Multi-component epoxy resin and hardener component for it

Description

AREA OF INVENTION

[0001] The invention relates to a multi-component epoxy resin compound, in particular an epoxy resin compound for fastening purposes, and a hardener component for the epoxy resin compound, which contains at least one Mannich base as a hardener component for epoxies. TECHNICAL BACKGROUND

[0002] Multi-component mortars based on curable epoxy resins and amine hardeners have long been known and are used as adhesives, fillers for crack filling and chemical anchors for fastening structural elements such as anchor rods, reinforcing bars and screws in boreholes in various substrates.

[0003] The use of Mannich bases as components of hardeners for epoxy resins is described, among other things, in DE 10 2013 113465 A and WO 2005 / 090433 A. Mannich bases are typically used in combination with polyamines and optionally other components as hardener components of multi-component epoxy resin compounds for fastening applications. Compared to polyamines such as mXDA, Mannich bases are nonpolar substances and therefore have the advantage of not being easily washed out in wet substrates. A curable compound containing a Mannich base in the hardener component will therefore exhibit higher pull-out strengths after curing in a wet borehole than a comparable compound with a hardener based on low-molecular-weight polyamines.

[0004] WO 2014 / 067095 A describes a hardener component for epoxides containing a combination of phenalkamin and styrenized phenol or styrenized phenol novolak. Phenalkamin is a special, highly hydrophobic Mannich base obtained by reacting cashew nut shell liquid (CNSL), formaldehyde, and polyamines such as diethylenediamine.

[0005] From EP 0 351 365 A epoxy resin compositions with a latent hardener and an accelerator are known, wherein the accelerator is formed from a Mannich base based on a novolac.

[0006] EP 1 716 195 B1 describes a multi-component kit for a curable compound for fastening purposes comprising an epoxy resin component (a) which includes curable epoxies and a hardener component (b) which includes a Mannich base formulation.

[0007] The curing rate of epoxy resin-based mortars containing Mannich bases can be controlled to some extent by the phenol content of the Mannich base. However, the curing rate is primarily dependent on the amine present in the mixture. Common commercially available epoxy resins with Mannich base-based hardeners, such as RE 100 (Hilti, Schaan, Liechtenstein) or FIS EM 390 S (Fischer, Waldachtal, Germany), have a curing time of at least 12 hours at 20°C, where the curing time refers to the time after which the structure can be loaded. Accelerating the curing process is advisable to shorten waiting times before the next work step. SUMMARY OF THE INVENTION

[0008] The object of the invention is therefore to provide a hardener component for multi-component epoxy resin compounds which contains a Mannich base as a hardener and which is suitable for fastening purposes, wherein the multi-component compound should have a shortened curing time compared to conventional mortar compounds with a comparably high pull-out strength.

[0009] The problem underlying the invention is solved by providing a hardener component according to claim 1. Preferred embodiments of the hardener component according to the invention are specified in the dependent claims, which can optionally be combined with one another.

[0010] The invention further relates to a multi-component epoxy resin mass according to claim 10.

[0011] Preferred embodiments of the epoxy resin composition according to the invention are specified in the dependent claims, which can be optionally combined with one another. According to the invention, a hardener component for a multi-component epoxy resin composition is provided, comprising as hardener at least one Mannich base and an amine reactive towards epoxy groups, as well as at least one polyphenol from the group of novolac resins as an accelerator. wherein the Mannich base is obtainable by reacting a phenolic compound selected from the group consisting of phenol, styrolated phenol, catechol, resorcinol, hydroquinone, hydroxyhydroquinone, phloroglucinol, pyrogallol, o-cresol, m-cresol, p-cresol and bisphenols, with an aldehyde or an aldehyde precursor and an amine having at least two active hydrogen atoms bonded to a nitrogen atom in the molecule, and wherein the novolac resin is contained in the hardener component in a proportion of 8 to 25 wt.% wt.%, based on the organic fraction of the hardener component.

[0012] The use of the hardener component according to the invention in a multi-component epoxy resin compound for fastening purposes leads to a significant acceleration of the curing reaction. The cured compounds exhibit excellent pull-out strength in wet drill holes and can be loaded after a short time, within approximately 6 hours.

[0013] The organic content of the hardener component refers to the weight of the hardener component minus the weight of the inorganic components such as sand and / or cement.

[0014] According to a preferred embodiment of the hardener component according to the invention, the amine reactive towards epoxy resins is selected from the group consisting of aliphatic, alicyclic, araliphatic, and aromatic amines. The amine preferably has, on average, at least two reactive hydrogen atoms per molecule bonded to a nitrogen atom.

[0015] The amines that can be used as hardeners for epoxy resins in the hardener component are generally known to those skilled in the art. Preferably, the amine is a polyamine with at least two amino groups in the molecule. Particularly stable networks can be obtained when using polyamines in the hardener component.

[0016] For the purposes of this invention, the terms used here and in the following description have the following meanings: "aliphatic compounds" are acyclic or cyclic, saturated or unsaturated carbon compounds, excluding aromatic compounds; "alicyclic compounds" are compounds with a carbocyclic ring structure, excluding benzene derivatives or other aromatic systems; "araliphatic compounds" are aliphatic compounds with an aromatic backbone, so that in the case of a functionalized aliphatic compound, any existing functional group is attached to the aliphatic and not the aromatic part of the compound; "aromatic compounds" are compounds that follow the Hückel (4n+2) rule; and "Amine"are compounds derived from ammonia by replacing one, two, or three hydrogen atoms with hydrocarbon groups and exhibiting the general structures RNH 2 (primary amines), R 2 NH (secondary amines), and R 3 N (tertiary amines) (see: IUPAC Compendium of Chemical Terminology, 2nd ed. (the "Gold Book"), Compiled by AD McNaught and A. Wilkinson, Blackwell Scientific Publications, Oxford (1997)).

[0017] Examples of amines suitable as epoxy hardeners are given below, without limiting the scope of the invention: 1,2-Diaminoethane(ethylenediamine), 1,2-Propanediamine, 1,3-Propanediamine, 1,4-Diaminobutane, 2,2-Dimethyl-1,3-propanediamine (neopentanediamine), Diethylaminopropylamine (DEAPA), 2-Methyl-1,5-diaminopentane, 1,3-Diaminopentane, 2,2,4- or 2,4,4-Trimethyl-1,6-diaminohexane and mixtures thereof (TMD), 3-Aminomethyl-3,5,5-trimethylcyclohexane (Isophoronediamine, IPDA), 1,3-Bis(aminomethyl)cyclohexane (1,3-BAC), 1,2-Bis(aminomethyl)cyclohexane, Hexamethylenediamine (HMD). 1,2- and 1,4-Diaminocyclohexane (1,2-DACH and 1,4-DACH), Bis(4-aminocyclohexyl)methane (PACM), Bis(4-amino-3-methylcyclohexyl)methane (MACM), Bis-(4-Amino-3,5-dimethylcyclohexyl)methane, Diethylenetriamine (DETA), 4-Azaheptane-1,7-diamine, 1,11-Diamino-3,6,9-trioxundecane, 1,8-Diamino-3,6-dioxaoctane, 1,5-Diamino-methyl-3-azapentane, 1,10-Diamino-4,7-dioxadecane, Bis(3-aminopropyl)amine, 1,13-Diamino-4,710-trioxatridecan, 4-Aminomethyl-1, 8-diaminooctan, 2-Butyl-2-ethyl-1, 5-diaminopentan, N, N-Bis-(3-aminopropyl)methylamin, Triethylentetramin (TETA), Tetraethylenpentamin (TEPA), Pentaethylenhexamin (PEHA), 1,3-Benzoldimethanamin (m-Xylylendiamin, mXDA), 1,4-Benzoldimethanamin (p-Xylylendiamin, pXDA), 5-(Aminomethyl)bicyclo[[2.2.1]hept-2-yl]methylamin (NBDA, Norbornandiamin), Dimethyldipropylentriamin, Dimethylaminopropyl-aminopropylamin (DMAPAPA), Diethylmethylbenzoldiamin (DETDA), 4,4'-Diaminodiphenylsulfon (Dapson), gemischte polycyclische Amine (MPCA) (z.B. Ancamine 2168), Dimethyldiaminodicyclohexylmethan (Laromin C260), 2,2-Bis(4-aminocyclohexyl)propan, (3(4),8(9)Bis(aminomethyldicyclo[5.2.1.0 2,6< ]decan (Isomerengemisch, tricyclischer primärer Amine; TCD-Diamin), 1,8-Diamino-p-menthan, N-Aminoethyl-piperazin (N-AEP), N-3-(Aminopropylpiperazin), Piperazin, 4-Methylcyclohexyl-diamin (mCDA).,

[0018] Preferred hardeners in the hardener component according to the invention are polyamines, such as 2-methylpentanediamine (DYTEK A), 1,2- and 1,4-diaminocyclohexane (1,2-DACH and 1,4-DACH), 3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), 1,3-benzenedimethanamine (m-xylylenediamine, mXDA), 1,4-benzenedimethanamine (p-xylylenediamine, PXDA), 1,6-diamino-2,2,4-trimethylhexane (TMD), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), bis(4-aminocyclohexyl)methane (PACM), bis(4-amino-3-methylcyclohexyl)methane (MACM). 5-(Aminomethyl)bicyclo[[2.2.1]hept-2-yl]methylamine (NBDA, norbornanediamine), 1,3-bisaminomethylcyclohexane (1,3-BAC), (3(4),8(9)Bis(aminomethyl)dicyclo[5. 2.1.0 2,6< ]decane (mixture of isomers, tricyclic primary amines; TCD-diamine), 1,14-diamino-4, 11-dioxatetradecane, dipropylenetriamine, 2-methyl-1, 5-pentanediamine, N, N'-dicyclohexyl-1, 6-hexanediamine, N, N'-dimethyl-1, 3-diaminopropane, N, N'-diethyl-1, 3-diaminopropane, N, N-dimethyl-1, 3-diaminopropane, secondary polyoxypropylenedi- and triamines, 2,5-diamino-2, 5-dimethylhexane, bis(amino-methyl)tricyclopentadiene, dipentylamine, N-(aminoethyl)piperazine (N-AEP), 4-Methylcyclohexyldiamine (mCDA).

[0019] The amines can be used individually or in a mixture of two or more of the mentioned amines.

[0020] The Mannich bases used in the hardener component according to the invention in combination with the amines described above are the reaction products of an amine and an aldehyde with a phenolic compound selected from the group consisting of phenol, catechol, resorcinol, hydroquinone, hydroxyhydroquinone, phloroglucinol, pyrogallol, o-cresol, m-cresol, p-cresol, bisphenols such as bisphenol F or bisphenol A, and combinations thereof.

[0021] To form the Mannich base, the phenolic compound is reacted with a preferably primary or secondary amine and an aldehyde or an aldehyde precursor, which decomposes to yield an aldehyde. The aldehyde or aldehyde precursor can advantageously be added to the reaction mixture as an aqueous solution, particularly at an elevated temperature of about 50°C to 90°C, and reacted with the amine and the phenolic compound.

[0022] The phenolic compound preferably used to form the Mannich base is phenol or a styrozyte phenol, resorcinol, styrozyte resorcinol, bisphenol A or bisphenol F, particularly preferably phenol or a styrozyte phenol, styrozyte resorcinol or bisphenol A.

[0023] The aldehyde used to form the Mannich base is preferably an aliphatic aldehyde, particularly preferably formaldehyde. Trioxane or paraformaldehyde, which decompose to formaldehyde upon heating in the presence of water, can preferably be used as the aldehyde precursor.

[0024] The amine used for the reaction with the aldehyde and the phenolic compound to form the Mannich base is preferably one of the above-mentioned epoxide-reactive amines, and preferably a polyamine. Preferably, the amine is present in excess, such that the Mannich base contains free amino groups.

[0025] The novolac resin corresponds to the following formula (II): wherein R1 represents H; R2 represents a C1-C15 alkyl group, preferably a methyl or tert-butyl group; m is 0, 1, or 2, and preferably 1; and n is 1 to 15. Most preferably, the novolac resin corresponds to the above formula (II), wherein R2 represents CH3 and m is 1 or 2, or R2 represents tert-butyl or a C1-C15 alkyl group and m is 1, and wherein n is 1 to 15.

[0026] The hardener component according to the invention contains the novolac resin in a proportion of 8 to 25 wt.%, based on the weight of the organic component of the hardener component.

[0027] The amine, which is reactive towards epoxy resins, is preferably present in the hardener component according to the invention in a proportion of 20 to 80 wt.%, particularly preferably 35 to 60 wt.%. Furthermore, the hardener component contains the at least one Mannich base preferably in a proportion of 10 to 70 wt.%, particularly preferably 30 to 65 wt.%, in each case based on the weight of the organic portion of the hardener component.

[0028] In another embodiment, the hardener component comprises further additives from the group of solvents, further phenolic accelerators, co-accelerators, adhesion promoters and inorganic fillers.

[0029] Non-reactive diluents (solvents) may preferably be present in an amount of up to 30% by weight, based on the total weight of the hardener component, for example, from 1% to 20% by weight. Examples of suitable solvents are low alkyl ketones such as acetone, di-low alkyl low alkanoylamides such as dimethylacetamide, low alkylbenzenes such as xylenes or toluene, phthalic acid esters, or paraffins. Preferably, the hardener component is solvent-free.

[0030] The other phenolic accelerators are preferably selected from salicylic acid, styrolyzed phenols and cardanol, as well as mixtures thereof. These can be present in a proportion of 0 to 10 wt% in the hardener component, based on the total weight of the hardener component.

[0031] Examples of co-accelerators include benzyl alcohol, tertiary amines, imidazoles or tertiary aminophenols, organophosphines, Lewis bases or acids such as phosphate esters, or mixtures of two or more of these. The co-accelerators may also be present in the epoxy resin component (A), provided they are compatible with the epoxy resins.

[0032] Preferably, the co-accelerators are included in the hardener composition in a weight fraction of 0.001 to 5 wt.%, based on the total weight of the hardener composition.

[0033] Examples of suitable co-accelerators include, in particular, tris-2,4,6-dimethylaminomethylphenol, 2,4,6-tris(dimethylamino)phenol, and bis[(dimethylamino)methyl]phenol. A suitable co-accelerator mixture contains 2,4,6-tris(dimethylaminomethyl)phenol and bis(dimethylaminomethyl)phenol. Such mixtures are commercially available, for example, as Ancamine® < K54 (AirProducts, Belgium).

[0034] The use of a bonding agent improves the cross-linking of the borehole wall with the mortar, thus increasing adhesion in the hardened state. Suitable bonding agents are selected from the group of silanes functionalized with further reactive organic groups, such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminoethyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropylmethyldimethoxysilane. Particularly preferred as adhesion promoters are 3-Aminopropyl-trimethoxysilane (AMMO), 3-Aminopropyltriethoxysilane (AMEO), 2-Aminoethyl-3-aminopropyl-trimethoxysilane (DAMO) and Trimethoxysilylpropyldiethylenetetramine (TRIAMO).

[0035] The adhesion promoter can be present in an amount of up to 10 wt.%, preferably 0.1 to 5 wt.%, based on the total weight of the hardener component.

[0036] Inorganic fillers are used, in particular cements such as Portland cement or aluminate cement, as well as other hydraulically setting inorganic materials, quartz, glass, corundum, porcelain, earthenware, barite, fluorite, gypsum, talc, and / or chalk, and mixtures thereof. Thickeners such as pyrogenic silica can also be used as inorganic fillers. The inorganic fillers can be added in the form of sands, powders, or shaped particles, preferably in the form of fibers or spheres. The fillers can be present in one or all components of the multi-component mortar.

[0037] The proportion of fillers is preferably 0 to 75 wt.%, for example 10 to 75 wt.%, more preferably 15 to 75 wt.%, and more preferably 20 to 50 wt.%, and even more preferably 25 to 40 wt.%, based on the total weight of the hardener component. The present invention further relates to a multi-component epoxy resin composition, preferably a two-component epoxy resin composition, comprising an epoxy resin component (A) containing at least one curable epoxy resin and at least one hardener component (B) with the composition described above.

[0038] The multi-component epoxy resin compound is primarily used for construction purposes. The term "for construction purposes" means the bonding of concrete / concrete, steel / concrete, or steel / steel, or any of the aforementioned materials, to other mineral materials; the structural reinforcement of components made of concrete, masonry, and other mineral materials; the reinforcement applications with fiber-reinforced polymers of building structures; the chemical bonding to surfaces made of concrete, steel, or other mineral materials, in particular the chemical bonding of structural elements and anchors such as anchor rods, anchor bolts, (threaded) rods, (threaded) sleeves, reinforcing bars, screws, and the like, in boreholes in various substrates such as (reinforced) concrete, masonry, other mineral materials, metals (e.g., steel), ceramics, plastics, glass, and wood.The epoxy resin masses according to the invention are particularly preferred for the chemical fastening of anchoring elements.

[0039] A variety of compounds known to those skilled in the art and commercially available for this purpose are suitable as the curable epoxy in the epoxy resin component (A). These compounds contain, on average, more than one epoxy group, preferably two epoxy groups, per molecule. These epoxy resins can be saturated or unsaturated, as well as aliphatic, alicyclic, aromatic, or heterocyclic, and may also contain hydroxyl groups. Furthermore, they can contain substituents that do not cause interfering side reactions under the mixing or reaction conditions, such as alkyl or aryl substituents, ether groups, and the like. Trimeric and tetrameric epoxides are also suitable within the scope of the invention.

[0040] Preferably, the epoxy resins are glycidyl ethers derived from polyhydric alcohols, in particular from polyhydric phenols such as bisphenols and novolacs, especially those with an average glycidyl group functionality of 1.5 or greater, in particular of 2 or greater, for example of 2 to 10.

[0041] The epoxy resins can have an epoxy equivalent weight (EEW) of 120 to 2000 g / EQ, preferably 140 to 400, particularly 155 to 195, for example 165 to 185. Mixtures of several epoxy resins can also be used.

[0042] Examples of polyhydric phenols used in the production of epoxy resins are resorcinol, hydroquinone, 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A), isomer mixtures of dihydroxyphenylmethane (bisphenol F), tetrabromo-bisphenol A, novolacs, 4,4'-dihydroxyphenylcyclohexane and 4,4'-dihydroxy-3,3'-dimethyldiphenylpropane.

[0043] Preferably, the epoxy resin is a diglycidyl ether of bisphenol A or bisphenol F, or a mixture thereof. Particularly preferred are liquid diglycidyl ethers based on bisphenol A and / or F with an EEW of 180 to 190 g / EQ.

[0044] Other examples include hexanediol diglycidyl ethers, trimethylolpropane triglycidyl ethers, bisphenol-A epichlorohydrin resins and / or bisphenol-F epichlorohydrin resins, for example with an average molecular weight of Mn ≤ 2000 g / mol.

[0045] The proportion of epoxy resin is >0 to 100 wt.%, preferably 10 to 70 wt.% and particularly preferably 30 to 60 wt.%, based on the total weight of the resin component (A).

[0046] In addition to the epoxy resins, the epoxy resin component (A) may optionally contain at least one reactive diluent. Glycidyl ethers of aliphatic, alicyclic, or aromatic mono- or, in particular, polyalcohols are used as reactive diluents, which have a lower viscosity than epoxides containing aromatic groups. Examples of reactive diluents are monoglycidyl ethers, e.g., o-cresyl glycidyl ethers, and glycidyl ethers with an epoxide functionality of at least 2, such as 1,4-butanediol diglycidyl ether (BDDGE), cyclohexanedimethylethanol diglycidyl ether, and hexanediol diglycidyl ether, as well as triglycidyl or higher glycidyl ethers, such as glycerol triglycidyl ether, pentaerythritol triglycidyl ether, or trimethylolpropane triglycidyl ether (TMPTGE).Mixtures of two or more of these reactive diluents can also be used, preferably mixtures containing triglycidyl ethers, particularly preferably as a mixture of 1,4-butanediol diglycidyl ether (BDDGE) and trimethylolpropane triglycidyl ether (TMPTGE).

[0047] The reactive diluents are preferably present in an amount of 0 to 60 wt.%, in particular 1 to 20 wt.%, based on the total weight of the resin component (A).

[0048] The proportion of the epoxy component (A) in the total mass of the multi-component mortar mass is preferably 5 to 90 wt.%, in particular 20 to 80 wt.%, 30 to 70 wt.% or 40 to 60 wt.%.

[0049] Suitable epoxy resins and reactive diluents can also be found in the standard work by Michael Dornbusch, Ulrich Christ and Rob Rasing, "Epoxy Resins", Vincentz Network GmbH & Co KG (2015), ISBN 13: 9783866308770. These compounds are referenced here.

[0050] Furthermore, the epoxy resin component (A) may contain common additives, in particular adhesion promoters and fillers, as already described for the hardener composition.

[0051] The adhesion promoter may be present in an amount of up to 10 wt.%, preferably 0.1 to 5 wt.%, based on the total weight of the epoxy resin component (A).

[0052] The proportion of fillers is preferably 0 to 75 wt.%, for example 10 to 75 wt.%, preferably 15 to 75 wt.% and further preferably 20 to 50 wt.%, even more preferably 25 to 40 wt.%, based on the total weight of the epoxy resin component (A).

[0053] Other conceivable additives to the multi-component epoxy resin mass include thixotropic agents such as, if necessary, organically post-treated pyrogenic silica, bentonites, alkyl and methyl celluloses and castor oil derivatives, plasticizers such as phthalic acid or sebacic acid esters, stabilizers, antistatic agents, thickeners, flexibilizers, curing catalysts, rheology aids, wetting agents, coloring additives such as dyes or pigments, for example for different coloring of the components for better control of their mixing, as well as wetting agents, phlegmatizing agents, dispersing agents and other control agents for the reaction rate, or mixtures of two or more of them.

[0054] The multi-component epoxy resin mass is preferably in cartridges, cartridges or foil bags, which are characterized in that they comprise two or more separate chambers in which the epoxy resin component (A) and the hardener component (B) of the mortar mass are arranged separately from each other in a reaction-inhibiting manner.

[0055] For intended use, the epoxy resin component (A) and the hardener component (B) are emptied from their separate chambers and mixed in a suitable device, such as a static mixer or a dissolver. The mixture of epoxy resin component (A) and hardener component (B) is then injected into the previously cleaned borehole using a known injection device. The component to be fixed is then inserted into the mortar mixture and adjusted. The reactive components of the hardener component (B) react with the epoxides of the resin component (A) via polyaddition, causing the epoxy resin mixture to cure under ambient conditions within a desired time, preferably within a few minutes or hours.

[0056] Components A and B are preferably mixed in a ratio that results in a balanced stoichiometry according to the EEW and AHEW values.

[0057] The AHEW value (amine hydrogen equivalent weight,The H equivalent indicates the amount of the hardener component containing 1 mol of reactive H. The determination of the AHEW is carried out in a manner known to those skilled in the art by formulating the reaction mixture from the known H equivalents of the reactants and raw materials used, from which they are calculated.

[0058] The calculation of the AHEW is explained below using the example of meta-xylylenediamine (MW = 136 g / mol, functionality = 4 eq / mol): AHEW = M W Funkzionalit ä t = 136 4 g eq = 34 g eq

[0059] The EEW (epoxide equivalent weight, Epoxy equivalent values ​​(EEV) are usually specified by the manufacturers of the respective epoxy resin components used, or they are calculated using established methods. EEV indicates the amount in grams of epoxy resin that contains 1 mole of epoxy groups.

[0060] The AHEW (Axis High Hydroxide Value) was experimentally determined by measuring the glass transition temperature (Tg) of a mixture of epoxy resin (with a known EEW) and an amine component. The glass transition temperatures of epoxy resin / amine mixtures with different ratios were determined. The sample was cooled from 21°C to -70°C at a heating rate of -20 K / min, heated to 250°C in a first heating cycle (heating rate 10 K / min), then cooled back to -70°C (heating rate -20 K / min), and finally heated to 200°C (20 K / min). The mixture with the highest glass transition temperature in the second heating cycle ("Tg 2") has the optimal ratio of epoxy resin to amine. The AHEW value can be calculated from the known EEW and the optimal epoxy resin / amine ratio.

[0061] Example: EEW = 158 g / mol

[0062] Amine / epoxy resin mixture with maximum Tg 2: 1 g amine with 4.65 g epoxy resin AHEW = 1 4 , 65 ⋅ 158 = 34 g eq DETAILED DESCRIPTION OF EXAMPLES OF EXECUTION

[0063] Further advantages of the invention will become apparent from the following description of preferred embodiments, which, however, are in no way to be understood as limiting. Production of the Mannich base General manufacturing instructions

[0064] The preparation of Mannich bases can be carried out according to known procedures, as described below: 2 mol of one or more amines are placed in a 250 ml three-necked flask equipped with a thermometer, a dropping funnel, and a stirring device. With stirring, the amine is mixed with about 1 mol of phenol or styrenized phenol. The mixture is heated to about 80°C. Then, with vigorous stirring, about 0.7 mol of formaldehyde, as a 37% formaldehyde solution in water, is added dropwise over about 45 minutes. After the addition of formaldehyde, the reaction mixture is further heated to about 105°C and held at this temperature for about 120 minutes. Water is then distilled off under increasing vacuum at a suitable temperature (e.g., about 110°C). As soon as the pressure is sufficiently reduced (e.g.,(to about 50 mbar), the temperature can be further increased to about 130°C and then held at this temperature for some time, for example about 60 min, to remove the remaining water from the reaction mixture. Synthesis of Mannich base MBS2

[0065] In a 1 L three-necked flask equipped with a KPG stirrer and internal thermometer, 220 g (0.91 mol) of Novares LS 500 (styrenized phenol from Rütgers Novares GmbH, Germany; average molar mass 243 g / mol) are mixed with 190.4 g (221 ml, corresponding to 1.64 mol; 1.8 eq) of 1,5-diamino-2-methylpentane, and the reaction mixture is heated to 80°C (internal temperature). Then, 115 ml (1.46 mol; 1.6 eq) of formaldehyde (37%; 10–15% MeOH as stabilizer, d = 1.09 g / cm³) are carefully added dropwise. During the addition of formaldehyde, the temperature of the reaction mixture should not exceed 90°C (exothermic reaction). After the formaldehyde solution has been completely added, the reaction mixture is stirred for another 45 minutes at 85 to 90°C. The mixture is then heated to 100°C and held at this temperature for 1 hour. Finally, at approximately 140°C, the resulting water and excess formaldehyde are removed by a strong stream of nitrogen over a period of 3 hours.The product solidifies upon cooling to room temperature.

[0066] The yield of Mannich base is 456 g of crude product. Synthesis of Mannich base MBS1

[0067] In a 2 L three-necked flask equipped with a KPG stirrer and internal thermometer, 504 g (2.07 mol) of Novares LS 500 are mixed with 601 mL (4.6 mol; 2.2 eq; d = 1.032 g / cm³) of m-xylylenediamine, and the reaction mixture is heated to 80°C (internal temperature). Then, 327 mL (4.15 mol) of formaldehyde (37%; 10–15% MeOH as stabilizer, d = 1.09 g / cm³) are added dropwise over approximately 1.5 h. During the addition of formaldehyde, the temperature of the reaction mixture should not exceed 90°C (exothermic reaction). After complete addition of the formaldehyde solution, the reaction mixture is stirred for a further 2 h at an internal temperature of 85–95°C. The mixture is then heated to 100°C and held at this temperature for approximately one hour. Afterwards, at approximately 140°C, the resulting water and excess formaldehyde are blown off in a strong stream of nitrogen for about three hours. The product solidifies upon cooling to room temperature.

[0068] The yield of Mannich base is 1.13 kg of crude product. Examples 1 to 4 and comparative examples 1 and 2 Determination of reaction kinetics by temperature measurement

[0069] Hardener components with varying proportions of novolac resin and different novolac resins were produced to monitor the curing of the mixtures of hardener component and epoxy resin component via the temperature profile of the curing reaction. It was found that the temperature profile of the curing reaction can be adjusted over a wide range by varying the novolac resin and its proportion in the hardener component.

[0070] The quantities specified in the following examples refer to weight percent (wt%).

[0071] To produce epoxy resin component A, the ingredients listed in Table 1 below were mixed in a speed mixer. The epoxy equivalent (EEW) of the mixture was 158 g / EQ.

[0072] Furthermore, various hardener components B were prepared with the compositions specified in Table 2 below. The Mannich base MBS2, obtained according to the synthesis procedure described above, and m-xylylenediamine (mXDA; manufacturer: Aldrich, Germany) were used as amine hardeners. The phenol novolac resin available under the trade name Phenolite TD-2093 Y from DIC Europe, Germany, was used as an accelerator. Table 1: Composition of epoxy resin component A Material function % by weight Trade name Manufacturer country Bisphenol A-based epoxy resin epoxy resin 52 DER 330 Dow Europe CH Bisphenol F-based epoxy resin epoxy resin 28 DER 354 Dow Europe CH 1,4-Butanediol diglycidyl ether Reactive diluents 10 Polypox R3 Dow Europe CH Trimethylol propane triglycidyl ether Reactive diluents 10 Araldite DY-T Huntsman BE Table 2: Composition of hardener component B MBS2 mXDA Phenol novolak AHEW Weight ratio of component A : B Comparative example 1 20 80 0 140,77 3,88 Comparative example 2 50 50 0 58,12 2,72 Example 1 50 48 2 60,18 2,63 Example 2 50 45 5 63,55 2,49 Example 3 20 65 15 49,71 3,18 Example 4 10 68 22 48,78 3,24

[0073] Epoxy component A was mixed with each of the hardener components B in the weight ratio specified in Table 2 using a speed mixer. The mixture was then transferred to a 20 ml round-top glass container. A temperature sensor was placed in the center of the container, and the temperature change of the mixture was recorded (device: Yokogawa DAQ station, model: DX1006-3-4-2). The temperature change over time serves as a measure of the curing of the mixture. If the curing process accelerates, the temperature maximum is reached at shorter intervals. Furthermore, in most cases, a higher temperature maximum also occurs. The time t + 10 K after which a temperature increase of 10 K has occurred, the reached temperature maximum Tmax, and the time tTmax after which the temperature maximum was reached were measured.

[0074] The results of the temperature changes obtained for the various hardener components B during the curing reaction are given in Table 3 below. Table 3: Temperature profile during curing t +10K [h:min:sec] T max [°C] t Tmax [h:min:sec] Comparative example 1 - 29,1 04:26:57 Comparative example 2 1:26:45 129,6 02:39:55 Example 1 1:13:51 138,3 01:39:28 Example 2 00:53:25 151,9 01:15:01 Example 3 00:35:40 150,1 01:09:33 Example 4 00:19:24 189,3 00:39:27

[0075] The temperature profiles of the curing reaction obtained for the various hardener components B show that the composition of comparison example 1 does not achieve a temperature increase of 10 K. The maximum temperature measured after approximately 4.5 hours is only 29°C. Hardener component B from comparison example 2 results in a temperature increase of 10 K after about 1.5 hours, and the maximum temperature of 130°C is measured after approximately 2.65 hours.

[0076] The hardener components B according to examples 1 to 4 reach a temperature increase of 10 K after 19 to 74 minutes, with maximum temperatures of 138 to 190°C. These maximum temperatures are significantly higher than those of the comparison examples. In particular, the maximum temperatures are reached after a time of between 39 minutes and 1.65 hours, at least one hour earlier than in comparison example 2. The addition of the novolak resin therefore leads to a significant acceleration of the reaction and thus the curing process. This acceleration depends on the concentration of the phenol novolak, with higher concentrations resulting in a significantly faster curing, and also on the type of phenol novolak used. Examples 5 and 6, and comparative example 3 Determination of reaction kinetics by temperature measurement

[0077] To produce epoxy resin component A, the ingredients listed in Table 1 above were mixed in a speed mixer. The epoxy equivalent of the mixture was 158 g / EQ.

[0078] Furthermore, various hardener components B with the compositions specified in Table 4 below were prepared. The amine hardeners used were a Mannich base based on bisphenol A and the amine mXDA, available under the trade name Epikure 132 from Momentive Specialty Chemicals, Netherlands, as well as mXDA (manufacturer: Aldrich, Germany) and 1,3-cyclohexanediemethanamine (1,3-BAC) from Itochu, Germany. The accelerator used was a phenol novolac resin available under the trade name Phenolite TD-2131 from DIC Europe, Germany. Table 4: Composition of hardener component B Epicurus 132 mXDA 1,3-BAC Phenol novolak AHEW Weight ratio of component A : B Example 5 50 38 0 12 48,50 3,26 Example 6 50 0 38 12 63,55 2,49 Comparative example 3 100 0 0 0 53,0 2,98

[0079] Epoxy component A was mixed with each of the hardener components B in the weight ratio specified in Table 2. The mixture was filled into a 20 ml round-topped glass container. A temperature sensor was placed in the center of the container, and the temperature change of the mixture was recorded (device: Yokogawa, DAQ station, model: DX1006-3-4-2). The temperature change over time serves as a measure of the curing of the mixture. If curing is accelerated, the temperature maximum is shifted to shorter times. Furthermore, in most cases, a higher temperature maximum also occurs. The time t + 10 K after which a temperature increase of 10 K has occurred, the reached temperature maximum Tmax, and the time hTmax after which the temperature maximum was reached are measured.

[0080] The results of the temperature changes obtained for the various hardener components B during the curing reaction are given in Table 5 below. Table 5: Temperature change during curing t +10K [h:min:sec] T max [°C] t Tmax [h:min:sec] Example 5 00:22:49 183,8 00:48:03 Example 6 00:13:36 200,0 00:36:18 Comparative example 3 00:33:30 80,0 01:27:06

[0081] Again, the masses with the hardener components B according to the invention, as shown in Examples 5 and 6, exhibit faster curing behavior than the comparative example 3. Both the temperature increase of 10 K and the time after which the maximum temperature is reached are shorter than in the comparative example. The maximum temperature reached for the hardener components B of Examples 5 and 6, at 184°C and 200°C respectively, is also significantly higher than the maximum temperature of 80°C reached for the hardener component of comparative example 3. Examples 7 to 10 and comparative examples 4 to 7 Determination of the failure load after different curing times

[0082] To produce epoxy resin component A, the ingredients listed in Table 6 below were mixed in a speed mixer. The epoxy equivalent (EEW) of the mixture was 257 g / EQ. Table 6: Composition of epoxy resin component A ingredient function wt.% Trade name Manufacturer 3-Glycidyloxy-propyltrimethoxysilane Liability mediator 2,6 Dynasylan GLYMO Evonik Industries, DE Bisphenol A-based epoxy resin epoxy resin 31,1 DER 330 Dow Europe, CH Bisphenol F-based epoxy resin epoxy resin 16,6 DER 354 Dow Europe, CH 1,4-Butanediol diglycidyl ether Reactive diluents 6 Polypox R3 Dow Europe, CH Trimethylolpropane triglycidyl ether Reactive diluents 6 Araldite DY-T Huntsman, BE quartz filler 35 Millisil W12 Quartz Works Frechen, DE Silica , thickener 2,7 Cab-O-Sil TS-720 Cabot Rheinfelden, DE

[0083] The components listed in Table 7 below were used to produce the various hardener components B and mixed together in the composition shown in Table 8 below. The mXDA-resorcinol-based Mannich base was synthesized analogously to the synthesis procedure in EP 0 645 408. The mXDA-resorcinol-based Mannich base was used as the hardener in solution with mXDA. The free mXDA content was 60%. Table 7: Components of the hardener components B ingredient function Trade name Manufacturer country Mannich Base MBS2 Harder Mannich Base MBS1B Harder mXDA-Bisphenol A-based Mannich base in mXDA Harder Epicurus 132 Momentive Specialty Chemicals NL mXDA-resorcinol-based Mannich base, dissolved in mXDA Harder Novolak accelerator Phenolite TD-2131 DIC Europe DE 4,4'-Dihydroxydiphenylmethan accelerator Bisphenol F TCI Europe BE 2,4'-Dihydroxydiphenylmethan accelerator 2,4-Bisphenol F TCI Europe BE 1,3-Cyclohexanedimethanamine Harder 1,3-BAC Itochu Germany DE m-Xylylenediamine Harder mXDA Itochu Germany DE 3-Aminopropyl triethoxysilane Liability mediator Dynasylan AMEO Evonik Degussa DE 2,4,6-Tris(dimethylaminomethyl)phenol, bis[(dimethylamino)methyl]phenol accelerator Ancamine K54 Air Products NL quartz filler Millisil W12 Frechen Quartz Works DE Silica Thickener Cab-O-Sil TS-720 Cabot Rheinfelden DE Table 8: Composition of hardener components B ingredient Example 7 Comparative example 4 Example 8 Comparative example 5 MBS2 26,3 26,3 MBS1B (MBS1, 75% solved in mXDA) 35,2 35,2 Novolak 6,3 6,3 1,3-BAC 26,1 32,4 mXDA 17,1 23,4 3-Aminopropyl triethoxysilane 1,9 1,9 1,9 1,9 Ancamine K54 1,9 1,9 1,9 1,9 quartz 35 35 35,1 35,1 Silica 2,5 2,5 2,5 2,5 AHEW 113 g / EQ 94 g / EQ 92 g / EQ 78 g / EQ Table 8 (continued): Composition of hardener component B Material Example 9 Comparison example 6 Example 10 Comparative example 7 Epicurus 132 47,4 54 mXDA-resorcinol-based Mannich base in mXDA 49,3 49,3 Novolak 6,4 6,7 mXDA 3,9 3,4 6,7 3-Aminopropyl triethoxysilane 1,9 2 2 2 Ancamine K54 1,9 2 2 2 quartz 35,9 36 37,3 37,3 Silica 2,6 2,6 2,7 2,7 AHEW 97 g / EQ 88 g / EQ 96 g / EQ 81 g / EQ Table 8 (continued): Composition of hardener component B Material Example 11 Example 12 Example 13 I Example 14 Epicurus 132 - 49,0 49,0 50,8 mXDA-resorcinol-based Mannich base in mXDA 49,3 - - - 4,4'-Dihydroxydiphenylmethan 6,7 5,0 2,5 1.5 II< 2,4'-Dihydroxydiphenylmethan - - 2,5 1,6 mXDA - 3,4 3,4 3,5 3-Aminopropyl triethoxysilane 2,0 2,0 2,0 2,0 Ancamine K54 2,0 2,0 2,0 2,0 quartz 37,3 36,0 36,0 36,0 Silica 2,7 2,6 2,6 2,6 AHEW 96 g / EQ 96 g / EQ 96 g / EQ 93 g / EQ

[0084] Examples 11-14 are comparative examples. To produce curable epoxy resin compounds, components A and B are mixed in a speed mixer in a ratio that results in a balanced stoichiometry according to the EEW and AHEW values. The mixture is filled into a 1K cartridge, ensuring it is as bubble-free as possible, and immediately injected into the borehole.

[0085] For pull-out tests with M12 threaded rods, the following procedure is performed according to ETAG 001 PART 5: First, boreholes (14 mm diameter; 72 mm deep) are drilled into a horizontally positioned concrete test specimen (concrete type C20 / 25) using a hammer drill. The boreholes are cleaned with compressed air (2 x 6 bar), a wire brush (2 x), and then again with compressed air (2 x 6 bar). Next, the boreholes are filled to two-thirds capacity from the bottom with the curable epoxy resin for fastening purposes being tested. A threaded rod is pressed into each borehole by hand. Excess mortar is removed with a spatula. After the time specified for the respective test, the threaded rod is pulled out until failure, and the failure load is measured. Table 9: Failure loads in N / mm² after predetermined curing time: 3 h 6 h 24 h Composition of the organic component of the hardener Example 7 0,5 28,2 37,3 45% MBS2 + 12% novolak + 43%1,3-BAC Comparative example 4 < 0,4 2,4 37,8 45% MBS2 + 55% 1,3-BAC Example 8 1,2* 21,3 38,2 45% MBS1B + 12% novolak + 43% mXDA Comparative example 5 < 0,4 0,9 38,8 45% MBS1B + 55% mXDA Example 9 4 33,8 39,1 83% Epicure 132 + 12% Novolak + 5% mXDA Comparative example 6 < 0,4 26,1 39,0 94% Epicurean 132 + 6% mXDA Example 10 1,8 29,2 37,1 88% mXDA-resorcinol-based Mannich base in mXDA + 12% novolak Comparative example 7 < 0,4 23,5 38,9 88% mXDA-resorcinol-based Mannich base in mXDA + 12% mXDA Example 11 4,5 34,0 35,6 88% mXDA-resorcinol-based Mannich base in mXDA + 12% Bisphenol F Example 12 1,5 30,9 32,6 92% Epicure 132 + 8 Bisphenol F Example 13 1,2 31,4 37,8 92% Epicure 132 + 8% Bisphenol F isomer mixture Example 14 <0,4 29,8 38,3 95% Epicure 132 + 5% Bisphenol F isomer mixture *after 4.5 hours

[0086] The epoxy resin compositions according to the invention with hardener components according to the

[0087] Examples 7 to 10 show a significantly faster curing time than the epoxy resin compounds with the hardener components of comparative examples 4 to 7. The mortar compounds for fastening purposes produced with the hardener components according to the invention are load-bearing after only 6 hours. This allows waiting times before the next work step to be considerably reduced and subsequent work to be carried out much earlier.

Claims

1. Hardener component for accelerating the curing reaction of a multicomponent epoxy resin composition, which comprises as the hardener at least one Mannich base and an amine reactive to epoxy groups, and at least one polyphenol from the group of novolak resins as the accelerator, wherein the Mannich base is obtained by reacting a phenolic compound, selected from the group consisting of phenol, styrenated phenol, pyrocatechol, resorcinol, hydroquinone, hydroxyhydroquinone, phloroglucinol, pyrogallol, o-cresol, m-cresol, p-cresol, and bisphenols, with an aldehyde or an aldehyde precursor and an amine having at least two active hydrogen atoms in the molecule which are bonded to a nitrogen atom, wherein the novolak resin is contained in the hardener component in a proportion of from 8 to 25 wt.%, based on the organic proportions of the hardener component, and wherein the novolak resin corresponds to the following formula: where R1 represents H; R2 represents a C1-C15 alkyl; m is 0, 1 or 2; and n is 1 to 15.

2. Hardener component according to claim 1, characterized in that the amine that is reactive to epoxy resins is an amine selected from the group consisting of aliphatic, alicyclic, araliphatic, and aromatic amines, the amine having on average at least two reactive hydrogen atoms per molecule which are bonded to a nitrogen atom, and preferably being a polyamine having at least two amino groups in the molecule.

3. Hardener component according to claim 1 or 2, characterized in that the phenolic compound is selected from phenol and styrenated phenol, and mixtures thereof.

4. Hardener component according to any of the preceding claims, characterized in that the aldehyde is an aliphatic aldehyde, preferably formaldehyde, and in that the aldehyde precursor comprises trioxane or paraformaldehyde.

5. Hardener component according to any of the preceding claims, characterized in that the Mannich base is formed using at least one amine that is reactive to epoxide, preferably using a polyamine.

6. Hardener component according to any of the preceding claims, characterized in that R2 represents -CH3 and m is 1 or 2, or R2 represents tert-Butyl or a C1-C15 alkyl and m is 1.

7. Hardener component according to any of the preceding claims, characterized in that the Mannich base is contained in a proportion of from 10 to 70 wt.% in the hardener component, based on the organic proportion of the hardener component.

8. Hardener component according to any of the preceding claims, characterized in that the amine is contained in the hardener component in a proportion of from 20 to 80 wt.%, based on the organic proportion of the hardener component.

9. Hardener component according to any of the preceding claims, characterized in that the hardener component comprises further additives from the group of diluents, solvents, accelerators, silanes, thickeners, and inorganic fillers.

10. Multicomponent epoxy resin composition comprising an epoxy resin component (A) containing at least one curable epoxy resin and optionally a reactive diluent, at least one hardener component (B) according to any of the preceding claims, wherein the epoxy resin component (A) and the hardener component (B) are separate from one another.

11. Multicomponent epoxy resin composition according to claim 10, wherein the multicomponent epoxy resin composition comprises further additives selected from the group consisting of co-accelerators, adhesion promoters, reactive diluents, thickeners, and fillers.