Two-component mortar compounds with temperature-responsive inhibitors

Abstract

In a general form of the invention, the invention comprises a two-component mortar compound having a resin component (A) containing at least one radically curable resin as a curable component and a curing component (B) containing a curing agent for the radically curable resin of the resin component (A), the resin component (A) contains one or more polymerization inhibitors selected from the group consisting of phenolic polymerization inhibitors, phenothiazine and / or derivatives thereof, stable organic radicals, oximes and pyrimidinol or pyrimidinol compounds substituted in the para-position of the hydroxyl group, characterised in that the resin component (A) further contains an alkoxyamine compound (I) of the formula R-O-N (R 'R "), where R represents an alkyl group and R'or R" each represents an organic group, and said compound has an activation energy Ea for the homocleavage of the R-O bond in the range of 100 kJ / mol to 120 kJ / mol. In another embodiment, the invention comprises a two-component mortar compound having a resin component (A) containing at least one free-radical curable resin as a curable component and a curing component (B) containing a curing agent for the free-radical curable resin of the resin component (A), the resin component (A) contains one or more polymerization inhibitors selected from the group consisting of phenolic polymerization inhibitors, phenothiazine and / or derivatives thereof, stable organic radicals, oximes and pyrimidinol or pyrimidinol compounds substituted in the para-position of the hydroxyl group, characterised in that the resin component (A) further contains an alkoxyamine compound # imgabs0 # of the following formula (II). The invention relates to the use of the two-component mortar compound for chemically fastening fastening elements, such as anchoring threaded rods, reinforcing bars, threaded sleeves and screws, in drill holes present in building materials, such as wood or mineral substrates.

Description

Technical Field

[0001] The present invention relates to a two-component mortar compound having a resin component (A) and a curing component (B), wherein the resin component (A) contains at least one free-radical curable resin as a curable component, and the curing component (B) contains a curing agent for the free-radical curable resin of the resin component (A). The resin component (A) of the two-component mortar compound according to the present invention also contains one or more conventional polymerization inhibitors, which are selected from phenolic polymerization inhibitors, phenothiazines and / or their derivatives, stable organic free radicals, oximes and pyrimidinol or pyridinol compounds substituted in the para position of the hydroxyl group. The two-component mortar compound of the present invention is characterized in that the resin component (A) also contains an alkoxyamine compound as a temperature-responsive inhibitor. The present invention also relates to the use of the mortar compound for chemically fastening elements such as threaded anchor rods, reinforcement bars, threaded sleeves and screws in drilled holes formed in mineral substrates. Background Art

[0002] In order to securely fasten fastening elements (such as threaded anchor rods, reinforcement bars, threaded sleeves and screws) in a mineral substrate (such as concrete, natural stone or plaster of Paris), a borehole for receiving the fastening element to be fastened is first drilled into the mineral substrate with an appropriate size. The drill hole is then cleaned of drilling dust and a two-component mortar compound is introduced into the borehole after mixing the resin component with the curing component. The fastening element to be fastened is then inserted into the borehole filled with the mortar compound and adjusted. After the mortar compound has cured by reaction of the resin component with the curing component, the fastening element is securely held in the mineral substrate.

[0003] The load-bearing properties of a fastening element fastened in this way depend on a number of influencing variables, which are generally classified as internal and external variables. The internal influencing variables include the chemical composition of the mortar compound, its production method and the packaging of the mortar compound, which generally comprises the components present in two separate containers.

[0004] External influencing variables include the type of borehole cleaning, the quality of the mineral substrate (eg concrete), its moisture and temperature and the type of borehole production.

[0005] Two-component mortar compounds based on urethane (meth)acrylate resins which cure by free-radical polymerization are known from EP 0 432 087 and EP 0 589 831.

[0006] Mortar compounds based on free-radical curing reactive resins known in the prior art and used as chemically bonded anchors usually contain polymerization inhibitors. Such conventional polymerization inhibitors are selected from phenolic polymerization inhibitors, phenothiazines and / or their derivatives, stable organic free radicals, oximes and pyrimidinol or pyridinol compounds substituted in the para position of the hydroxyl group. The polymerization inhibitors can be used on the one hand to ensure a specific storage stability of the mortar compound and on the other hand to set a desired working time. The working time is to be understood as the time during which the mortar compound is still liquid so that the fastening element can be inserted. The working time must not be too short in order to be able to insert the fastening element to be fastened into the drilled hole filled with the mortar compound and to align the drilled hole appropriately. On the other hand, the working time must not be too long, otherwise the workflow at the construction site will be unnecessarily delayed.

[0007] However, the working time is strongly temperature-dependent. The temperature prevailing on the building site is an external influencing variable which cannot be influenced or controlled. Due to the increased reactivity of the components in the mortar compound at elevated temperatures, the working time decreases with increasing temperature. For mortar compounds which have a suitable working time at room temperature (approximately 20° C.), the working times obtained at, for example, 40° C. are too short. By increasing the amount of polymerization inhibitor, a suitable working time at 40° C. can be obtained. However, in the case of such mortar compounds with higher amounts of polymerization inhibitor, the working times at lower temperatures are clearly too long. Summary of the invention

[0008] Therefore, there is a need for a chemical mortar that is storage-stable and has a working time suitable for practical use in a wider temperature range. That is, an object of the present invention is to provide a chemical mortar that exhibits inhibition of polymerization at both low and elevated temperatures and provides a practically useful working time in a wide temperature range.

[0009] Surprisingly, it has been shown that the abovementioned problem is solved by a two-component mortar compound according to claim 1 or according to claim 3 .

[0010] Preferred embodiments of the mortar compound according to the invention are provided in the dependent claims, which can optionally be combined with one another.

[0011] The invention also relates to the use of the mortar compound for chemically fastening fastening elements, such as threaded anchor rods, reinforcement bars, threaded sleeves and screws, in drilled holes present in building materials, such as wood or mineral substrates, preferably concrete.

[0012] The present invention is based on the idea of ​​additionally providing otherwise conventional mortar compounds with a temperature-responsive polymerization inhibitor. According to the present invention, a "temperature-responsive polymerization inhibitor" is to be understood as an inhibitor which shows no or hardly any inhibitory effect at low temperatures or room temperature, but makes a significant inhibitory contribution at higher temperatures. In interaction with conventional polymerization inhibitors already established in mortar systems, such temperature-responsive polymerization inhibitors may have the effect that storage-stable mortar compounds may be obtained which have a working time suitable for practical use both at low temperatures and at elevated temperatures. Therefore, a specific object of the present invention is to find compounds which are compatible with specific chemical substances in complex mortar compounds, which typically have many different ingredients, and which show no or hardly any inhibitory effect on free radical curing reactions at low temperatures, such as room temperature, but show a significant inhibitory effect at elevated temperatures, such as 40°C or higher.

[0013] In a general embodiment, the present invention comprises a two-component mortar compound having a resin component (A) containing at least one radically curable resin as a curable component and a curing component (B) containing a curing agent for the radically curable resin of the resin component (A), the resin component (A) containing one or more polymerization inhibitors selected from phenolic polymerization inhibitors, phenothiazines and / or their derivatives, stable organic free radicals, oximes and pyrimidinol or pyridinol compounds substituted at the para position of the hydroxyl group, characterized in that the resin component (A) further contains an alkoxyamine compound (I) having an activation energy E for homolytic cleavage of the RO bond in the range of 100 kJ / mol to 120 kJ / mol a .

[0014] Alkoxyamines are compounds containing the structural element RON(R'R"), where R represents an alkyl group and R' or R" each represents an organic group. The NOR group in the alkoxyamine undergoes homolytic cleavage of the RO bond, i.e. a thermoreversible equilibrium is established between the alkoxyamine compound on the one hand and the alkyl radical R· and the nitroxyl radical ·ON(R'R") on the other hand. For a given alkoxyamine compound, the homolytic cleavage has a specific activation energy E a , which can be measured (or calculated). The determination of activation energy is generally known to those skilled in the art.

[0015] According to the present invention, the activation energy is determined by measuring the reaction rate constant k of the homolysis reaction at a temperature of 50° C. using electron spin resonance (ESR; electron paramagnetic resonance, EPR). The activation energy E is then calculated from the measured reaction rate constant k via the Arrhenius equation. a .

[0016]

[0017] Here the pre-exponential factor A is A = 2.4*10 14 s -1 R is the universal gas constant and T is the absolute temperature in [K]. For the measurements, a concentration of 10 -4 mol l -1 A solution of an alkoxyamine in tert-butylbenzene.

[0018] According to the present invention, the activation energy E of the homolytic cleavage of the RO bond is selected a The present inventors have found that the activation energy E of homolytic RO bond cleavage is 100 kJ / mol to 120 kJ / mol. a In the range of 40°C or more, there is hardly any homolytic cleavage at room temperature, so that there is hardly any free radical that may inhibit the free radical curing reaction of the free radical curable resin of the resin component (A) at room temperature. Therefore, the free radical curing reaction of the free radical curable resin of the resin component (A) at room temperature proceeds without being affected by the additional presence of the alkoxyamine compound (I). However, at higher temperatures, such as at a temperature of 40°C or more, the activation energy E of the homolytic cleavage of the RO bond is a In the case of the range of 100 kJ / mol to 120 kJ / mol, homolysis has already occurred significantly, so that there are sufficient free radicals to further inhibit the free radical curing reaction of the free radical curable resin of the resin component (A). Therefore, at higher temperatures, the additional presence of the alkoxyamine compound (I) has a significant inhibitory effect on the free radical curing reaction of the free radical curable resin of the resin component (A), that is, there is an extended working time at higher temperatures compared to the case where the alkoxyamine compound (I) is not present. In this way, according to the present invention, a mortar compound can be provided that exhibits a practical working time both at low temperatures and at elevated temperatures.

[0019] In a preferred embodiment, the activation energy E for homolytic cleavage of the RO bond in the alkoxyamine compound (I) is a In a more preferred embodiment, the activation energy E of the homolytic cleavage of the RO bond in the alkoxyamine compound (I) is a In the range of 100 kJ / mol to 108 kJ / mol.

[0020] In another general embodiment, the present invention comprises a two-component mortar compound having a resin component (A) containing at least one radically curable resin as a curable component and a curing component (B) containing a curing agent for the radically curable resin of the resin component (A), the resin component (A) containing one or more polymerization inhibitors selected from phenolic polymerization inhibitors, phenothiazines and / or their derivatives, stable organic radicals, oximes and pyrimidinol or pyridinol compounds substituted at the para position of the hydroxyl group, characterized in that the resin component (A) further contains an alkoxyamine compound of the following formula (II):

[0021]

[0022] in

[0023] R 1 C 3-10 Alkyl groups;

[0024] R 2 C 2-10 An alkyl group, wherein R 1 and R 2 together with the N atom to which they are bound, are capable of forming an optionally substituted, optionally unsaturated heteroalkyl ring,

[0025] R 3 H or C 1-4 Alkyl groups,

[0026] R 4 C 1-4 an alkyl group, and

[0027] R 5 is an aryl or heteroaryl group.

[0028] In the alkoxyamine compound of formula (II), R 3 R 4 R 5 The CO bond undergoes thermally reversible homolytic cleavage according to the following reaction equation:

[0029]

[0030] From the alkoxyamine compound of formula (II), through R 3 R 4 R 5 The homolytic cleavage of CO bond forms ON(R 1 R 2 ) and the nitroxyl radical of formula (R 3 R 4 R 5)C·. According to the invention, at least one of the free radicals formed in the process should be a good inhibitor of the free radical polymerization of the free radical-curable resin for resin component (A). Otherwise, the free radicals formed should not interfere with the partially complex chemistry in the mortar system. According to the invention, this is achieved by appropriate substitution in the alkoxyamine compound of formula (II).

[0031] Therefore, R in the alkoxyamine compound of formula (II) 1 Represents C 3-10 Preferably, R 1 C 4-8 Alkyl group. 1 It can be straight chain or branched chain. 1 In a preferred embodiment, R 1 represents a C branched at the α-position of the nitrogen atom 4-8 Alkyl group. 1 It may be substituted or unsubstituted.

[0032] R in the alkoxyamine compound of formula (II) 2 Represents C 2-10 Alkyl groups, such as C 4-8 Alkyl group. 2 It can be straight chain or branched chain. 2 In addition or alternatively, R 2 Optionally, branching may also be carried out in the α-position relative to the nitrogen atom. 2 It may be substituted or unsubstituted. For example, R 2 It can be substituted at the alpha position to the nitrogen atom.

[0033] Alternatively, R 1 and R 2 Together with the N atom to which they are bonded, they may optionally form a heteroalkyl ring. The heteroalkyl ring may be unsubstituted or optionally substituted. In addition, the heteroalkyl ring may be saturated or optionally partially unsaturated.

[0034] R in the alkoxyamine compound of formula (II) 3 Indicates H or C 1-4 Alkyl group. 3 It may be substituted or unsubstituted. 3 It can be straight chain or branched. In one embodiment, R 3 A hydrogen atom.

[0035] In the alkoxyamine compound of formula (II), R 4 C 1-4This means that the formula (R 3 R 4 R 5 The unpaired electrons in the alkyl radical of )C· are located on (at least) a secondary C atom or a tertiary C atom. 4 It may be substituted or unsubstituted. 4 It can be straight chain or branched. In one embodiment, R 4 A methyl group.

[0036] In the alkoxyamine compound of formula (II), R 5 is an aryl or heteroaryl group, such as C 6-20 An aryl group such as phenyl, naphthyl, anthracenyl or pyrenyl. 3 R 4 R 5 The unpaired electrons in the alkyl radical of )C· are located in the α-position of the conjugated π-system. 5 Can be substituted or unsubstituted. In one embodiment, R 5 is naphthyl or pyrenyl, preferably pyrenyl.

[0037] Optionally substituted groups R 1 , R 2 , R 3 , R 4 or R 5 The optional substituents are not particularly limited and may be selected from, for example, alkyl substituents (such as C 1-4 alkyl) or a halogen atom, etc. In one embodiment, R 1 , R 2 , R 3 , R 4 or R 5 Optionally, it may also contain a protonatable, deprotonatable or hydrolysable group. 1 , R 2 , R 3 , R 4 or R 5 Examples of protonatable optional substituents in include, but are not limited to, amine groups such as dialkylamines (e.g., di-C 1-4 alkylamine). 1 , R 2 , R 3 , R 4 or R 5 Examples of deprotonatable optional substituents in R include, but are not limited to, carboxylic acid groups, sulfonic acid groups, sulfinic acid groups, or phosphonic acid groups. 1 , R 2 , R 3 , R 4 or R 5Examples of hydrolyzable optional substituents in include, but are not limited to, alkyl esters of carboxylic acids, sulfonic acids, sulfinic acids, or phosphonic acids (e.g., C 1-4 In one embodiment, R 2 The nitrogen atom is substituted in the α-position, wherein the substituent is preferably selected from the group consisting of an alkyl carboxylate group, a sulfinate group, a sulfonate group and a phosphonate group.

[0038] In one embodiment, R in the alkoxyamine compound of formula (II) is homolytically cleaved 3 R 4 R 5 The activation energy E of the CO bond a In a preferred embodiment, the homolytic cleavage of R 3 R 4 R 5 The activation energy E of the CO bond a In a more preferred embodiment, the homolytic cleavage of R 3 R 4 R 5 The activation energy E of the CO bond a In the range of 100 kJ / mol to 108 kJ / mol.

[0039] As mentioned above, the two-component mortar composition of the present invention contains one or more conventional polymerization inhibitors in the resin component (A). According to the present invention, the (conventional) polymerization inhibitor is selected from phenolic polymerization inhibitors, phenothiazines and / or their derivatives, stable organic free radicals, oximes and pyrimidinol or pyridinol compounds substituted in the para position of the hydroxyl group. Such polymerization inhibitors are generally present in an amount of 0.1% to 1.0% by weight relative to the amount of free radical curable resin of the resin component (A).

[0040] Examples of such polymerization inhibitors are, in particular, hydroquinones, substituted hydroquinones, for example 4-methoxyphenol, phenothiazine, benzoquinone or tert-butylcatechol, as described, for example, in EP 1935860 A1 or EP 0965619 A1, nitroxyl compounds, in particular stable nitroxyl radicals, also called N-oxyl radicals, such as piperidinyl-N-oxyl or tetrahydropyrrolyl-N-oxyl, as described in DE 19531649 A1. Particularly preferably, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-N-oxyl (hereinafter referred to as tempol) is used for stabilization.

[0041] The polymerization inhibitor is preferably selected from phenolic compounds and non-phenolic compounds, such as stable free radicals and / or phenothiazines.

[0042] Possible phenolic polymerization inhibitors include phenols such as 2-methoxyphenol, 4-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol, 2,4,6-trimethylphenol, 2,4,6-tris(dimethylaminomethyl)phenol, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-isopropyldienediol, 6,6'-di-tert-butyl-4,4'-bis(2,6-di-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4 -hydroxybenzyl)benzene, 2,2'-methylene-di-p-cresol, catechol and butylcatechols such as 4-tert-butylcatechol, 4,6-di-tert-butylcatechol, hydroquinones such as hydroquinone, 2-methylhydroquinone, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butylhydroquinone, 2,6-dimethylhydroquinone, 2,3,5-trimethylhydroquinone, benzoquinone, 2,3,5,6-tetrachloro-1,4-benzoquinone, methylbenzoquinone, 2,6-dimethylbenzoquinone, naphthoquinone or a mixture of two or more thereof, which are typically components of commercial free radical curing reactive resins.

[0043] Phenothiazines, such as phenothiazine and / or its derivatives or combinations, or stable organic free radicals, such as galvinoxyl free radicals and N-oxyl free radicals, are preferably considered as non-phenolic polymerization inhibitors.

[0044] Suitable stable N-oxyl radicals (nitroxyl radicals) can be selected from 1-oxy-2,2,6,6-tetramethylpiperidine, 1-oxy-2,2,6,6-tetramethylpiperidin-4-ol (also known as TEMPOL), 1-oxy-2,2,6,6-tetramethylpiperidin-4-one (also known as TEMPON), 1-oxy-2,2,6,6-tetramethyl-4-carboxy-piperidine (also known as 4-carboxy-TEMPO), 1-oxy-2,2,5,5-tetramethylpyrrolidine, 1-oxy-2,2,5,5-tetramethyl-3-carboxypyrrolidine (also known as 3-carboxy-PROXYL), aluminum-N-nitrosophenylhydroxylamine and diethylhydroxylamine, as described in DE 199 56 509. Other suitable N-oxyl compounds are oximes, such as acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, salicyl oxime, benzoxime, glyoximes, dimethylglyoxime, acetone-O-(benzyloxycarbonyl)oxime, etc. In addition, pyrimidinol or pyridinol compounds substituted in the para position to the hydroxyl group can be used as polymerization inhibitors, as described in DE 10 2011 077 248 B1.

[0045] Depending on the desired properties and use of the resin mixture, the polymerization inhibitors can be used alone or as a combination of two or more of them. The combination of phenolic polymerization inhibitors and non-phenolic polymerization inhibitors can produce a synergistic effect, which is also shown by the essentially drift-free setting of the gel time of the reactive resin composition.

[0046] In one embodiment, the mortar compound contains 0.5 to 100 equivalents of the alkoxyamine compound (I) or the alkoxyamine compound of formula (II) relative to one equivalent of the above-mentioned (conventional) polymerization inhibitor, preferably 1 to 10 equivalents of the alkoxyamine compound (I) or the alkoxyamine compound of formula (II) per one equivalent of the conventional polymerization inhibitor.

[0047] The use of the two-component mortar compound according to the present invention to fasten the fastening elements results in a practical working time at low and elevated temperatures. According to the present invention, this is achieved by including a temperature-responsive photoinitiator, i.e., an alkoxyamine compound (I) or an alkoxyamine compound of formula (II), in the resin component (A) of the mortar compound in addition to a conventional polymerization initiator.

[0048] Further advantages of the present invention will be apparent from the following description of preferred embodiments.

[0049] For the purposes of the present invention, a "two-component mortar compound" is understood to mean a mortar compound consisting of a curable resin component and a curing component for the resin component, wherein the resin component and the curing component are stored separately from one another, so that the curing component does not react with the resin component during storage. The curing of the reactive resin is initiated by mixing the curing component with the reactive resin immediately before applying the mortar compound.

[0050] The mortar compound according to the invention may also contain at least one inorganic additive as a further component in the resin component (A) and / or the curing component (B). The term "inorganic additive" refers to all inorganic components of the mortar compound. The use of inorganic additives in mortar compounds is known in the prior art. In this context, the mortar compound according to the invention may contain a large amount of inorganic additives. For example, the amount of inorganic additives is in the range of 40 wt. % to 75 wt. % relative to the total weight of the mortar compound. In one embodiment, the amount of inorganic additives is in the range of 15 wt. % to 65 wt. %, such as in the range of 30 wt. % to 60 wt. % relative to the total weight of the mortar compound.

[0051] The inorganic additives may be selected, for example, from inorganic fillers, hydraulically setting or polycondensable inorganic compounds, modifiers, and mixtures thereof.

[0052] Preferably, the inorganic additive comprises a filler, which may be contained in the resin component (A) and / or the curing component (B). Examples of suitable fillers are BaSO4, quartz, glass, corundum, porcelain, stoneware, barite, pumice, gypsum, talc, fly ash and / or chalk and mixtures thereof, for example in the form of sand, powder or moldings, preferably in the form of fibers or balls.

[0053] According to one embodiment of the present invention, the inorganic additive further comprises a hydraulically setting or polycondensable inorganic compound, such as cement and / or gypsum, preferably a cement containing no iron oxide or only a small amount of iron oxide, such as aluminate cement. The hydraulically setting or polycondensable inorganic compound is preferably contained in the curing component (A). In this case, in addition to the curing agent and the water optionally included for desensitizing the curing agent, the curing component (B) also comprises additional water for curing the hydraulically setting or polycondensable inorganic compound.

[0054] Finally, the inorganic additives in the resin component (A) and / or the curing component (B) may contain other inorganic modifiers such as thickeners and thixotropic agents, for example precipitated or fumed silica, bentonite and / or kaolin.

[0055] The two-component mortar compound of the present invention further comprises at least one free radical curable resin as a curable component in the resin component (A). Free radical curable resins for mortar compounds are known in the prior art. Suitable free radical curable compounds according to the present invention include, for example, ethylenically unsaturated compounds, compounds having carbon-carbon triple bonds and thiol-alkyne / ene resins as known to those skilled in the art.

[0056] Among these compounds, preference is given to the group of ethylenically unsaturated compounds, which group includes: styrene and its derivatives, (meth)acrylates, vinyl esters, unsaturated polyesters, vinyl ethers, allyl ethers, itaconates, dicyclopentadiene compounds and unsaturated fats, of which unsaturated polyester resins and vinyl ester resins are particularly suitable and are described, for example, in the applications EP 1935 860 A1, DE 195 31 649 A1 and WO 10 / 108939 A1. In this case, vinyl ester resins are most preferred due to their hydrolysis resistance and excellent mechanical properties.

[0057] Examples of suitable unsaturated polyesters that can be used in the two-component mortar compounds according to the invention are classified as follows:

[0058] (1) Ortho-resins: They are based on phthalic anhydride, maleic anhydride or fumaric acid and glycols such as 1,2-propylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol or hydrogenated bisphenol-A;

[0059] (2) Meta-type resins: These are prepared from isophthalic acid, maleic anhydride or fumaric acid and diols. These resins can contain a higher proportion of reactive diluents than ortho-type resins;

[0060] (3) Bisphenol A fumarate esters: These are based on ethoxylated bisphenol A and fumaric acid;

[0061] (4) HET acidic resins (hexachloroendomethylenetetrahydrophthalic acid resins): These are resins obtained from chlorine / bromine-containing anhydrides or phenols during the preparation of unsaturated polyester resins.

[0062] In addition to these resin classes, the resins known as dicyclopentadiene resins (DCPD resins) can also be distinguished as unsaturated polyester resins. The class of DCPD resins is obtained by modifying one of the above-mentioned resin types by a Diels-Alder reaction with cyclopentadiene, or alternatively by a first reaction of a diacid (e.g. maleic acid) with dicyclopentadiene and then by a second reaction which usually produces an unsaturated polyester resin, the latter being known as DCPD maleate resins.

[0063] The unsaturated polyester resin preferably has a molecular weight M in the range of 500 Dalton to 10,000 Dalton, more preferably in the range of 500 Dalton to 5,000 Dalton, and even more preferably in the range of 750 Dalton to 4,000 Dalton. n (according to ISO 13885-1). The unsaturated polyester resin has an acid value in the range of 0 mg KOH / g resin to 80 mg KOH / g resin, preferably in the range of 5 mg KOH / g resin to 70 mg KOH / g resin (according to ISO 2114-2000). If a DCPD resin is used as the unsaturated polyester resin, the acid value is preferably 0 mg KOH / g resin to 50 mg KOH / g resin.

[0064] Vinyl ester resins within the meaning of the present invention are oligomers or polymers having at least one (meth)acrylate end group, which are referred to as (meth)acrylate functionalized resins, which also include urethane (meth)acrylate resins and epoxy (meth)acrylates.

[0065] For example, by reacting epoxy oligomers or polymers (such as bisphenol A diglycidyl ether, phenol novolac type epoxy resins or epoxy oligomers based on tetrabromobisphenol A) with, for example, (meth) acrylic acid or (meth) acrylamide, a vinyl ester resin containing only unsaturated groups at the terminal position is obtained. Preferred vinyl ester resins are (meth) acrylate functionalized resins and resins obtained by reacting epoxy oligomers or epoxy polymers with methacrylic acid or methacrylamide, preferably with methacrylic acid. Examples of such compounds are known according to applications US 3297745 A, US 3772404 A, US 4618658A, GB 2217722 A1, DE 3744390A1 and DE 4131457 A1. In this context, reference is made to application US2011 / 071234.

[0066] The vinyl ester resin preferably has a molecular weight M in the range of 500 Dalton to 3,000 Dalton, more preferably in the range of 500 Dalton to 1,500 Dalton. n (According to ISO 13885-1). The vinyl ester resin has an acid value (according to ISO 2114-2000) in the range of 0 mg KOH / g resin to 50 mg KOH / g resin, preferably in the range of 0 mg KOH / g resin to 30 mg KOH / g resin.

[0067] Ethoxylated bisphenol A di(meth)acrylates having a degree of ethoxylation of 2 to 10, preferably 2 to 4, difunctional, trifunctional or higher functional urethane (meth)acrylate oligomers, or mixtures of these curable components are particularly suitable as vinyl ester resins.

[0068] Examples of such epoxy (meth)acrylates are those of formula (A):

[0069]

[0070] Therein n represents a number greater than or equal to 1 (if a mixture of different molecules is present with different n values ​​and is represented by formula (A), non-integer values ​​may also be taken as average values).

[0071] Other examples of propoxylated or, in particular, ethoxylated aromatic diols such as bisphenol A, bisphenol F or phenolic resins, in particular di-(meth)acrylates, are those of formula (B):

[0072]

[0073] wherein a and b each independently represent a number greater than or equal to 0, with the proviso that preferably at least one of these values ​​is greater than 0, preferably both are greater than 1 or more (if a mixture of different molecules with different (a and b) values ​​is present and represented by formula (B), non-integer numbers may also be taken as average values).

[0074] The known reaction products of diisocyanates or polyisocyanates with hydroxyalkyl methacrylates (described, for example, in DE 2312 559 A1), the adducts of (di)isocyanates and 2,2-propanebis[3-(4-phenoxy)-1,2-hydroxypropane-1-methacrylate] according to US Pat. No. 3,629,187, and the adducts of isocyanates and methacryloylalkyl ethers, alkoxybenzenes or alkoxycycloalkanes described in EP 44352 A1 are very particularly suitable. In this context, reference is made to DE 2312559 A1, DE 19902685 A1, EP 0684906 A1, DE 4111828 A1 and DE 19961342 A1.

[0075] Of course, mixtures of suitable monomers can also be used.

[0076] All these resins that can be used according to the invention can be modified according to methods known to those skilled in the art, for example to achieve a lower acid, hydroxide or anhydride value, or can be made more flexible by introducing flexible units into the backbone, etc.

[0077] Additionally, the resin may contain other reactive groups that can polymerize with free radical initiators, such as peroxides, for example reactive groups derived from itaconic acid, citraconic acid and allyl groups, etc., as described, for example, in WO 2010 / 108939 (itaconates).

[0078] The percentage proportion of the radically curable resin in the resin component (A) (in % by weight of the reactive resin) is advantageously greater than about 5%, preferably greater than about 15%, and particularly preferably greater than about 20%. The percentage proportion of the radically curable resin in the resin component (in % by weight of the resin component) is advantageously from about 10% to about 90%, preferably from about 15% to about 80%, more preferably from about 20% to about 60%, more preferably from about 25% to about 55%, even more preferably from about 30% to about 55%, particularly preferably from about 30% to about 50%, and very particularly preferably from about 32% to about 45%.

[0079] The radical curable resin in component (A) of the mortar compound according to the present invention preferably comprises a urethane (meth)acrylate resin and / or a (meth)acrylate-modified epoxy resin. In a preferred embodiment, the radical curable resin is a urethane (meth)acrylate resin.

[0080] To prepare suitable urethane (meth)acrylate resins, at least a difunctional isocyanate may be reacted with one or more hydroxyl-functional ethylenically unsaturated compounds, in particular a hydroxyl-functional (meth)acrylic compound.

[0081] The at least difunctional isocyanates used for preparing the urethane (meth)acrylate resins may be aromatic isocyanates, aliphatic isocyanates, in particular cycloaliphatic isocyanates and prepolymers containing isocyanate groups, which can also be used in the form of a mixture with one another.

[0082] Examples of suitable aliphatic and aromatic isocyanates include m-phenylene diisocyanate, toluene-2-4-diisocyanate, toluene-2-6-diisocyanate, hexamethylene-1,6-diisocyanate, tetramethylene-1,4-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrotoluene diisocyanate, naphthylene-1,5-diisocyanate, methoxyphenyl-2,4-diisocyanate, diphenylmethane-4,4′-diisocyanate, 4,4′-biphenyl diisocyanate, 3,3'-dimethoxy-4,4'-diphenyl diisocyanate, 3,3'-dimethyl-4,4'-diphenyl diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4',4"-triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate (PMDI), toluene-2,4,6-triisocyanate and 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate.

[0083] Diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate and mixtures thereof are collectively referred to as MDI, and all may be used. Toluene-2,4-diisocyanate, toluene-2,6-diisocyanate and mixtures thereof are generally referred to as TDI, and all may also be used.

[0084] Preferably, the polyisocyanate is selected from diphenylmethane diisocyanate (MDI), polymeric diphenylmethane diisocyanate (PMDI), toluene diisocyanate (TDI), hexane diisocyanate (HDI), isophorone diisocyanate (IPDI) and mixtures thereof.

[0085] It is also possible to use isocyanate prepolymers which are prepared by reacting a stoichiometric excess of any polyisocyanate with an isocyanate-reactive compound as chain extender, optionally in the form of a mixture with the abovementioned aromatic and aliphatic isocyanates.

[0086] Examples of such chain extenders are divalent alcohols such as ethylene glycol, diethylene glycol or triethylene glycol and polyethylene glycols, propylene glycol, dipropylene glycol, tripropylene glycol and polypropylene glycols, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and diethanolamine, further aromatic alcohols such as bisphenol A or bisphenol F or ethoxylated, hydrogenated and / or halogenated products thereof, higher alcohols such as glycerol, trimethylolpropane, hexanetriol and pentaerythritol, polyethers containing hydroxyl groups, for example Oligomers of aliphatic or aromatic oxiranes and / or higher cyclic ethers such as ethylene oxide, propylene oxide, styrene oxide and furan, polyethers containing aromatic structural units in the main chain, such as polyethers of bisphenol A and bisphenol F, polyesters containing hydroxyl groups based on the above alcohols and polyethers and dicarboxylic acids or their anhydrides such as adipic acid, phthalic acid, tetrahydrophthalic acid or hexahydrophthalic acid, heteroacids, maleic acid, fumaric acid, itaconic acid, sebacic acid.

[0087] Chain extenders with aromatic structural units are used to harden the chains of the resin. Hydroxyl compounds with unsaturated structural units, such as fumaric acid, can be used to increase the crosslink density during curing. Branched or star-shaped hydroxy compounds as chain extenders, in particular triols and higher alcohols and polyethers and / or polyesters containing their structural units, produce branched or star-shaped urethane (meth) acrylates that exhibit lower resin viscosity and improved solubility in reactive diluents.

[0088] The hydroxyl-functional (meth)acrylic compound used to prepare the urethane (meth)acrylate resin of resin component (A) is preferably a hydroxyalkyl (meth)acrylate, such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, polyoxyethylene (meth)acrylate, polyoxypropylene (meth)acrylate, or a hydroxyl group-containing (meth)acrylate of a polyol, such as pentaerythritol tri(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane di(meth)acrylate and neopentyl glycol mono(meth)acrylate.

[0089] The name "(meth)acryloyl..." or "...(meth)acryloyl..." as used herein and hereinafter means that the name is intended to include both acrylic and methacrylic groups.

[0090] The reaction of the at least difunctional isocyanate with the hydroxy-functional ethylenically unsaturated compound is carried out in such a way that the resulting free-radically curable resin of the resin component (A) is substantially free of free isocyanate groups. Here, "substantially free" means that the resin has an NCO content of less than 2%, preferably less than 1%, and particularly preferably less than 0.3%. For this purpose, the hydroxy-functional ethylenically unsaturated compound is used in a stoichiometric excess relative to the isocyanate groups.

[0091] Other free-radically curable resins which can be used are, for example, vinyl esters, epoxy (meth)acrylates, unsaturated polyester resins and mixtures thereof, alone or also together with the abovementioned (poly)urethane (meth)acrylates.

[0092] The unsaturated polyester resin is obtained by reacting an unsaturated dicarboxylic acid such as phthalic acid and / or isophthalic acid, maleic acid and fumaric acid with a diol.

[0093] Epoxy (meth)acrylates are generally condensates of (meth)acrylic acid with the glycidyl ether of bisphenol A, bisphenol F or novolac.

[0094] The radically curable resin is present in the mortar compound in a proportion of 10% to 40% by weight, for example.

[0095] According to a preferred embodiment of the present invention, the resin component (A) in all the above embodiments contains at least one reactive diluent as a further component, the reactive diluent having at least one ethylenically unsaturated group. Specifically, suitable reactive diluents are (meth)acrylate compounds as well as allyl compounds and vinyl compounds.

[0096] Suitable reactive diluents are described in EP 1 935 860 A1 and DE 195 31 649 A1. Preferably, the resin mixture contains (meth)acrylates as reactive diluents, particularly preferably aliphatic or aromatic C5-C6 acrylates. 15(Meth)acrylates. Suitable examples include: hydroxypropyl (meth)acrylate, 1,2-ethylene glycol di(meth)acrylate, 1,3-propylene glycol di(meth)acrylate, 1,2-butylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate (BBDMA), trimethylolpropane tri(meth)acrylate, phenylethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, triethylene glycol ethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminomethyl (meth)acrylate, acetoacetoxyethyl (meth)acrylate, isobornyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, diethylene glycol di(meth)acrylate, methoxypolyethylene glycol mono(meth)acrylate, trimethylcyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate and / or di(meth)acrylate. ) tricyclopentadienyl acrylate, bisphenol A-(meth)acrylate, novolac epoxy di(meth)acrylate, di-[(meth)acryloyl-maleoyl]-tricyclo-5.2.1.0.2.6-decane, dicyclopentenyloxyethyl crotonate, 3-(meth)acryloyl-oxymethyl-tricyclo-5.2.1.0.2.6-decane, 3-(meth)cyclopentadienyl (meth)acrylate, isobornyl (meth)acrylate and decalyl-2-(meth)acrylate; PEG-di(meth)acrylates such as PEG200 di(meth)acrylate, tetraethylene glycol di(meth)acrylate, acetone (meth)acrylate acetal, cyclohexyl (meth)acrylate, phenoxyethyl di(meth)acrylate, methoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, tert-butyl (meth)acrylate and norbornyl (meth)acrylate.

[0097] In principle, other customary free-radically curable compounds can also be used, alone or in a mixture with (meth)acrylates, for example styrene, α-methylstyrene, alkylated styrenes such as tert-butylstyrene, divinylbenzene and allyl compounds, of which representatives which are not subject to mandatory labeling are preferred.

[0098] Particularly preferred reactive diluents are hydroxypropyl(meth)acrylate, 1,4-butanediol di(meth)acrylate and butanediol-1,2-di(meth)acrylate.

[0099] The reactive diluent acts as a solvent for the free-radically curable resin on the one hand and as a comonomer which participates in the free-radical polymerization of the resin component on the other hand. The use of reactive diluents leads to a further improvement in the adhesion of the cured mortar compound to the surface of the mineral substrate and / or the fastening element to be fastened.

[0100] The reactive diluent is present in the mortar compound, for example, in a proportion of 0% to 25% by weight, such as 4% to 25% by weight, or 8% to 15% by weight. All radically curable compounds are preferably present in the mortar compound in a proportion of up to 30% by weight.

[0101] According to another preferred embodiment of the present invention, the resin component (A) comprises at least one accelerator for the curing agent. Suitable accelerators that are usually added to the resin mixture are known to those skilled in the art. These accelerators are, for example, amines, preferably tertiary amines and / or metal salts.

[0102] Suitable amines are selected from the following compounds, for example, the compounds described in application US2011071234 A1: dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-propylamine, isopropylamine, diisopropylamine, triisopropylamine, n-butylamine, isobutylamine, tert-butylamine, di-n-butylamine, diisobutylamine, triisobutylamine, amylamine, isoamylamine, diisoamylamine, hexylamine, octylamine, dodecylamine, laurylamine, stearylamine, aminoethanol, diethanolamine, triethanolamine, aminohexanol, ethoxyaminoethane, dimethyl(2-chloroethyl)amine, 2-ethylhexylamine, bis(2-chloroethyl)amine, 2-ethylhexylamine, bis(2-ethylhexyl)amine, N-methylstearylamine, dialkylamines, ethylenediamine, N,N'-dimethylethylenediamine, tetramethylethylenediamine, diethylenetriamine, permethyl Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,2-diaminopropane, dipropylenetriamine, tripropylenetetramine, 1,4-diaminobutane, 1,6-diaminohexane, 4-amino-1-diethylaminopentane, 2,5-diamino-2,5-dimethylhexane, trimethylhexamethylenediamine, N,N-dimethylaminoethanol, 2-(2-diethylaminoethoxy)ethanol, bis(2-hydroxyethyl)oleylamine, tris[2(2-hydroxyethoxy)ethyl]amine, 3-amino-1-propanol, methyl (3-aminopropyl) ether, ethyl-(3-aminopropyl) ether, 1,4-butanediol-bis(3-aminopropyl ether), 3-dimethylamino-1-propanol, 1-amino-2-propanol, 1 -Diethylamino-2-propanol, diisopropanolamine, methyl-bis(2-hydroxypropyl)amine, tris(2-hydroxypropyl)amine, 4-amino-2-butanol, 2-amino-2-methylpropanol, 2-amino-2-methylpropanediol, 2-amino-2-hydroxymethylpropanediol, 5-diethylamino-2-pentanone, 3-methylaminopropionitrile, 6-aminocaproic acid, 11-aminoundecanoic acid, 6-aminocaproic acid ethyl ester, 11-aminocaproic acid-isopropyl ester, cyclohexylamine, N-methylcyclohexylamine, N,N-dimethylcyclohexylamine, dicyclohexylamine, N-ethylcyclohexylamine, N-(2-hydroxyethyl)cyclohexylamine, N,N-bis(2-hydroxyethyl)cyclohexylamine, N-(3-aminopropyl)cyclohexylamine, aminomethylcyclohexane, hexahydro Toluidine, hexahydrobenzylamine, aniline, N-methylaniline, N,N-dimethylaniline, N,N-diethylaniline, N,N-dipropylaniline, isobutylaniline, toluidine, diphenylamine, hydroxyethylaniline, bis(hydroxyethyl)aniline, chloroaniline, aminophenol, aminobenzoic acid and its esters, benzylamine, dibenzylamine, tribenzylamine, methyldibenzylamine, α-phenylethylamine, dimethylaniline, diisopropylaniline, dodecylaniline, aminonaphthalene, N-methylaminonaphthalene, N,N-dimethylaminonaphthalene, N,N-dibenzylnaphthalene, diaminocyclohexane, 4,4'-diamino-dicyclohexylmethane, diamino-dimethyl-dicyclohexylmethane, phenylenediamine, phenylenediamine, diaminobiphenyl, naphthalenediamine, toluidine, benzidine, 2,2-Bis(aminophenyl)propane, aminoanisole, aminothiophenol, aminodiphenyl ether, aminocresol, morpholine, N-methylmorpholine, N-phenylmorpholine, hydroxyethylmorpholine, N-methylpyrrolidine, pyrrolidine, piperidine, hydroxyethylpiperidine, pyrrole, pyridine, quinoline, indole, indoline, carbazole, pyrazole, imidazole, thiazole, pyrimidine, quinoxaline, aminomorpholine, dimorpholineethane, [2,2,2]-diazabicyclooctane and N,N-dimethyl-p-toluidine.

[0103] Preferred amines are aniline derivatives and N,N-bisalkylarylamines, such as N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-toluidine, N,N-bis(hydroxyalkyl)arylamine, N,N-bis(2-hydroxyethyl)aniline, N,N-bis(2-hydroxyethyl)toluidine, N,N-bis(2-hydroxypropyl)aniline, N,N-bis(2-hydroxypropyl)toluidine, N,N-bis(3-methacryloyl-2-hydroxypropyl)-p-toluidine, N,N-dibutoxyhydroxypropyl-p-toluidine and 4,4′-bis(dimethylamino)diphenylmethane.

[0104] Polymeric amines, such as those obtained by polycondensation of N,N-bis(hydroxyalkyl)anilines with dicarboxylic acids or by polyaddition of ethylene oxide and these amines, are also suitable as accelerators.

[0105] Suitable metal salts are, for example, cobalt octoate or cobalt naphthenate and vanadium, potassium, calcium, copper, manganese or zirconium carboxylates.

[0106] The resin mixture may also contain a co-promoter, in particular when a transition metal compound is used as a promoter. Depending on the selected transition metal compound, a person skilled in the art will be able to select a suitable co-promoter to achieve the desired curing characteristics. When a cobalt compound is used as a promoter, the co-promoter is preferably an amine and / or a 1,3-dioxo compound. When a copper compound is used as a promoter, the co-promoter is preferably an amine, acetoacetamide, potassium salt, imidazole and / or gallic acid ester or a mixture thereof. When a manganese compound is used as a promoter, the co-promoter is preferably a 1,3-dioxo compound, a thiol and / or a potassium salt or a lithium salt or a mixture thereof. When an iron compound is used as a promoter, the co-promoter is preferably a 1,3-dioxo compound and / or a thiol, preferably in combination with an alkali metal salt. Suitable 1,3-dioxo compounds are acetylacetone, acetoacetate and acetoacetamide.

[0107] For example, the accelerator and / or co-accelerator is present in the mortar compound in a proportion of 0 wt % to 1 wt %, such as 0.01 wt % to 0.7 wt %.

[0108] Finally, the mortar compound may contain further organic additives, such as adhesion improvers based on silane compounds, as are known to the person skilled in the art, for example from EP 2 371 782 A2 and WO 2011 / 072789 A1.

[0109] The curing agent of the radical-curable resin of the resin component (A) contained in the curing component (B) of the two-component mortar compound according to the present invention preferably comprises at least one organic peroxide, for example dibenzoyl peroxide, methyl ethyl ketone peroxide, tert-butyl perbenzoate, cyclohexanone peroxide, lauryl peroxide, cumene hydroperoxide and / or tert-butyl peroxy-2-ethylhexanoate.

[0110] The organic peroxide is preferably desensitized, in particular by adding water as desensitizing agent and / or solvent. Suitable curing components are known to those skilled in the art and are commercially available.

[0111] Alternatively, a peroxide-free curing system may be used for curing, which contains the following ingredients:

[0112] - at least one manganese compound as promoter, and

[0113] - 1,3-dioxo compounds as initiators.

[0114] For this purpose, reference is made to DE 10 2011 078 785 A1.

[0115] Also alternatively, a curing system comprising the following ingredients may be used for curing:

[0116] - at least one metal salt as a promoter, and

[0117] - at least one compound containing thiol and / or thiol ester groups as initiator.

[0118] For this purpose, see DE 10 2013 114 061 A1.

[0119] As a result of the combination or mixing of these two components, free radicals can be formed which, instead of the free radical formers customary before, can initiate the polymerization of nonaromatic double bonds, for example olefinic double bonds, such as acrylates or methacrylates.

[0120] As another alternative, a curing system comprising the following ingredients may be used for curing:

[0121] - at least one metal salt as a promoter, and

[0122] - as initiator at least one CH-acidic compound of the formula

[0123]

[0124] in

[0125] (i)

[0126] -A means -C(R 1 )(R 2 )-,

[0127] -X- indicates -NR 3 -or-(CR 4 R 5 ) p -key or -O-,

[0128] Y stands for NR 6 or (CR 7 R 8 ) q or O,

[0129] If X represents O, then Y also represents O;

[0130] Wherein X preferably represents (CR 4 R 5 ) p And Y represents CR 7 R 8 ,

[0131] Or X means NR 3 And Y represents NR 6 ;

[0132] Z 1 represents O, S, S=O or S(=O)2,

[0133] Z 2 represents O, S, S=O or S(=O)2,

[0134] Z 3 Indicates O, S, S=O or S(=O)2 or R 9 and R 10 ,

[0135] p represents 1, 2 or 3, preferably 1 or 2

[0136] q represents 1, 2 or 3, preferably 1;

[0137] And the functional group R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10Each independently represents hydrogen, alkyl, aryl, aralkyl, cycloalkyl or cycloalkylalkyl, and is unsubstituted or substituted and / or heteroatoms (replacing C atoms;

[0138] is preferably selected from O, N (such as NH or N-alkyl) and S, provided that the functional group R 1 and R 2 At least one of represents hydrogen,

[0139] or

[0140] (ii) open chain compounds,

[0141] The bridge-forming connection -C(=Z 3 )-,

[0142] -A- means -C(R 1 )(R 2 )-, X and Y each independently represent in each case unbranched or branched, unsubstituted or substituted C1-C4-alkyl or C1-C4-alkoxy, which optionally has heteroatoms (instead of C atoms; in particular selected from O, N (such as NH or N-alkyl) and S) or in each case preferably represent unsubstituted or substituted C1-C4-alkoxycarbonylmethyl or C1-C4-alkylcarbonylmethyl, which optionally has heteroatoms (instead of C atoms; in particular selected from O, N (such as NH or N-alkyl) and S),

[0143] R 1 and R 2 are all hydrogen, and

[0144] Z 1 and Z 2 has the meaning given above;

[0145] or X in each case denotes an unbranched or branched, unsubstituted or substituted C1-C4-alkyl group or a C1-C4-alkoxy group or a C1-C4-alkoxycarbonylmethyl group or a C1-C4-alkylcarbonylmethyl group, which optionally has heteroatoms (instead of the C atoms; in particular selected from O, N (such as NH or N-alkyl) and S),

[0146] Y and Z 2 Together with the bonded carbon atom it is -CN,

[0147] Z 1 has the meaning given above, and

[0148] R 1 and R 2 as defined above in each case, with the proviso that at least one of the functional groups is hydrogen;

[0149] and / or their salts. For this purpose, see DE 10 2015 003 221 A1.

[0150] In both cases, the component used as promoter in the form of metal salts (also including metal complexes and metal oxides) is preferably one or more metal salts or in particular salts of organic and / or inorganic acids with metals selected, for example, from cobalt, zirconium, zinc, cerium, tin, bismuth or preferably vanadium, manganese, copper or iron, or mixtures of two or more thereof, wherein the organic acids are preferably saturated, wherein vanadium and iron or in particular manganese and copper are preferred, optionally in the presence of one or two co-promoters having a metal content from the group of the abovementioned metals, in particular in the form of salts or complexes with inorganic acids and / or carboxylate functional groups, such as with CH3, C2-C 20 Alkyl, C6-C 24 Aryl functional group or C7-C 30 Carboxylates of aralkyl functional groups, for example octanoates, for example 2-ethylhexanoate (isooctanoate), other neodecanoates or acetylacetonates. Particularly preferred are manganese carbonates or carboxylates, such as manganese acetate or octanoate; copper carboxylates, such as copper octanoate or copper naphthenate, copper quinolinate; iron carboxylates, such as iron octanoate; and / or vanadium carboxylates; and / or the group of metal salts with inorganic acids, for example including iron chloride, iron sulfate and copper chloride.

[0151] In another alternative, a hardening system comprising the following ingredients may be used for curing:

[0152] - at least one metal salt as a promoter, and

[0153] - at least one aldehyde and / or ketone and at least one primary amine as initiator, and / or

[0154] -b2) at least one imine comprising one or more imine structural extensions of the following formula:

[0155]

[0156] Each of which independently:

[0157] Q represents the organic functional group of the amine used (in each case), or represents hydrogen; and

[0158] R 2 and R 3 Each independently is hydrogen and / or an unsubstituted or substituted, mono-branched or poly-branched or linear organic functional group, which organic functional group optionally has double bonds and / or heteroatoms and comprises at least one aliphatic, heteroaliphatic, alicyclic or heterocyclic molecular structure, or a combination of two or more of the above molecular structures;

[0159] and / or their salts,

[0160] For this purpose, see DE 10 2016 124 075 A1.

[0161] In order to set a suitable viscosity, the curing component may contain a certain proportion of an inorganic filler and a modifier such as a thixotropic agent.

[0162] The two-component mortar compound according to the invention is preferably present in a capsule, cartridge or film bag, characterized in that it contains two or more separate chambers, in which the resin component (A) and the curing component (B) of the mortar compound are arranged separately in order to prevent reaction.

[0163] For intended use, the resin component (A) and the curing component (B) are discharged from separate chambers and mixed in a suitable device (e.g., a static mixer). The mixture of the resin component (A) and the curing component (B) is then introduced into a previously cleaned borehole using a known injection device. The fastening element to be fastened is then inserted into the mortar compound and aligned. The curing agent of the curing component (B) initiates free radical polymerization of the resin component (A), so that the mortar compound cures within a few hours under ambient conditions.

[0164] The invention therefore also relates to the use of a two-component mortar compound according to the invention for chemically fastening fastening elements, in particular anchor threaded rods, reinforcement bars, threaded sleeves and screws, in drilled holes present in building materials such as wood or mineral substrates, preferably concrete. DETAILED DESCRIPTION

[0165] The present invention is described below based on preferred exemplary embodiments, which however should not be understood as being limiting in any way.

[0166] Example:

[0167] Preparation of components

[0168] The compositions of the resin components used in Comparative Example V1 and Application Example A1 below are shown in Table 1 below.

[0169] Table 1:

[0170]

[0171] * Urethane methacrylate resin according to WO 2019 / 007667, Example C1

[0172] Table 2 below shows the compositions of Comparative Example V1 and Application Example A1, in each case in parts by weight. In Application Example A1, the following compound (AV1) was used as alkoxyamine compound of the formula (I):

[0173]

[0174] The alkoxyamine compound AV1 (diethyl (1-(tert-butyl (1-(pyrene-1-yl) ethoxy) amino) -2,2-dimethylpropyl) phosphonate; MW: 523.6 g / mol) has an activation energy E for homolytic RO bond of 105.32 kJ / mol. a The amount of AV1 used in Application Example A1 corresponds to 4 equivalents relative to one equivalent of the polymerization inhibitor (Tempol).

[0175] Table 2:

[0176]

[0177] In each case, Perkadox 20S was used as B component, which is a mixture containing 20% ​​by weight of dibenzoyl peroxide on calcium sulfate / basic magnesium carbonate, available from Akzo Nobel. 3 g of the corresponding A component were tempered in a low-speed mixer at 5° C. for at least 3 hours. Then, 900 mg of the B component were mixed in a high-speed mixer (1500 rpm / 60 s) and the sample was immediately weighed into a DSC crucible (aluminum 40 μL-D).

[0178] After this, isothermal measurements of the curing curves at 20°C, 40°C and 60°C were performed. The crucible tempered at 5°C was placed in a DSC chamber tempered at the measuring temperature and the measurement was started. The gel time (time to peak) was measured from the mixing time. The measurement was carried out under N2 (duration: 120 minutes). The results obtained here (in [min]) are shown in Table 3.

[0179] Table 3:

[0180] Measuring temperature V1 A1 extend 20℃ 10 12.5 25％ 40℃ 2.1 3 42％ 60℃ 0.55 0.95 72％

[0181] At room temperature, the addition of the alkoxyamine compound AV1 showed only a slight extension of the gel time of 25%. At 40° C., the extension of the gel time by the addition of the alkoxyamine compound AV1 was already significant at 42%. The extension of the gel time by the addition of the alkoxyamine compound AV1 was particularly significant at 60° C. at 72%.

[0182] Components used:

[0183] BDDMA Evonik Performance Materials GmbH / DE HPMA Evonik Performance Materials GmbH / DE Pd Saltigo GMBH, Leverkusen / DE Tempol Evonik Performance Materials GmbH / DE TS 720 Cabot / Switzerland Perkadox 20S Akzo Nobel / USA

Claims

1. A two-component mortar compound, comprising a resin component (A) containing at least one radically curable resin as a curable component and a curing component (B) containing a curing agent for the radically curable resin of the resin component (A), wherein the resin component (A) contains one or more polymerization inhibitors selected from phenolic polymerization inhibitors, phenothiazines and / or their derivatives, stable organic free radicals, oximes and pyrimidinol or pyridinol compounds substituted at the para position of the hydroxyl group, It is characterized in that The resin component (A) further contains an alkoxyamine compound (I) of the formula RON(R'R"), wherein R represents an alkyl group, and R' and R" each represent an organic group, and which has an activation energy E for homolytic cleavage of the RO bond in the range of 100 kJ / mol to 120 kJ / mol. a .

2. The mortar compound according to claim 1, wherein the alkoxyamine compound (I) has an activation energy E for homolytic cleavage of the RO bond in the range of 100 kJ / mol to 110 kJ / mol, preferably 100 kJ / mol to 108 kJ / mol. a .

3. A two-component mortar compound, comprising a resin component (A) containing at least one radically curable resin as a curable component and a curing component (B) containing a curing agent for the radically curable resin of the resin component (A), wherein the resin component (A) contains one or more polymerization inhibitors selected from phenolic polymerization inhibitors, phenothiazines and / or their derivatives, stable organic radicals, oximes and pyrimidinol or pyridinol compounds substituted at the para position of the hydroxyl group, It is characterized in that The resin component (A) further contains an alkoxyamine compound of the following formula (II): in R 1 C 3-10 Alkyl groups; R 2 C 2-10 An alkyl group, wherein R 1 and R 2 together with the N atom to which they are bound, are capable of forming an optionally substituted, optionally unsaturated heteroalkyl ring, R 3 H or C 1-4 Alkyl groups, R 4 C 1-4 an alkyl group, and R 5 is an aryl or heteroaryl group.

4. The mortar compound according to claim 3, wherein in the alkoxyamine compound of formula (II) R 1 Branched at the α-position of the nitrogen atom, preferably C 4-8 Alkyl groups, R 2 branched in the β-position to the nitrogen atom, and optionally branched or substituted in the α-position to the nitrogen atom, wherein the substituents are preferably selected from alkyl carboxylate groups, sulfinate groups, sulfonate groups and phosphonate groups, and R 5 is unsubstituted or substituted C 6-20 an aryl group, and Where R 1 , R 2 , R 3 , R 4 or R 5 Optionally, it also contains protonatable, deprotonatable or hydrolysable groups.

5. The mortar compound according to any one of claims 3 or 4, wherein the alkoxyamine compound of formula (II) has a carbonyl group for homolytic cleavage of R in the range of 100 kJ / mol to 120 kJ / mol, preferably 100 kJ / mol to 110 kJ / mol, more preferably 100 kJ / mol to 108 kJ / mol. 3 R 4 R 5 The activation energy E of the CO bond a .

6. The mortar compound according to any one of the preceding claims, wherein the alkoxyamine compound (I) or the alkoxyamine compound of formula (II) is present in an amount of 0.5 to 100 equivalents, preferably 1 to 10 equivalents, relative to one equivalent of the polymerization inhibitor.

7. The mortar composition according to any one of the preceding claims, wherein the resin component (A) and / or the curing component (B) comprises as a further ingredient at least one inorganic additive selected from the group consisting of inorganic fillers, hydraulically setting or polycondensable inorganic compounds, modifiers and mixtures thereof.

8. The mortar composition according to claim 7, wherein the inorganic additive comprises a filler selected from the group consisting of: BaSO4, quartz, glass, corundum, porcelain, stoneware, barite, pumice, gypsum, talc, fly ash, chalk and mixtures thereof.

9. A mortar composition according to any one of claims 7 or 8, wherein the inorganic additive comprises a hydraulically setting or polycondensable inorganic compound selected from cement and gypsum and mixtures thereof, preferably aluminate cement.

10. Mortar compound according to any one of claims 7 to 9, wherein the inorganic additive comprises a modifier selected from thickeners, plasticizers, thixotropic agents and mixtures thereof, preferably precipitated or fumed silica, bentonite and / or kaolin.

11. The mortar compound according to any one of the preceding claims, wherein the radically curable resin is selected from the group consisting of urethane (meth)acrylate-based compounds, epoxy (meth)acrylate-based compounds, methacrylates of alkoxylated bisphenols and compounds based on other ethylenically unsaturated compounds, wherein the radically curable resin is preferably selected from the group consisting of urethane (meth)acrylate-based compounds, epoxy (meth)acrylate-based compounds and methacrylates of alkoxylated bisphenols, and wherein more preferably the radically curable resin comprises a urethane (meth)acrylate resin. 12 . The mortar compound according to claim 1 , wherein the resin component (A) comprises at least one reactive diluent as a further constituent.

13. The mortar compound according to any one of the preceding claims, wherein the resin component (A) comprises at least one accelerator as a further ingredient.

14. The mortar composition according to any one of the preceding claims, wherein the curing component (B) comprises at least one organic peroxide, in particular dibenzoyl peroxide, methyl ethyl ketone peroxide, tert-butyl perbenzoate, cyclohexanone peroxide, lauryl peroxide, cumene hydroperoxide and / or tert-butyl peroxy-2-ethylhexanoate as a curing agent.

15. The mortar compound according to any one of the preceding claims, wherein the composition is in a capsule, cartridge or film bag, the resin component (A) and the curing component (B) being arranged in separate chambers.

16. Use of a two-component mortar compound according to any of the preceding claims for chemically fastening fastening elements such as threaded anchor rods, reinforcement bars, threaded sleeves and screws in drill holes present in building materials such as wood or mineral substrates.

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