators and surface-active compounds.

[0081] Suitable thinners are particularly those with a boiling point of at least 200 °C at atmospheric pressure, in particular 2-phenoxyethanol, 2-benzyloxyethanol, benzyl alcohol, ethylene glycol dibutyl ether, ethylene glycol diphenyl ether, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butylyl ether, propylene glycol phenyl ether, dipropylene glycol, dipropylene glycol di-n-butyl ether, diphenylmethane, diisopropylnaphthalene, propylated biphenyl, tert. Butylphenol, nonylphenol, dodecylphenol, cardanol (from cashew shell oil, containing as main components 3-(7-pentadecenyl)phenol, 3-(7,10,14-pentadecatrienyl)phenol and 3-(7,10-pentadecadienyl)phenol), styrenized phenol, bisphenols, aromatic hydrocarbon resins, in particular types containing phenol groups, adipates, sebacates, phthalates, benzoates, organic phosphoric or sulfonic acid esters or sulfonamides.

[0082] Preferred are benzyl alcohol, styrenated phenol, ethoxylated phenol such as in particular 2-phenoxyethanol, aromatic hydrocarbon resins containing phenol groups, in particular the Novares® types LS 500, LX 200, LA 300 or LA 700 (from Rütgers), diisopropylnaphthalene, propylated biphenyl or cardanol.

[0083] The adhesive preferably contains only a low content of thinners. The adhesive preferably contains a maximum of 30 parts by weight, in particular a maximum of 25 parts by weight, preferably a maximum of 20 parts by weight, particularly preferably a maximum of 10 parts by weight, in particular a maximum of 5 parts by weight, of thinner per 100 parts by weight of the sum of all epoxy and amine group-containing components. This enables bonds with particularly high resistance to moisture.

[0084] Suitable fillers are, in particular, ground or precipitated calcium carbonates, which may be coated with fatty acids, in particular stearates, barite (barite), talc, quartz flour, quartz sand, silicon carbide, iron mica, dolomite, wollastonite, kaolin, mica (potassium aluminum silicate), molecular sieve, aluminum oxide, aluminum hydroxide, magnesium hydroxide, silica, cement, gypsum, fly ash, carbon black, graphite, metal powders such as aluminum, copper, iron, zinc, silver or steel, PVC powder or hollow spheres.

[0085] The adhesive preferably contains mineral fillers, in particular selected from calcium carbonate, barite, talc, quartz flour, quartz sand, kaolin and combinations of these fillers.

[0086] The adhesive preferably contains 60 to 90% by weight, in particular 70 to 85% by weight, of mineral fillers based on the total adhesive.

[0087] Suitable accelerators are, in particular, acids or compounds hydrolyzable to acids, in particular organic carboxylic acids such as acetic acid, benzoic acid, salicylic acid, 2-nitrobenzoic acid, lactic acid, organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid or 4-dodecylbenzenesulfonic acid, sulfonic acid esters, other organic or inorganic acids or acid esters; furthermore, nitrates such as, in particular, calcium nitrate; tertiary amines, imidazoles, ammonium salts, amidines, guanidines, phenols, phenol resins or Mannich bases such as, in particular, 2,4,6-tris(dimethylaminomethyl)phenol, or compounds containing mercapto groups.

[0088] Preferred accelerators are acids, nitrates, tertiary amines or Mannich bases, in particular salicylic acid, calcium nitrate or 2,4,6-tris(dimethylaminomethyl)phenol or a combination of these accelerators.

[0089] Suitable surface-active compounds include, in particular, thickeners, wetting agents, defoamers, or deaerators. The adhesive is preferably not water-based. It preferably contains less than 5% by weight, in particular less than 1% by weight, of water based on the total adhesive.

[0090] The adhesive may contain other auxiliary substances and additives, such as

[0091] - other reactive diluents, in particular epoxidized soybean oil or linseed oil, compounds containing acetoacetate groups, butyrolactone, carbonates, aldehydes, isocyanates or silicones containing reactive groups,

[0092] - solvents,

[0093] - other amines, in particular aromatic polyamines such as 4,4'-, 2,4' and / or 2,2'-diaminodiphenylmethane, 2,4- and / or 2,6-toluenediamine,

[0094] 3,5-Dimethylthio-2,4- and / or -2,6-toluenediamine, 3,5-Diethyl-2,4- and / or -

[0095] 2.6-toluenediamine,

[0096] - other compounds containing dimethylamino groups, in particular (meth)acrylamides such as 3-dimethylaminopropylmethacrylamide,

[0097] - 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,

[0098] - 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,

[0099] - Fibers, in particular glass fibers, carbon fibers, metal fibers, ceramic fibers, plastic fibers such as polyamide fibers or polyethylene fibers or bio-based fibers such as wood fibers, cellulose fibers, hemp fibers, flax (linen), jute or coconut fibers, - Nanofillers, in particular carbon nanotubes,

[0100] - Pigments, in particular titanium dioxide, iron oxides or chromium(III) oxide,

[0101] - adhesion promoters, especially organoalkoxysilanes,

[0102] - flame-retardant substances or

[0103] - other additives, in particular stabilizers against oxidation, heat, light or UV radiation or biocides.

[0104] A preferred adhesive for use according to the invention contains, based on the total adhesive,

[0105] - 10 to 20% by weight of aromatic epoxy liquid resins,

[0106] - 1 to 4% by weight of reactive diluents containing epoxy groups,

[0107] - 3-(3-Dimethylaminopropylamino)propylamine,

[0108] - Isophoronediamine,

[0109] - at least one amine A2-1 having an amine hydrogen equivalent weight of at least 80 g / eq, preferably at least 90 g / eq,

[0110] - 60 to 90% by weight mineral fillers and, if necessary, other ingredients.

[0111] The epoxy resins and the reactive diluents containing epoxy groups are part of the resin component, the amines are part of the hardener component and the mineral fillers and any other components present are part of the resin and / or the hardener component or can be present as a separate, additional component.

[0112] Suitable soft PVC membranes for the inventive use are commercially available membranes such as those used for sealing tunnels, foundations, bridges, roofs, silos, swimming pools, sewage treatment plants, ponds, or tanks. They consist largely of plasticized polyvinyl chloride, typically with plasticizer contents of 20 to 50% by weight based on the entire membrane. They have a thickness of 1 to 5 mm and are usually available in the form of rolled sheets with a width of approximately 0.2 to 3 m. For use, they are typically cut to the desired size and / or joined together by hot-air welding. The soft PVC membrane can contain an internal polyester fabric or glass fiber fleece for reinforcement.

[0113] Some commercially available soft PVC membranes have visually distinct top and bottom surfaces. In the case of membranes used underground, for example, for sealing tunnels or foundations, the top and bottom surfaces are typically pigmented differently to provide a better overview during installation. Sikaplan® WP 2110-21 HL (from Sika), for example, has a yellow-pigmented top surface and a black-pigmented bottom surface, with the black-pigmented bottom surface resting on the substrate to be waterproofed.

[0114] Membranes for roof waterproofing also typically have a differently colored top and bottom. In certain roof waterproofing membranes, the top side is coated with a particularly light- and UV-stable layer.

[0115] Particularly suitable membranes made of soft PVC for the use according to the invention are the products from Sika available under the brand names Sikaplan® or Sarnafil®, for example Sikaplan® WP 1100, Sikaplan® WP 2110, Sarnafil® G 410 (with UV-stable surface seal), Sarnafil® S 327 (with UV-stable surface seal), Sikaplan® G, Sikaplan® VG, Sikaplan® SGmA, as well as membranes made of soft PVC from other suppliers.

[0116] Both the top and bottom of the membrane can be glued. Typically, the bottom of the membrane is glued.

[0117] A key aspect of the inventive use is that it is not necessary to use a soft PVC membrane with an adhesion-promoting surface coating to achieve a resilient adhesive bond. In particular, it is not necessary to apply a primer or activator to the membrane prior to applying the adhesive. Furthermore, it is not necessary to use a special membrane that is fully or partially coated with a surface coating to improve adhesion, as is the case, for example, with Sikaplan® WP Tape-200 (from Sika).

[0118] Thus, the soft PVC membrane for use according to the invention preferably does not have an adhesion-promoting surface coating.

[0119] However, it may be beneficial to clean the membrane of dust and dirt before bonding, for example by blowing, vacuuming, wiping, or cleaning with a solvent, for example. If a clean membrane is used fresh from the roll, such cleaning prior to use is typically not necessary.

[0120] Another substrate suitable for use according to the invention is in particular

[0121] - a plastic such as rigid and soft PVC, polycarbonate, polystyrene, polyester, polyamide, PMMA, ABS, SAN, epoxy resins, phenolic resins, PUR, POM, TPO, PE, PP, EPM or EPDM, in each case untreated or surface-treated, for example by means of plasma, corona or flames;

[0122] - Concrete, mortar, cement screed, fiber cement, brick, tile, plaster, natural stones such as granite or marble, glass or glass ceramic;

[0123] - asphalt or bitumen;

[0124] - Repair or levelling compounds based on PCC (polymer-modified cement mortar) or ECC (epoxy resin-modified cement mortar);

[0125] - Fiber-reinforced plastics, such as carbon fiber-reinforced plastics (CFRP), glass fiber-reinforced plastics (GRP), natural fiber-reinforced plastics (NFRP) or sheet molding compounds (SMC);

[0126] - 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;

[0127] - Metals or alloys such as aluminum, iron, steel, copper, other non-ferrous metals, including surface-treated metals or alloys such as galvanized or chrome-plated metals;

[0128] - Insulating foams, in particular made of EPS, XPS, PUR, PIR, rock wool, glass wool or foamed glass (foam glass); - Coated or painted substrates, in particular painted tiles, painted concrete, powder-coated metals or alloys or painted sheets, in particular sheets coated with polyvinylidene fluoride;

[0129] - Coatings, paints or varnishes, especially coated floors.

[0130] The additional substrate can be pretreated, if necessary, prior to applying the adhesive, in particular by physical and / or chemical cleaning processes or by applying an activator or primer. It is preferably not pretreated other than surface cleaning, in particular removing dust.

[0131] Preferably, the further substrate is selected from soft PVC, polyolefin, modified polyethylene, concrete, mortar, cement screed, fiber cement, brick, tile, natural stone, steel, metals coated with polyvinylidene fluoride and other plastics.

[0132] In a preferred embodiment of the use, the further substrate is a further membrane made of soft PVC, or a membrane made of another plastic such as in particular polyolefin, for example Sikaplan® WT 1200 (from Sika), or a membrane made of modified polyethylene such as in particular Hypalon®.

[0133] In a particularly preferred embodiment of the use, the further substrate is a non-flexible material with a solid surface, in particular concrete, mortar, cement screed, fiber cement, brick, tile, natural stone, steel, metals coated with polyvinylidene fluoride or other plastics such as rigid PVC, fiber-reinforced plastics or SMC, in particular concrete, mortar or metals coated with polyvinylidene fluoride.

[0134] Polyvinylidene fluoride-coated metals include, in particular, metal sheets, commercially available as Kynar® 500 (from Arkema) coated metal sheets, especially for roofing. The described adhesive exhibits surprisingly good adhesion to such coated metal sheets, which is particularly advantageous, for example, at transitions from pitched roof surfaces with a Kynar® 500 metal covering to flat roof surfaces sealed with a PVC membrane, or in flat roofs with Kynar® 500 metal frames, for permanently bonding the two materials. The use of the adhesive for bonding a soft PVC membrane to a polyvinylidene fluoride-coated metal is therefore particularly preferred.

[0135] For the inventive use, the resin and hardener components, and any other components present in the adhesive, are mixed using a suitable method. The mixing ratio is preferably selected such that the molar ratio of the groups reactive toward epoxy groups to the epoxy groups is in the range of 0.5 to 1.5, in particular 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 1:2 to 20:1, in particular 1:1 to 5:1.

[0136] The components are mixed continuously or batchwise using a suitable process, ensuring that the time between mixing the components and applying the mixed adhesive is not too long, so that the application is completed within the adhesive's pot life. Mixing and application of the adhesive preferably take place at ambient temperature, which typically ranges from approximately 5 to 40°C, preferably approximately 10 to 35°C.

[0137] For the use according to the invention, the mixed adhesive is applied to the soft PVC membrane and / or to the other substrate within the pot life.

[0138] The adhesive is preferably applied by hand using a spatula or trowel. It can also be applied from a cartridge or with a hydraulic conveyor system.

[0139] Preferably, the adhesive is applied in such an amount that after joining and pressing the substrates, the adhesive joint has a thickness of 0.5 to 10 mm, preferably 1 to 5 mm.

[0140] The soft PVC membrane can be bonded over the entire surface or in one or more partial areas. Bonding is preferably done in one or more partial areas. Following application of the mixed adhesive, the joint is joined within the adhesive's open time. The pot life and open time of the adhesive depend on its ingredients, the presence of accelerators, and the temperature. At room temperature, the open time is typically approximately 15 minutes to approximately 2 hours.

[0141] Depending on the geometry of the bond, it is advantageous to fix the bond after joining using a suitable method to prevent the joined parts from shifting as long as the adhesive has not yet cured enough to hold the joined parts in the selected position.

[0142] After the bond is formed, the adhesive cures. The adhesive preferably cures under ambient conditions.

[0143] The adhesive cures through a chemical reaction between the ingredients. The amine hydrogens of primary and secondary amino groups, and any other epoxy-reactive groups present, react with the epoxy groups, causing their ring opening. Furthermore, the dimethylamino groups present catalyze the homopolymerization of the epoxy groups. As a result of these reactions, the adhesive polymerizes and thus cures. Curing typically takes several hours to several days. The duration depends, among other things, on the temperature, the reactivity of the components, their stoichiometry, and the presence or amount of accelerators.

[0144] Another object of the invention is an adhesive composite obtained from the use as described above.

[0145] The adhesive bond preferably has an adhesive layer thickness of 0.5 to 10 mm, in particular 1 to 5 mm.

[0146] The adhesive bond preferably has a peel strength value of at least 1 N / mm, preferably at least 1.5 N / mm, determined both after a) 7 days of curing in standard climate, and after b) 7 days of curing in standard climate followed by 28 days of storage at 70 °C and 100% relative humidity followed by 3 days of storage in standard climate.

[0147] In the event that the soft PVC membrane is bonded to another membrane, the peel strength is determined according to DIN EN 14173 at a tensile speed of 100 mm / min.

[0148] In the case that the soft PVC membrane is bonded to a solid surface, the peel strength is determined in accordance with DIN EN 14173 at a pulling speed of 100 mm / min with a pulling angle of 90° between the soft PVC membrane and the solid surface.

[0149] The resulting adhesive bond is preferably part of a waterproofing system for tunnels, foundations, archive rooms, service rooms, sports stadiums, subway stations, underpasses, military installations, ponds, swimming pools, sewage treatment plants, silos, tanks, terraces or parking decks.

[0150] Furthermore, the adhesive bond obtained is preferably part of a roof seal, in particular a seal of slightly inclined roof surfaces, in particular flat roofs with ballast or mechanically fastened flat roofs.

[0151] The resulting adhesive bond is able to connect the bonded parts reliably and durably and enables reliable sealing against penetrating water and gases such as methane or radon.

[0152] Examples

[0153] The following are exemplary embodiments intended to further illustrate the described invention. Of course, the invention is not limited to these described exemplary embodiments.

[0154] “AHEW” stands for the amine hydrogen equivalent weight.

[0155] “EEW” stands for epoxy equivalent weight.

[0156] The "standard climate" ("NC") is defined as a temperature of 23±1 °C and a relative humidity of 50±5%. Unless otherwise stated, the chemicals used were from Sigma-Aldrich Chemie GmbH.

[0157] Substances and abbreviations used:

[0158] BADGE Bisphenol-A diglycidyl ether, EEW approx. 187 g / eq (Araldite®

[0159] GY 250, from Huntsman)

[0160] BD-DGE 1,4-butanediol diglycidyl ether, EEW approx. 128 g / eq (Grilonit® RV

[0161] 1806, by EMS-Chemie)

[0162] HD-DGE 1,6-hexanediol diglycidyl ether, EEW approx. 147 g / eq (Grilonit®

[0163] RV 1812, from EMS-Chemie)

[0164] DY-E monoglycidyl ether from C12 to Cu alcohols, EEW approx. 290 g / eq (Araldite® DY-E, from Huntsman)

[0165] Rütasolv® BP M propylated biphenyl (from Rütgers)

[0166] DMAPAPA 3-(3-Dimethylaminopropylamino)propylamine, AHEW 53 g / eq

[0167] (DMAPAPA, by Arkema)

[0168] DMAPA 3-Dimethylaminopropylamine, AHEW 51 g / eq (DMAPA, from

[0169] Arkema)

[0170] DMAP-MXDA N-(3-Dimethylaminopropyl)-1,3-bis(aminomethyl)benzene,

[0171] AHEW 73.7 g / eq, prepared as described below

[0172] IPDA isophoronediamine, AHEW 42.6 g / eq (Vestamin® IPD, from

[0173] Evonik)

[0174] LITE 3025 phenalkamide hardener, AHEW approx. 103 g / eq (Cardolite® LITE 3025, from Cardolite)

[0175] Adduct-1 Adduct of N-benzyl-1,2-ethanediamine to bisphenol A-

[0176] Diglycidyl ether, AHEW 116.6 g / eq, prepared as described below

[0177] Quartz flour grain size 0 to 75 pm

[0178] Quartz sand grain size 0.1 to 0.3 mm coated CaCO3 precipitated, surface-treated chalk (Winnofil® SPT, from Imerys Performance Minerals)

[0179] DMAP-MXDA: N-(3-Dimethylaminopropyl)-1,3-bis(aminomethyl)benzene. 39.2 g (0.30 mol) of 3-formylbenzonitrile was dissolved in 750 ml of isopropyl alcohol, mixed with 32.0 g (0.315 mol) of 3-dimethylaminopropylamine (DMAPA, from Arkema) and stirred for 1 hour. The mixture was then hydrogenated at 65 °C, 75 bar hydrogen pressure, and a flow rate of 5 ml / min on a continuously operating hydrogenation apparatus with a Raney nickel fixed-bed catalyst. The hydrogenated solution was concentrated on a rotary evaporator at 65 °C, removing unreacted 3-dimethylaminopropylamine, water, and isopropanol. The resulting reaction mixture was purified by distillation at 130 °C under vacuum. A colorless liquid was obtained with a content of N-dimethylaminopropyl-1,3-bis(aminomethyl)benzene of > 97%, determined by GC, which was subsequently used as DMAP-MXDA.

[0180] Adduct-1 :

[0181] 45.0 g (0.3 mol) of N-benzyl-1,2-ethanediamine were initially charged under a nitrogen atmosphere and heated to 80 °C. With vigorous stirring, 36.8 g (0.2 mol of epoxy groups) of bisphenol A diglycidyl ether (Araldite® GY 250, ex Huntsman) were slowly added, maintaining the temperature of the reaction mixture between 70 and 90 °C for one hour. A clear, slightly yellowish liquid was obtained.

[0182] Production of adhesives and bondings:

[0183] Examples 1 to 12:

[0184] For each example, a resin component (resin comp.) was prepared by mixing the resin component ingredients listed in Tables 1 and 2 in the specified amounts (in parts by weight) using a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.) and storing the mixture in an atmosphere protected from moisture.

[0185] Furthermore, a hardener component (hardener comp.) was prepared for each example by mixing the hardener component ingredients listed in Tables 1 and 2 in the specified amounts (in parts by weight) using a centrifugal mixer and storing the mixture in a dry, dry place. For each example, the resin component and the hardener component were then processed into a homogeneous paste using a centrifugal mixer and immediately tested as follows:

[0186] The peel strength (T-Peel) was determined by bonding two 50 x 200 mm membrane strips (Sikaplan® WP 2110-21 HL, a waterproofing membrane for tunnel construction made of soft PVC, from Sika) onto a surface measuring 50 x 150 mm and with an adhesive thickness of 2 mm, ensuring that the two black sides were bonded together. For testing, the composites were pulled apart at an angle of 180° at a tensile speed of 100 mm / min in accordance with DIN EN 14173, and the strength was evaluated at the center 100 mm. The peel strength was determined after 7 days of curing under standard conditions (7d NK), as well as after additional storage for 28 days at 70 °C and 100% relative humidity (= cataplasm), followed by 3 days under standard conditions (+ 28d 70 / 100).

[0187] To determine the tensile strength of the adhesive, the mixed adhesive was applied to a silicone mold under standard climate conditions to form dumbbell-shaped test specimens with a thickness of 10 mm, a length of 150 mm, a web length of 80 mm and a web width of 10 mm. After 7 days, the specimens were removed from the mold and the tensile strength was determined according to EN ISO 527 at a tensile speed of 1 mm / min.

[0188] The results are presented in Tables 1 and 2. Examples marked with "(Ref.)" are comparative examples.

[0189] Table 1 shows that an adhesive without DMAPAPA (= Amine A1) (Example 1 (Ref.)) and an adhesive with too low a DMAPAPA content (Example 2 (Ref.)) exhibit insufficient peel strength and adhesion. Examples 3 and 4 with the inventive DMAPAPA content show good to very good adhesion to soft PVC with peel strength values ​​of more than 1 MPa, even after the bond has been stored for 4 weeks in a warm, humid climate. The adhesive from Example 5 (Ref.) with too high a DMAPAPA content does show very good adhesion to soft PVC after curing in a standard climate, but after the bond has been stored for 4 weeks in a warm, humid climate, the peel strength and adhesion are insufficient. The bond has insufficient water resistance.

[0190]

[0191] Table 1: Composition and properties of examples 1 to 8.

[0192] "nb" stands for "not determined".

[0193] 1 Content of Amine A1 based on the sum of the liquid components of the hardener component in weight %

[0194] 2 Proportion of amine hydrogen equivalents from amine A1 relative to the total number of amine hydrogen equivalents in the hardener component

[0195] 3 Parts by weight of thinner per 100 parts by weight of epoxies and amines

[0196] 4 Bonding of soft PVC with soft PVC

[0197] 5 of the adhesive

[0198] Table 2: Composition and properties of examples 9 to 12.

[0199] 1 Content of Amine A1 based on the sum of the liquid components of the hardener component in weight %

[0200] 2Proportion of amine hydrogen equivalents from amine A1 relative to the total number of amine hydrogen equivalents in the hardener component

[0201] 3 Parts by weight of thinner per 100 parts by weight of epoxies and amines

[0202] 4 Bonding of soft PVC with soft PVC

[0203] Further tests were conducted with the adhesives from Examples 4 and / or 9 as described below: The peel strength (T-Peel) was determined with additional soft PVC membranes as specified in Table 3 as previously described. In some cases, the peel strength was also tested after 7 days in a standard climate followed by 28 days immersed in deionized water at room temperature followed by 3 days in a standard climate (+ 28d H2O).

[0204] The tensile shear strength was tested on rigid PVC. Composites were created by bonding two untreated rigid PVC sheets together in such a way that the overlapping adhesive joint had dimensions of 12 x 25 mm and a thickness of 2 mm, with the sheets protruding at the ends. After storing the composites for 7 days under standard conditions, the tensile shear strength was tested according to DIN EN 1465 at a tensile speed of 20 mm / min.

[0205] The peel strength (T-Peel) was also determined on dry and damp concrete. For this purpose, a dry concrete garden slab was provided under standard conditions. Another garden slab was immersed in tap water for 24 hours and then dabbed dry with a cloth (= damp concrete). Three membrane strips (Sikaplan® WP 2110-21 HL, a waterproofing membrane for tunnel construction made of soft PVC, from Sika) measuring 50 x 200 mm were bonded to each of these concrete surfaces over an area measuring 50 x 150 mm with an adhesive thickness of 2 mm. After curing for 7 days under standard conditions, the bonded membrane was pulled away from the concrete surface at an angle of 90° at a tensile speed of 100 mm / min in accordance with DIN EN 14173, and the peel strength was evaluated over the middle 100 mm.

[0206] The peel strength (T-Peel) was also determined on a Kynar® metal. For this purpose, three 50 x 200 mm membrane strips (Sarnafil® S 327-15 EL, a soft PVC roofing membrane from Sika) were bonded to an aluminum sheet coated with polyvinylidene fluoride (Kynar® 500 from Arkema) over a surface area of ​​50 x 150 mm with an adhesive thickness of 2 mm without pretreatment. After curing for 7 days in a standard climate, the bonded membrane was pulled away from the concrete surface at an angle of 90° at a tensile speed of 100 mm / min in accordance with DIN EN 14173, and the peel strength was evaluated for the center 100 mm.

[0207] The results are shown in Table 3.

[0208]

[0209] Table 3: additional properties of examples 4 and / or 9.

[0210] "nb" stands for "not determined"

[0211] 1Bonding of a membrane for roof waterproofing made of soft PVC, from Sika, top side to bottom side, each without pretreatment

[0212] 2 Bonding a soft PVC membrane to concrete

[0213] 3 Bonding a soft PVC membrane to Kynar® metal

Claims

Patent claims: 1 . Use of an adhesive for bonding a membrane made of soft PVC to another substrate, characterized in that the adhesive - a resin component containing at least one epoxy resin and - containing a hardener component (a) at least one amine A1 having at least one dimethylamino group and at least one amine hydrogen, and (b) at least one further amine A2 having at least three amine hydrogens which is free from dimethylamino groups, wherein the hardener component has a content of amines A1 of 10 to 45% by weight, preferably 15 to 40% by weight, based on the sum of all liquid or dissolved constituents contained in the hardener component.

2. Use according to claim 1, characterized in that the resin component contains at least one aromatic epoxy liquid resin.

3. Use according to one of claims 1 or 2, characterized in that the amine A1 is selected from the group consisting of 2-dimethylaminoethylamine, 3-dimethylaminopropylamine, 4-dimethylaminobutylamine, 6-dimethylaminohexylamine, 2-(2-dimethylaminoethylamino)ethylamine, 2-(3-dimethylaminopropylamino)ethylamine, 3-(2-dimethylaminoethylamino)propylamine, 3-(3-dimethylaminopropylamino)propylamine, N-(3-dimethylaminopropyl)-1,3-bis-(aminomethyl)benzene, N-(3-dimethylaminopropyl)-1,4-bis(aminomethyl)benzene, 2,4,6-tris(4-dimethylamino-2-azabutyl)phenol, bis(2-dimethylaminoethyl)amine, bis(3-dimethylaminopropyl)amine and bis(6-dimethylaminohexyl)amine, in particular 3-(3-Dimethylaminopropylamino)propylamine.

4. Use according to one of claims 1 to 3, characterized in that the number of amine hydrogen equivalents from amines A1 based on the total number of amine hydrogen equivalents in the hardener component is in the range from 20 to 60%, preferably 25 to 55%. Use according to one of claims 1 to 4, characterized in that the amine A2 is selected from the group consisting of 1,5-diamino-2-methylpentane, 1,6-hexanediamine, 2,2(4),4-trimethyl-1,6-hexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, isophoronediamine, 1,3-bis(aminomethyl)benzene, 1,4-bis(aminomethyl)benzene, 2,5-bis(aminomethyl)furan, 2,5-bis(aminomethyl)tetrahydrofuran, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1 ,4-diaminocyclohexane, 2(4)-methyl-1,3-diaminocyclohexane, 2,5(2,6)-bis(aminomethyl)bicyclo[2.2.1]heptane, N-benzyl-1,2-ethanediamine, N-furfuryl-1,2-ethanediamine, N-tetrahydrofurfuryl-1,2-ethanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, N-(2-aminoethyl)-1,3-propanediamine, N,N'-bis(3-aminopropyl)ethylenediamine, bis(1,6-hexylene)triamine, phenalkamines, phenalkamides, polyamidoamines, amine-functional adducts of the above-mentioned amines with epoxides, and combinations of two or more of these amines. Use according to one of claims 1 to 5, characterized in that at least one amine A2-1 with an amine hydrogen equivalent weight of at least 80 g / eq, preferably at least 90 g / eq, is present as amine A2, in particular a phenalkamine or phenalkamide or an amine-functional adduct of N-benzyl-1,2-ethanediamine with at least one polyepoxide, in particular an aromatic epoxy liquid resin.Use according to claim 6, characterized in that amine A2 comprises a combination of at least one amine A2-1 and at least one amine A2-2 having two primary amino groups and four amine hydrogens, wherein amine A2-2 is preferably selected from isophoronediamine, 1,3-bis(aminomethyl)benzene, 1,3-bis(aminomethyl)cyclohexane, 1,2-diaminocyclohexane, and 2(4)-methyl-1,3-diaminocyclohexane. Use according to any one of claims 1 to 7, characterized in that the hardener component is a combination of 3-(3-dimethylaminopropylamino)propylamine, isophoronediamine, and at least one amine. from phenalkamines, phenalkamides and amine-functional adducts of N-benzyl-1,2-ethanediamine with at least one aromatic epoxy liquid resin.

9. Use according to one of claims 1 to 8, characterized in that the adhesive contains at least one further ingredient selected from thinners, fillers, accelerators and surface-active compounds.

10. Use according to one of claims 1 to 9, characterized in that the adhesive contains, based on 100 parts by weight of the sum of all components containing epoxy and amine groups, at most 30 parts by weight, in particular at most 25 parts by weight, preferably at most 20 parts by weight, particularly preferably at most 10 parts by weight, in particular at most 5 parts by weight, of thinner.

11. Use according to one of claims 1 to 10, characterized in that the adhesive contains 60 to 90% by weight, in particular 70 to 85% by weight, of mineral fillers, based on the total adhesive.

12. Use according to one of claims 1 to 11, characterized in that the adhesive, based on the total adhesive - 10 to 20% by weight of aromatic epoxy liquid resins, - 1 to 4% by weight of reactive diluents containing epoxy groups, - 3-(3-Dimethylaminopropylamino)propylamine, - Isophoronediamine, - at least one amine A2-1 with an amine hydrogen equivalent weight of at least 80 g / eq, - Contains 60 to 90% by weight of mineral fillers and possibly other ingredients.

13. Use according to one of claims 1 to 12, characterized in that the further substrate is selected from soft PVC, polyolefin, modified polyethylene, concrete, mortar, cement screed, fiber cement, brick, tile, natural stone, steel, metals coated with polyvinylidene fluoride and other plastics.

14. Adhesive composite obtained from the use according to one of claims 1 to 13.

15. Adhesive composite according to claim 14, characterized in that the value for the peel strength is in each case at least 1 N / mm, determined both after a) 7 days of curing in standard climate, and after b) 7 days of curing in standard climate followed by 28 days of storage at 70 °C and 100% relative humidity followed by 3 days of storage in standard climate, wherein in the case that the membrane made of soft PVC is bonded to another membrane, the determination of the peel strength is carried out in accordance with DIN EN 14173 at a tensile speed of 100 mm / min, and wherein in the case that the membrane made of soft PVC is bonded to a solid surface, the determination of the peel strength is carried out in accordance with DIN EN 14173 at a tensile speed of 100 mm / min with a tensile angle of 90° between the membrane made of soft PVC and the solid surface.

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