Curing agent composition containing thiocyanate salts

Abstract

The present invention relates to a curable composition comprising at least one amine and at least one salt of a thiocyanate that are reactive with an epoxy group. The present invention further relates to the use of at least one salt of a thiocyanate in a multi-component epoxy resin material for anchor fixing means. The present invention further relates to a multi-component epoxy resin material, a mortar composition, and a method for chemical fixing of construction elements in boreholes.

Description

[Technical Field]

[0001] The present invention relates to a curable composition comprising at least one amine and at least one thiocyanate salt that are reactive with epoxy groups. The present invention further relates to the use of at least one thiocyanate salt in a multi-component epoxy resin material for anchor fixing means. The present invention further relates to a multi-component epoxy resin material, a mortar composition, and a method for chemical fixing of construction elements in boreholes.

[0002] Multicomponent mortar systems based on curable compositions containing curable epoxy resins and amines are known in the art. Such multicomponent mortar systems are typically used as adhesives, spackling pastes for repairing cracks, and chemical anchors for fixing construction elements such as anchor rods, reinforcing bars, and screws into boreholes in various substrates. In the art, nitrates, triflates, bisphenols, and novolac resins are used as accelerators in curable compositions containing amines.

[0003] For example, International Publication No. 2020 / 058017(A1) describes a composition for anchor fixing means in which nitrates and triflates are used as accelerators in an epoxy resin composition containing isophoronediamine and 1,3-bis(aminomethyl)cyclohexane. Similarly, International Publication No. 2021 / 185607(A1) teaches the use of nitrate and triflate salts as accelerators in an epoxy resin system containing m-xylylenediamine, 1,2-diaminocyclohexane, and 1,3-bis(aminomethyl)cyclohexane. Nitrites, such as calcium nitrate tetrahydrate used in the above literature, introduce water of crystallization into the formulation, which is detrimental when silanes, cements, or other water-sensitive materials need to be used in the same component. Triflates are expensive and were not REACH registered as of the filing date, thereby hindering their use in the European Union. International Publication No. 2019 / 101563(A1) discloses bisphenol and novolac resins used as accelerators for curing epoxy resin compositions comprising m-xylylenediamine, 1,2-diaminocyclohexane, and 1,3-bis(aminomethyl)cyclohexane.

[0004] Therefore, there remains a need to find new accelerators for curing compositions that, when used in mortar for fixing purposes, would impart improved pull-out strength / load values ​​in dry boreholes. Furthermore, there is a need for new accelerators that are less expensive, REACH registered, and do not contain crystal water.

[0005] Surprisingly, it was found that thiocyanate salts could be used instead of calcium nitrate or calcium triflate in curable compositions containing at least one amine reactive with epoxy groups. Even more surprisingly, mortar compositions containing thiocyanate salts in the curable composition showed improved pull-out strength / load values ​​in dry boreholes under standard conditions and at high temperatures (80°C) compared with mortars containing calcium nitrate or calcium triflate as part of the curable composition.

[0006] Therefore, an object of the present invention is to provide a curable composition containing an accelerator that is less expensive, does not contain crystalline water, and is REACH registered. Another object of the present invention is to provide a multi-component epoxy resin material suitable for fastening means that has improved pull-out strength / load values ​​under standard conditions and high temperatures (e.g., 45°C to 55°C) when used in dry boreholes.

[0007] The object of the present invention is achieved by providing the curable composition described in claim 1. Preferred embodiments of the curable composition according to the present invention are provided in the dependent claims and the following preferred embodiments, which can be optionally combined with each other.

[0008] The present invention further relates to a multi-component epoxy resin material as described in claim 9. Preferred embodiments of the multi-component epoxy resin material according to the present invention are provided in the dependent claims and the following preferred embodiments, which can be optionally combined with one another.

[0009] The present invention further relates to the mortar composition according to claim 15, the use of at least one salt of the thiocyanate according to claim 16, and the method for chemical fixation according to claim 17.

[0010] To better understand the present invention, the following explanation of terms used herein is considered useful. Within the meaning of the present invention, The article "a" or "an" preceding a chemical compound class means that it may refer to one or more compounds belonging to that chemical compound class. In preferred embodiments, these articles refer to only a single compound. "Aliphatic compounds" are acyclic or cyclic, saturated or unsaturated carbon compounds, excluding aromatic compounds. "Alicyclic compounds" are compounds having a carbocyclic ring structure, excluding benzene derivatives or other aromatic compounds. An "araliphatic compound" is an aliphatic compound that has an aromatic main chain, in the case of a functionalized arapatic compound, where the functional groups present are bonded to the aliphatic part of the compound rather than the aromatic part. Aromatic compounds are compounds that follow Hückel's (4n+2) rule. "At least one" numerically means "one or more." In a preferred embodiment, the term numerically means "1," and in another embodiment, the term may mean "2," "3," "4," "5," "6," "7," "8," "9," "10," or any number greater than "1." "Amines" are compounds derived from ammonia by replacing one, two, or three hydrogen atoms with a hydrocarbon group, and have the general structures RNH2 (primary amines), R2NH (secondary amines), and R3N (tertiary amines) (see IUPAC Compendium of Chemical Terminology, 2nd ed. (the "Gold Book"), edited by ADMcNaught and A. Wilkinson, Blackwell Scientific Publications, Oxford (1997)). A "salt" is a compound composed of positively charged ions (cations) and negatively charged ions (anions). Ionic bonds exist between these ions. The expression "thiocyanate salt" refers to a salt of thiocyanate (SCN) as the anion. - This section lists compounds containing ). Thiocyanates, also known as rhodamine, are conjugate bases of thiocyanic acid. "Include" and "comprising" mean that other components may exist in addition to those mentioned. These terms mean comprehensive and therefore include "consisting of." "Consisting of" means definitive and means that no further components may exist. In another embodiment, the terms "include" or "comprising" mean "consisting of," A range defined by numbers, such as "80-120% by weight," means that two corner values ​​and each value within that range are disclosed separately.

[0011] All standards cited in this text (e.g., DIN standards) were used in the most current version available as of the filing date of this application.

[0012] Therefore, the present invention relates to a curable composition comprising at least one amine and at least one salt of a thiocyanate that are reactive with an epoxy group. According to the present invention, it is understood that the at least one salt of a thiocyanate functions as an accelerator in the curable composition or in any one of the embodiments described herein.

[0013] The amount of at least one thiocyanate salt is preferably in the range of 0.1 to 15% by weight, more preferably 1 to 10% by weight, more preferably 2 to 8% by weight, more preferably 3 to 6% by weight, and more preferably 4 to 5% by weight, based on the total weight of the curable composition.

[0014] At least one salt of the thiocyanate is preferably selected from the group consisting of ammonium thiocyanate, sodium thiocyanate, potassium thiocyanate, imidazolinium thiocyanate, guanidine thiocyanate, copper(I) thiocyanate, tetrabutylammonium thiocyanate, calcium thiocyanate, lithium thiocyanate, magnesium thiocyanate, and two or more mixtures thereof, more preferably from the group consisting of ammonium thiocyanate, sodium thiocyanate, potassium thiocyanate, and two or more mixtures thereof, and more preferably at least one salt of the thiocyanate is ammonium thiocyanate and / or potassium thiocyanate.

[0015] At least one amine is preferably selected from the group consisting of aliphatic amines, alicyclic amines, aromatic aliphatic amines, aromatic amines, Mannich bases, and mixtures of two or more thereof, and at least one amine has at least two reactive hydrogen atoms on average per molecule bonded to a nitrogen atom, and preferably at least one amine is a polyamine having at least two amino groups in the polyamine molecule. The amount of at least one amine is preferably in the range of 10 to 90% by weight, more preferably in the range of 35 to 60% by weight, and more preferably in the range of 37 to 43% by weight, based on the total weight of the curable composition.

[0016] Examples of suitable amines that are reactive with epoxy groups are listed below, but are not limited to the scope of the present 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, 1,3-diaminopentane, 2,2,4- Or 2,4,4-trimethyl-1,6-diaminohexane and mixtures thereof (TMD), 1,3-bis(aminomethyl)-cyclohexane (1,3-BAC), 1,2-bis(aminomethyl)cyclohexane, hexamethylenediamine (HMD), 1,2-diaminocyclohexane (DCH), 1,4-diaminocyclohexane (1,4-diaminocyclohe xane (1,4-DACH), bis(4-amino-3-methylcyclohexyl)methane, diethylenetriamine (DETA), 4-azaheptan-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-4,7,10-trioxatridecane, 4-aminomethyl -1,8-diaminooctane, 2-butyl-2-ethyl-1,5-diaminopentane, N,N-bis(3-aminopropyl)methylamine, triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), 1,3-benzenedimethaneamine (m-xylylenediamine (smXDA)), 1,4-Benzene dimethaneamine (p-xylylenediamine, pXDA), 5-(aminomethyl)bicyclo[[2.2.1]hept-2-yl]methylamine (norbornane diamine, NBDA), dimethyldipropylenetriamine, dimethylaminopropylaminopropylamine (DMAPAPA), 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophorone diamine, IPDA), diaminodicyclohexyl methane (PACM), diethylmethylbenzenediamine (DETDA), 4,4'-diaminodiphenylsulfone (Dapson), mixed polycyclic amine (MPCA) (e.g., Ancamine® 2168), dimethyldiaminodicyclohexylmethane (Laromin C260), 2,2-bis(4-aminocyclohexyl)propane, (3(4),8(9)bis(aminomethyldicyclo[5.2.1.0, 2,6 Decane (a mixture of isomers, a tricyclic primary amine; TCD-diamine), methyldiaminocyclohexane (MDACH), N,N'-diaminopropyl-2-methylcyclohexane-1,3-diamine, N,N'-diaminopropyl-4-methylcyclohexane-1,3-diamine, N-(3-aminopropyl)cyclohexylamine, and 2-(2,2,6,6-tetramethylpiperidine-4-yl)propane-1,3-diamine.

[0017] Preferred amines that are reactive to epoxy groups in the curable composition according to the present invention are polyamines, for example, 2-methylpentanediamine (DYTEK® A), 3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), 1,3-benzenedimethaneamine (m-xylylenediamine, mXDA), 1,2-diaminocyclohexane (DCH), 1,4-benzenedimethaneamine (p-xylylenediamine, PXDA), 1,6-diamino-2,2,4-trimethylhexane (trimethylhexane, TMD), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), N-ethylaminopiperazine (N-ethylaminopiperazine, N-EAP), (3(4),8(9)bis(aminomethyl)dicyclo[5.2.1.0 2,6 Decane (mixture of isomers, tricyclic primary amine; 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 polyoxypropylene and triamines, 2,5-diamino-2,5-di These include methylhexane, bis(amino-methyl)tricyclopentadiene, 1,8-diamino-p-menthane, bis(4-amino-3,5-dimethylcyclohexyl)methane, 1,3-bis(aminomethyl)cyclohexane (1,3-BAC), dipentylamine, N-2-(aminoethyl)piperazine (N-AEP), N-3-(aminopropyl)piperazine, piperazine, and methyldiaminocyclohexane (MDACH).

[0018] All amines outlined above can be used both individually and in mixtures of two or more of the specified amines.

[0019] The Mannich base used in the curable composition according to the present invention in combination with the above-mentioned amine reactive with an epoxy group is a reaction product of an amine, an aldehyde, and a phenolic compound selected from the group consisting of phenol, pyrocatechol, resorcinol, hydroquinone, hydroxyhydroquinone, phloroglucinol, pyrogallol, o-cresol, m-cresol, p-cresol, bisphenols such as bisphenol F or bisphenol A, and combinations thereof.

[0020] To form the Mannich base, the phenolic compound preferably reacts with a primary or secondary amine and an aldehyde or an aldehyde precursor that yields an aldehyde as a result of decomposition. Advantageously, the aldehyde or aldehyde precursor is added to the reaction mixture as an aqueous solution, particularly at a high temperature of approximately 50 °C to 90 °C, and can be reacted with the amine and the phenolic compound.

[0021] Phenol or styrenated phenol, resorcinol, styrenated resorcinol, bisphenol A or bisphenol F is preferably used as the phenolic compound for forming the Mannich base, and the use of phenol or styrenated phenol, styrenated resorcinol or bisphenol A is particularly preferred.

[0022] The aldehyde used to form the Mannich base is preferably an aliphatic aldehyde, particularly preferably formaldehyde. Trioxane or paraformaldehyde that decomposes upon heating in the presence of water to form formaldehyde can preferably be used as the aldehyde precursor.

[0023] The amine used to react with the aldehyde and phenol compound to form a Mannich base is preferably one of the above amines that are reactive to epoxy groups, and is preferably 1,3-benzenedimethaneamine (mXDA), 3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), 1,3-bis(aminomethyl)cyclohexane (1,3-BAC), iamino(a)dicyclohexylmethane (PACM), methylcyclohexyldiamine (mCDA), and 5-(aminomethyl)bicyclo[[2.2.1]hept-2-yl]methylamine (NBDA). The amine is preferably present in excess so that the Mannich base has a free amino group.

[0024] Amines used to react with aldehydes and phenol compounds to form Mannich bases are also 3-aminoalkyltrialkoxysilanes, e.g., 3-aminopropyl-tri(m)ethoxysilane, 3-aminoalkylalkyldialkoxysilanes, e.g., 3-aminopropylmethyldi(m)ethoxysilane, N-(aminoalkyl)-3-aminoalkyltrialkoxysilanes, e.g., N-(2-aminoethyl)-3-aminopropyltri(m)ethoxysilane, N-(aminoalkyl)-3-aminoalkyl-alkyldialkoxysilanes, e.g., N-(2-aminoethyl)-3-aminopropylmethyldi(m)ethoxysilane, 3-[2-(2-Amin The aminosilane may be selected from the group consisting of noethylamino)ethylamino]propyltri(m)ethoxysilane, bis-(gamma-trimethoxysilylpropyl)amine, or mixtures thereof, or selected from the group consisting of N-cyclohexyl-3-aminopropyltri(m)ethoxysilane, N-cyclohexylaminomethylmethyldiethoxysilane, N-cyclohexylaminomethyltriethoxysilane, 3-ureidopropyltri(m)ethoxysilane, N-methyl[3-(trimethoxysilyl)-propylcarbamate, N-trimethoxysilylmethyl-o-methylcarbamate, and N-dimethoxy(methyl)silylmethyl-o-methylcarbamate.

[0025] According to the present invention, it is particularly preferable that at least one amine is selected from the group consisting of isophoronediamine (IPDA), 1,3-cyclohexanebis(methylamine) (1,3-BAC), m-xylylenediamine (mXDA), methyldiaminocyclohexane (MDACH), 1,2-diaminocyclohexane (DCH), and mixtures of two or more thereof. Preferably, at least one amine consists of IPDA and 1,3-BAC, or preferably at least one amine consists of mXDA, MDACH, and 1,3-BAC, or preferably at least one amine consists of mXDA, DCH, and 1,3-BAC.

[0026] The amount of at least one amine is preferably in the range of 10 to 90% by weight, more preferably 35 to 60% by weight, and more preferably 37 to 43% by weight, based on the total weight of the curable composition.

[0027] If the curable composition includes those listed in the paragraph above, but also includes other amines other than isophoronediamine (IPDA), 1,3-cyclohexanebis(methylamine), (1,3-BAC), m-xylylenediamine (mXDA), methyldiaminocyclohexane (MDACH), and 1,2-diaminocyclohexane (DCH), the amount of such other amines is preferably in the range of 0.01 to 20% by weight, more preferably in the range of 5 to 10% by weight, based on the total weight of the curable composition.

[0028] In any one of the embodiments described herein, it is particularly preferable that at least one amine has an active hydrogen equivalent weight of less than 100 g / EQ, and more preferably in the range of 70 to 95 g / EQ. It is also particularly preferable that each individual amine of the at least one amine contained in the curable composition has an active hydrogen equivalent weight of less than 75 g / EQ, more preferably in the range of 25 to 70 g / EQ, and more preferably in the range of 30 to 40 g / EQ.

[0029] It is also preferable that at least one amine in any one of the embodiments described herein is siloxane-free. Therefore, it is particularly preferable that at least one amine in any one of the embodiments described herein is siloxane-free, more preferably amine-functionalized polyorganosiloxane-free, and more preferably amine-functionalized polyorganosiloxane having an average degree of polymerization of 10 or more.

[0030] In any one of the embodiments disclosed herein, at least one amine is more preferably a monomer polyamine, more preferably a monomer diamine.

[0031] The curable composition of the present invention preferably further comprises at least one co-accelerator selected from the group consisting of benzyl alcohol, tertiary amines, novolacs, imidazoles, tertiary aminophenols, styrene-phenols, organophosphines, Lewis bases, Lewis acids, organophosphates, and combinations of two or more thereof. Preferably, the at least one co-accelerator is selected from the group consisting of 2,4,6-tris(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylamino)phenol, and bis[(dimethylamino)methyl]phenol. More preferably, the at least one co-accelerator contains a mixture of 2,4,6-tris(dimethylaminomethyl)phenol and bis(dimethylaminomethyl)phenol. Such mixtures are commercially available, for example, as Ancamine® K54 (Evonik, Germany).

[0032] The co-accelerator may also be present in the epoxy resin component (A) if it is compatible with the epoxy resin.

[0033] If the curable composition contains at least one co-accelerator, the amount of the at least one co-accelerator is preferably in the range of 0.001 to 5% by weight, more preferably 0.01 to 1% by weight, and more preferably 0.1 to 0.5% by weight, based on the total weight of the curable composition.

[0034] The use of an adhesion promoter improves crosslinking between the borehole wall and the mortar compound, thereby increasing adhesion in the cured state. A suitable adhesion promoter is selected from the group of silanes having at least one Si-bonded hydrolyzable group. Therefore, the curable composition of the present invention may further preferably contain at least one silane having at least one Si-bonded hydrolyzable group.

[0035] At least one silane is N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminoethyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane (aminopropyltrimethoxysilane, AMMO), 3-aminopropyltriethoxysilane (aminopropyltriethoxysilane, AMEO), 2-aminoethyl-3-aminopropyl The silanes are selected from the group consisting of 2-aminoethyl-3-aminopropyltrimethoxysilane (DAMO), trimethoxysilylpropyldiethylenetetramine (TRIAMO), and mixtures of two or more thereof, more preferably from the group consisting of 3-aminopropyltrimethoxysilane (AMMO), 3-aminopropyltriethoxysilane (AMEO), 2-aminoethyl-3-aminopropyltrimethoxysilane (DAMO), and trimethoxysilylpropyldiethylenetetramine (TRIAMO), and mixtures of two or more thereof. Further silanes are described, for example, in European Patent No. 3000792(A1), the contents of which are incorporated into this application.

[0036] The amount of at least one silane is preferably in the range of 0.01 to 10% by weight, more preferably in the range of 1 to 6% by weight, and more preferably in the range of 2 to 4% by weight, based on the total weight of the curable composition.

[0037] The curable composition of the present invention may also preferably further contain at least one nonreactive diluent (solvent). The amount of at least one nonreactive diluent is preferably in the range of 0.01 to 30% by weight, more preferably in the range of 1 to 20% by weight, and more preferably in the range of 2 to 5% by weight, based on the total weight of the curable composition. Examples of suitable solvents are alcohols such as methanol, ethanol, or glycol; dilow alkyl lower alkanoylamides such as dimethylacetamide; lower alkylbenzenes such as xylene or toluene; phthalates or paraffins.

[0038] The curable composition of the present invention preferably further comprises at least one filler, preferably at least one inorganic filler. The amount of the at least one filler is preferably in the range of 0.1 to 75% by weight, preferably 5 to 70% by weight, more preferably 10 to 65% by weight, more preferably 20 to 50% by weight, and more preferably 25 to 40% by weight, based on the total weight of the curable composition.

[0039] When the curable composition contains at least one filler, the at least one filler is preferably selected from the group consisting of Portland cement, aluminate cement, hydraulic inorganic substances, quartz, glass, corundum, porcelain, stoneware, barite, light spar, gypsum, talc, chalk, fumed silica, and mixtures of two or more thereof. Fumed silica can also be described as a thickener. Particularly preferred fillers are untreated quartz powder, fine quartz powder, and ultrafine quartz powder such as Millisil® W3, Millisil® W6, Millisil® W8, and Millisil® W12, preferably Millisil® W12. Silanized quartz powder, fine quartz powder, and ultrafine quartz powder can also be used. These are commercially available, for example, from the Silbond product series from Quarzwerke. The product series Silbond EST (epoxysilane modification) and Silbond AST (aminosilane treatment) are particularly preferred. Further, aluminum oxide-based fillers, for example, the ASFP type of aluminum oxide ultrafine filler (d 50 = 0.3 μm) from Denka, Japan, or grades such as DAW or DAM having type designation 45 (d 50 < 0.44 μm), 07 (d 50 > 8.4 μm), 05 (d 50 < 5.5 μm), and 03 (d 50 < 4.1 μm). Further, surface-treated fine and ultrafine fillers of the Aktisil AM type (aminosilane treatment, d 50 = 2.2 μm) and Aktisil EM (epoxysilane treatment, d50 = 2.2 μm) from Hoffman Mineral can be used.

[0040] According to the present invention, at least one filler may be in the form of sand, powder, powder, molded body, fiber, ball, or a mixture of two or more thereof, preferably at least one filler may be in the form of fiber and / or ball. At least one filler may be present in one or all of the components of the multi-component epoxy resin material described below. By using a suitable selection of fillers with respect to type and particle size distribution / (fiber) length, application-relevant properties such as rheological behavior, extrusion force, internal strength, tensile strength, pull-out force, and impact strength can be controlled.

[0041] The present invention further relates to a multi-component epoxy resin material comprising an epoxy resin component (A) and a curable component (B) comprising a curable composition according to any one of the embodiments disclosed herein, wherein the epoxy resin component (A) comprises at least one curable epoxy resin.

[0042] At least one salt of the thiocyanates described herein may be contained in the epoxy resin component (A) or the curable component (B), or in both the epoxy resin component (A) and the curable component (B). At least one salt of the thiocyanate is preferably contained in the curable component (B), preferably only in the curable component (B). In this case, the curable composition described above is used in a multi-component epoxy resin system.

[0043] At least one curable epoxy resin preferably has one, two, or more epoxy groups per curable epoxy resin, preferably two epoxy groups. At least one curable epoxy resin may be saturated, unsaturated, aliphatic, alicyclic, aromatic, and heterocyclic, or a combination of two or more thereof. At least one curable epoxy resin may have substituents that do not cause destructive secondary reactions under mixing or reaction conditions, such as alkyl or aryl substituents, ether groups, etc. In the context of the present invention, trimer and tetramer epoxides are also preferred.

[0044] According to the present invention, at least one curable epoxy resin is preferably selected from the group consisting of glycidyl ethers derived from polyhydric alcohols, more preferably from polyhydric phenols such as bisphenols and novolacs, and at least one curable epoxy resin preferably has a glycidyl ether functionality of 1.5 or more, preferably 2 or more, and more preferably 2 to 10.

[0045] Preferably, at least one curable epoxy resin has an epoxy equivalent weight (EEW) in the range of 120 to 2000 g / EQ, preferably 140 to 400 g / EQ, more preferably 155 to 195 g / EQ, and more preferably 165 to 185 g / EQ. Preferably, at least one curable epoxy resin contains a mixture of two or more epoxy resins described herein.

[0046] The polyhydric phenol is preferably selected from the group consisting of resorcinol, hydroquinone, 2,2-bis-(4-hydroxyphenyl)propane (bisphenol A), a mixture of isomers of dihydroxyphenylmethane (bisphenol F), tetrabromobisphenol A, novolac, 4,4'-dihydroxyphenylcyclohexane, and 4,4'-dihydroxy-3,3'-dimethyldiphenylpropane, and mixtures of two or more thereof.

[0047] It is also preferable that at least one curable epoxy resin is a diglycidyl ether of bisphenol A and / or bisphenol F. In particular, the liquid diglycidyl ether based on bisphenol A and / or F is preferably having an EEW in the range of 180 to 190 g / EQ.

[0048] It is also preferable that at least one curable epoxy resin be selected from the group consisting of hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, bisphenol A epichlorohydrin resin, bisphenol F epichlorohydrin resin, and two or more combinations thereof. It is also preferable that at least one curable epoxy resin has an average molecular weight of Mn ≤ 2000 g / mol.

[0049] The amount of at least one curable epoxy resin is preferably in the range of 0.01 to 100% by weight, more preferably in the range of 10 to 70% by weight, and more preferably in the range of 30 to 60% by weight, based on the total weight of epoxy resin component (A).

[0050] The epoxy resin component (A) described herein may further comprise at least one reactive diluent. The at least one reactive diluent according to the present invention may be selected from aliphatic, alicyclic, or aromatic monoalcohol glycidyl ethers, or in particular, a polyalcohol having a lower viscosity than an epoxide containing an aromatic group may be used as the reactive diluent. Examples of reactive diluents include monoglycidyl ethers, such as o-cresyl glycidyl ether, and glycidyl ethers having at least two epoxy functionalities, such as 1,4-butanediol diglycidyl ether (BDDGE), cyclohexanedimethanol diglycidyl ether, and hexanediol diglycidyl ether, as well as tri- or higher-order glycidyl ethers, such as glycerol triglycidyl ether, pentaerythritol tetraglycidyl ether, trimethylolpropane triglycidyl ether (TMPTGE), or trimethylolethane triglycidyl ether (TMETGE), with trimethylolethane triglycidyl ether being preferred. Mixtures of two or more of these reactive diluents can also be used. At least one reactive diluent is preferably selected from the group consisting of triglycidyl ether, 1,4-butanediol diglycidyl ether (BDDGE), trimethylolpropane triglycidyl ether (TMPTGE), 1,4-butanediol diglycidyl ether (BDDGE), trimethylolethane triglycidyl ether (TMETGE), and mixtures of two or more thereof, more preferably 1,4-butanediol diglycidyl ether (BDDGE) and trimethylolpropane triglycidyl ether (TMPTGE), and more preferably 1,4-butanediol diglycidyl ether (BDDGE) and trimethylolethane triglycidyl ether (TMETGE).

[0051] Suitable epoxy resins and reactive diluents can also be found in the standard reference of Michael Dornbusch, Ulrich Christ and Rob Rasing, "Epoxidharze," Vincentz Network GmbH & Co KG (2015), ISBN 13: 9783866308770. These compounds are incorporated herein by reference.

[0052] If the epoxy resin component (A) contains at least one reactive diluent, the amount of the at least one reactive diluent is preferably in the range of 0.01 to 60% by weight, more preferably in the range of 1 to 20% by weight, and more preferably in the range of 2 to 7% by weight, based on the total weight of the epoxy resin component (A).

[0053] The use of an adhesion promoter improves the bonding of the mortar to the concrete, and therefore increases the bonding in the cured state. Thus, in another embodiment, it is preferable that the epoxy resin component (A) according to any one embodiment of the present invention further comprises at least one silane having at least one Si-bonded hydrolyzable group. Preferred examples of at least one silane contained in component (A) are 3-glycidyloxypropyl trialkoxysilane, e.g., 3-glycidyloxypropyl trimethoxysilane (GLYMO), or -3-glycidyloxypropyl triethoxysilane; glycidyloxymethyl trialkoxysilane, e.g., glycidyloxymethyl trimethoxysilane or glycidyloxymethyl triethoxysilane; 3-glycidyloxypropyl methyl dialkoxysilane, e.g., 3-glycidyloxypropyl methyl dimethoxysilane or 3-glycidyloxypropyl methyl diethoxysilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; and / or tetraalkoxysilane, e.g., tetramethoxysilane, tetraethoxysilane, and / or tetrapropoxysilane, or mixtures of two or more thereof. Preferably, at least one silane contained in component (A) is 3-glycidyloxypropyltrimethoxysilane (e.g., Dynasylan® GLYMO by Evonik Industries, Germany).

[0054] The epoxy resin component (A) preferably contains at least one filler, preferably at least one inorganic filler. The at least one filler has already been described with respect to the curable composition. The amount of the at least one filler is preferably in the range of 0.01 to 75% by weight, preferably 5 to 70% by weight, more preferably 10 to 60% by weight, more preferably 20 to 50% by weight, and more preferably 25 to 40% by weight, based on the total weight of the epoxy resin component (A).

[0055] If the epoxy resin component (A) contains at least one filler, the at least one filler is preferably selected from the group consisting of Portland cement, aluminate cement, hydraulic inorganic materials, quartz, glass, corundum, porcelain, pottery, barite, lite spar, gypsum, talc, chalk, fumed silica, and mixtures of two or more thereof. Fumed silica can also be described as a thickener. Particularly preferred fillers are untreated quartz powder, fine quartz powder, and ultrafine quartz powder, such as Millisil® W3, Millisil® W6, Millisil® W8, and Millisil® W12, preferably Millisil® W12. Silane fossil quartz powder, fine quartz powder, and ultrafine quartz powder can also be used. These are commercially available, for example, from the Silbond product series from Quarzwerke. The Silbond EST (epoxysilane modified) and Silbond AST (aminosilane treated) product series are particularly preferred. Furthermore, aluminum oxide-based fillers, such as the ASFP type aluminum oxide ultrafine filler from Denka, Japan (d 50 =0.3μm), or type specified 45(d 50 <0.44μm), 07(d 50 >8.4μm), 05(d 50 <5.5μm), and 03(d 50 Grades such as DAW or DAM having <4.1μm). Furthermore, Aktisil AM type (aminosilane treatment, d) from Hoffman Mineral. 50 Fine and ultrafine fillers with surface-treated d50=2.2μm (=2.2μm) and Aktisil EM (epoxysilane treated, d50=2.2μm) may be used.

[0056] According to the present invention, at least one filler may be in the form of sand, powder, powder, molded body, fiber, ball, or a mixture of two or more thereof, preferably at least one filler may be in the form of fiber and / or ball. At least one filler may be present in one or all of the components of the multi-component epoxy resin material described below. By using a suitable selection of fillers with respect to type and particle size distribution / (fiber) length, application-relevant properties such as rheological behavior, extrusion force, internal strength, tensile strength, pull-out force, and impact strength can be controlled.

[0057] Further possible additives to the epoxy resin component (A) are also thixotropic agents, such as optionally organically post-treated fumed silica, bentonite, alkyl- and methylcellulose, and castor oil derivatives; plasticizers, such as phthalates or sebacates; stabilizers, antistatic agents, thickeners, softeners, curing catalysts, rheological aids, wetting agents; coloring additives, such as dyes or pigments, for different coloring of the components for improved control of their mixture, and other control agents for reaction rate, or mixtures of two or more thereof.

[0058] A multi-component epoxy resin material according to any one of the embodiments disclosed herein may also preferably be in the form of a two-component system consisting of component (A) and component (B).

[0059] The multi-component epoxy resin material is preferably present in a cartridge or film pouch comprising two or more separate chambers, each containing an epoxy resin component (A) and a curable component (B) arranged separately to prevent reaction.

[0060] The present invention further relates to a mortar composition comprising a multi-component epoxy resin material according to any one of the embodiments disclosed herein.

[0061] The present invention also relates to the use of at least one salt of a thiocyanate in a multi-component epoxy resin material for anchor fixing means that improves load values ​​compared to multi-component epoxy resin compositions containing calcium nitrate or calcium triflate.

[0062] For the intended use of the multi-component epoxy resin system, the epoxy resin component (A) and the curable component (B) are discharged from separate chambers and mixed in a suitable device, such as a static mixer or dissolver. The mixture of epoxy resin component (A) and curable component (B) is then introduced into a pre-cleaned borehole, preferably a dry borehole, by means of a known injection device. The components to be fixed are then inserted into the mortar compound and aligned. The reactive components of curable component (B) react with the epoxy resin of resin component (A) by polyaddition, thereby causing the epoxy resin compound to cure under environmental conditions within a desired time, preferably within a few minutes or hours, more preferably within 6 to 12 hours, to reach 90% of the final load.

[0063] The present invention relates to a method for chemically fixing construction elements in boreholes, wherein a mortar composition or multi-component epoxy resin material according to any one of the embodiments disclosed herein is used for chemical fixing. The method according to the present invention is particularly suitable for the structural bonding of concrete / concrete, steel / concrete, or steel / steel, or other mineral materials, structural reinforcement of components made of concrete, brick, and other mineral materials, reinforcement applications of buildings using fiber-reinforced polymers, chemical fixing of surfaces made of concrete, steel, or other mineral materials, and especially for chemical fixing of construction elements and anchor fixing means in boreholes in various substrates such as (reinforced) concrete, brick, other mineral materials, metal (e.g., steel), ceramics, plastics, glass, and wood, such as anchor rods, anchor bolts, (threaded) rods, (threaded) sleeves, reinforcing bars, screws, etc. The method according to the present invention is very particularly preferred for use in the chemical fixing of anchor fixing means.

[0064] Components A and B are preferably mixed in a ratio that yields a balanced stoichiometry according to the EEW and AHEW values.

[0065] The AHEW value (amine hydrogen equivalent weight, H equivalent) provides the amount of a curable composition containing 1 mol of reactive H. AHEWs are determined in a manner known to those skilled in the art, based on the formulation of the reaction mixture from the known H equivalents of the reactants and raw materials used in which they are calculated.

[0066] Meta-xylylenediamine (M W Using the example of (=136 g / mol, functionality = 4 eq / mol), the calculation of AHEW is explained below as an example.

[0067]

number

[0068] EEW (Epoxy Equivalent Weight) is generally provided by the manufacturer of the (curable) epoxy resin component used in each case, or calculated according to known methods. The EEW value is given in grams for the amount of epoxy resin containing 1 mole of epoxy groups.

[0069] In the experiment, AHEW was obtained by determining the glass transition temperature (Tg) of a mixture of epoxy resin (with a known EEW) and an amine component. In this case, the glass transition temperature of the epoxy resin / amine mixture was determined at different ratios. The sample was cooled from 21 to -70°C at a heating rate of -20 K / min, heated to 250°C in the first heating cycle (heating rate 10 K / min), then recooled to -70°C (heating rate -20 K / min), and heated to 200°C in the final step (20 K / min). The highest glass transition temperature (Tg) was determined in the second heating cycle. g The mixture having (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. Example: EWE = 158 g / mol

[0070] Max T g Amine / epoxy resin mixture containing 2: 1 g amine containing 4.65 g epoxy resin

[0071]

number

[0072] The use of at least one salt of thiocyanate as an accelerator in a curable composition of epoxy resin component (A) and curable component (B), particularly in multi-component epoxy resin materials, within the meaning of the present invention, allows for improved load values ​​compared to when calcium nitrate or calcium triflate are used as accelerators, respectively. Furthermore, the cured epoxy resin material or mortar has excellent pull-out strength / load values ​​when used in dry boreholes and / or at high temperatures, for example, in a temperature range of 35°C to 80°C.

[0073] All embodiments of the present invention can be combined with one another within the scope of the invention. Further advantages of the present invention can also be found in the following examples, but these are not intended to be understood as limiting. [Examples]

[0074] [Table 1]

[0075] [Table 2]

[0076] A-Component First, all the liquid components were mixed. Next, the filler and thickener were added to the respective liquid components and stirred under vacuum at 3500 rpm for 10 minutes in a dissolver (PC laboratory system, 1 L volume).

[0077] B-component The salts of thiocyanate and calcium triflate were dissolved as solids in their respective amine (curing agent) mixtures. Calcium nitrate tetrahydrate was dissolved in glycerol and then added to the respective amine mixtures to obtain an 80% solution of calcium nitrate tetrahydrate in glycerol.

[0078] Finally, all the liquids were mixed together, the filler and thickener were added, and the mixture was stirred under vacuum at 3500 rpm for 10 minutes in a dissolver (PC laboratory system, 1 L volume).

[0079] The formulations described in the following examples were mixed using a speed mixer (Hauschild, Hamm) and then filled into 1K cartridges before being introduced into the borehole. The mixing ratio was selected to yield a balanced stoichiometry of EEW and AHEW.

[0080] Example 1: IPDA, 1,3-BAC, ammonium thiocyanate

[0081] [Table 3]

[0082] [Table 4]

[0083] Example 2: mXDA, 1,3-BAC, MDACH, ammonium thiocyanate

[0084] [Table 5]

[0085] [Table 6]

[0086] Example 3: mXDA, 1,3-BAC, DCH, ammonium thiocyanate

[0087] [Table 7]

[0088] [Table 8]

[0089] Example 4: IPDA, 1,3-BAC, ammonium thiocyanate

[0090] [Table 9]

[0091] [Table 10]

[0092] Example 5: IPDA, 1,3-BAC, sodium thiocyanate

[0093] [Table 11]

[0094] [Table 12]

[0095] Example 6: IPDA, 1,3-BAC, potassium thiocyanate

[0096] [Table 13]

[0097] [Table 14]

[0098] Comparative Example 1: IPDA, 1,3-BAC, calcium nitrate tetrahydrate

[0099] [Table 15]

[0100] [Table 16]

[0101] Comparative Example 2: mXDA, 1,3-BAC, MDACH, calcium nitrate tetrahydrate

[0102] [Table 17]

[0103] [Table 18]

[0104] Comparative Example 3: mXDA, 1,3-BAC, DCH, calcium nitrate tetrahydrate

[0105] [Table 19]

[0106] [Table 20]

[0107] Comparative Example 4: mXDA, 1,3-BAC, DCH, calcium trifluoromethanesulfonate

[0108] [Table 21]

[0109] [Table 22]

[0110] Comparative Example 5: IPDA, 1,3-BAC, calcium nitrate tetrahydrate

[0111] [Table 23]

[0112] [Table 24]

[0113] A mortar composition with as few air bubbles as possible was filled into a 1L cartridge and immediately injected into a borehole prepared for the pull-out test. The pull-out strength of the mortar obtained by mixing the epoxy resin component (A) and the curing component (B) according to the example was measured using a high-strength threaded anchor rod M12 according to EAD 330499-01-0601 (December 2018), which was inserted into a hammer-drilled borehole with a diameter of 14 mm and a borehole depth of 62 mm for each mortar mass in C20 / 25 concrete. The borehole was cleaned with compressed air (2 times at 6 bar), a wire brush (2 times), and again with compressed air (2 times at 6 bar). Two-thirds of the borehole was filled with the mortar composition from the bottom. The threaded rod was then inserted by hand into the filled borehole, and excess mortar was removed with a spatula. The curing time was 24 hours at 25°C. A reference load R1 was tested immediately after the curing time. High-temperature load (B3) was tested after storage at 80°C for 48 hours. Extraction was also performed at 80°C. The breaking load was determined by pulling a threaded anchor rod with tight support from the center. The load values ​​obtained for the hardened mortar composition were standardized for each concrete strength and are disclosed in Table 3 below.

[0114] [Table 25]

[0115] As can be seen in Table 3, the examples of the present invention (Examples 1-5) show an improvement in load values ​​compared to the corresponding Comparative Examples 1-5. All examples of the present invention show an improvement in load values ​​compared to Comparative Examples 2-4. Furthermore, Example 1 of the present invention shows 39.1 N / mm 2 This shows the highest load value, which is the comparative example load value of 37.7 N / mm². 2 This represents a significant improvement. Similar advantages can be observed when comparing Example 5 with Comparative Example 5. Finally, the load values ​​measured at a high temperature of 80°C for Examples 4, 5, and 6 show an improvement in load values ​​compared to Comparative Example 5.

Claims

1. A curable composition comprising a salt of at least one amine and at least one thiocyanate that are reactive with an epoxy group.

2. The curable composition according to claim 1, wherein the amount of the salt of at least one thiocyanate is in the range of 0.1 to 15% by weight based on the total weight of the curable composition.

3. The curable composition according to claim 1 or 2, wherein the salt of at least one thiocyanate is selected from the group consisting of ammonium thiocyanate, sodium thiocyanate, potassium thiocyanate, imidazolinium thiocyanate, guanidine thiocyanate, copper(I) thiocyanate, tetrabutylammonium thiocyanate, calcium thiocyanate, lithium thiocyanate, magnesium thiocyanate, and mixtures of two or more thereof.

4. The curable composition according to any one of claims 1 to 3, wherein the at least one amine is selected from the group consisting of aliphatic amines, alicyclic amines, aromatic aliphatic amines, aromatic amines, Mannich bases, and mixtures of two or more thereof, and the at least one amine has an average of at least two reactive hydrogen atoms per molecule bonded to a nitrogen atom.

5. The curable composition according to any one of claims 1 to 4, wherein the at least one amine is selected from the group consisting of isophoronediamine (IPDA), 1,3-cyclohexanebis(methylamine) (1,3-BAC), m-xylylenediamine (mXDA), methyldiaminocyclohexane (MDACH), 1,2-diaminocyclohexane (DCH), and mixtures of two or more thereof.

6. A curable composition according to any one of claims 1 to 5, further comprising at least one filler.

7. The curable composition according to claim 6, wherein the amount of the at least one filler is in the range of 0.1 to 75% by weight based on the total weight of the curable composition.

8. A multi-component epoxy resin material, A multi-component epoxy resin material comprising an epoxy resin component (A) and a curable component (B) containing the curable composition described in any one of claims 1 to 7, wherein the epoxy resin component (A) contains at least one curable epoxy resin.

9. The multi-component epoxy resin material according to claim 8, wherein the at least one curable epoxy resin has one, two, or more epoxy groups.

10. The multi-component epoxy resin material according to claim 8 or 9, wherein the epoxy resin component (A) comprises at least one reactive diluent.

11. The multi-component epoxy resin material according to any one of claims 8 to 10, wherein the epoxy resin component (A) comprises at least one filler.

12. The multi-component epoxy resin material according to claim 11, wherein the amount of the at least one filler is in the range of 0.01 to 75% by weight based on the total weight of the epoxy resin component (A).

13. A multi-component epoxy resin material according to any one of claims 8 to 12, in the form of a two-component system consisting of component (A) and component (B).

14. A mortar composition comprising a multi-component epoxy resin material according to any one of claims 8 to 13.

15. Use of at least one thiocyanate salt in a multi-component epoxy resin material for anchor fixing means to improve load values.

16. A method for chemically fixing construction elements in a borehole, wherein the mortar composition according to claim 14 or the multi-component epoxy resin material according to any one of claims 8 to 13 is used for the chemical fixing.

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