A two-component mortar composition containing a temperature response inhibitor.

Abstract

In a general form, the present invention relates to a two-component mortar composition comprising a resin component (A) containing at least one radical-curable resin as a curable component, and a curing agent component (B) containing a curing agent for the radical-curable resin of the resin component (A), wherein the resin component (A) contains one or more polymerization inhibitors selected from phenolic polymerization inhibitors, phenothiazine and / or its derivatives, stable organic radicals, oximes, and pyrimidinol or pyridinol compounds substituted at the para position with respect to the hydroxyl group. In the mortar composition, the resin component (A) further contains an alkoxyamine compound (I) of the formula R-O-N(R’R”) (wherein R is an alkyl group and R’ or R” is an organic group), and this compound has an activation energy E for the homolysis of the R-O bond in the range of 100 kJ / mol to 120 kJ / mol a characterized by having the above. In another embodiment, the present invention relates to a two-component mortar composition comprising a resin component (A) containing at least one radical-curable resin as a curable component, and a curing agent component (B) containing a curing agent for the radical-curable resin of the resin component (A), wherein the resin component (A) contains one or more polymerization inhibitors selected from phenolic polymerization inhibitors, phenothiazine and / or its derivatives, stable organic radicals, oximes, and pyrimidinol or pyridinol compounds substituted at the para position with respect to the hydroxyl group, and the resin component (A) further contains an alkoxyamine compound of the following formula (II) TIFF2025518937000015.tif18150. Furthermore, the present invention relates to the use of a two-component mortar composition for chemically fixing fixing elements such as anchor threaded rods, reinforcing bars, threaded sleeves, and screws in drilled holes of building materials such as wood or mineral substrates.

Description

[Technical Field]

[0001] A two-component mortar composition comprising a resin component (A) containing at least one radical-curable resin as a curable component, and a solidifying agent component (B) containing a solidifying agent for the radical-curable resin of resin component (A). The resin component (A) of the two-component mortar composition according to the present invention further contains one or more conventional polymerization inhibitors selected from phenolic polymerization inhibitors, phenothiazines and / or derivatives thereof, stable organic radicals, oximes, and pyrimidinol or pyridinol compounds substituted at the para position with respect to a hydroxyl group. The two-component mortar composition of the present invention is characterized in that the resin component (A) further contains an alkoxyamine compound as a temperature-responsiveness inhibitor. The present invention also relates to the use of a mortar composition for chemically fixing elements such as threaded anchor rods, reinforcing bars, threaded sleeves and screws in boreholes made in a mineral substrate.

[0002] To securely fasten fastening elements such as threaded anchor rods, reinforcing bars, threaded sleeves, and screws to a mineral substrate such as concrete, natural stone, or plaster, a borehole for receiving the fastening elements is first drilled in the mineral substrate to the appropriate dimensions. Next, drilling dust is removed from the borehole, and a two-component mortar composition is introduced into the borehole after mixing the resin component with the hardening agent component. Then, the fastening elements to be fastened are inserted into the borehole filled with the mortar composition and adjusted. After the mortar composition hardens due to the reaction between the resin component and the hardening agent component, the fastening elements are firmly held in the mineral substrate.

[0003] The load-bearing behavior of such fixed elements depends on several influencing variables, which are typically classified as internal and external variables. Influencing internal variables include the chemical composition of the mortar composition, its production process, and the packaging of the mortar composition, which typically contains components present in two separate containers.

[0004] External variables that have an impact include the type of cleanliness of the borehole, the quality of the mineral substrate such as concrete, its moisture and temperature, and the type of borehole formation.

[0005] Two-component mortar compositions based on urethane (meth)acrylate resins that harden by free radical polymerization are known from European Patent No. 0432087 and European Patent No. 0589831.

[0006] Mortar compositions based on radical-curing reactive resins, known in the prior art and used as chemical bond anchors, typically contain polymerization inhibitors. Such conventional polymerization inhibitors are selected from phenolic polymerization inhibitors, phenothiazines and / or their derivatives, stable organic radicals, oximes, and pyrimidinol or pyridinol compounds substituted at the para position relative to the hydroxyl group. Polymerization inhibitors can be used, on the one hand, to ensure a certain storage stability of the mortar composition, and on the other hand, to set a desired working time. Working time is understood as the time during which the mortar composition is still liquid and can be used to insert fixed elements. The working time should not be too short to allow for the insertion and proper alignment of fixed elements to be fixed into boreholes filled with the mortar composition. On the other hand, the working time should not be too long, otherwise the workflow at the construction site will be unnecessarily delayed.

[0007] However, working time is highly temperature-dependent. The temperature encountered at a construction site is an influencing external variable that cannot be influenced or controlled. As the reactivity of components in the mortar composition increases at high temperatures, the working time decreases with increasing temperature. For example, a mortar composition with a suitable working time at room temperature (approximately 20°C) will have a working time that is too short at 40°C. A suitable working time at 40°C can be obtained by increasing the amount of polymerization inhibitor. However, in such a mortar composition provided with a larger amount of polymerization inhibitor, the working time at lower temperatures is clearly too long.

[0008] Therefore, there is a need for a chemical mortar that is stable under storage conditions and has a working time suitable for practical use over a wider temperature range. In other words, the object of the present invention is to provide a chemical mortar that exhibits inhibition of polymerization reactions at both low and high temperatures and provides a practically useful working time over a wide temperature range.

[0009] Surprisingly, it has been shown that the above problems can be solved by the two-component mortar composition described in claim 1 or claim 3.

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

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

[0012] The present invention is based on the idea of ​​providing a temperature-responsive polymerization inhibitor in addition to conventional mortar compositions, which are otherwise conventional. According to the present invention, a "temperature-responsive polymerization inhibitor" is understood to be an inhibitor that shows no or little inhibitory effect at low temperatures or room temperature, but contributes significantly to inhibition at high temperatures. In interaction with conventional polymerization inhibitors already established in mortar systems, such a temperature-responsive polymerization inhibitor may have the effect of obtaining a storage-stable mortar composition that has a working time suitable for practical use at both low and high temperatures. Therefore, a particular object of the present invention is to find a compound that has compatibility with specific chemical properties in composite mortar compositions, which typically have many different components, and that shows no or little inhibitory effect on radical curing reactions at low temperatures (such as room temperature), but shows a significant inhibitory effect at high temperatures (such as 40°C or above).

[0013] In a typical embodiment, the present invention relates to a two-component mortar composition comprising a resin component (A) containing at least one radical-curable resin as a curable component, and a solidifying agent component (B) containing a curing agent for the radical-curable resin of resin component (A), wherein resin component (A) contains one or more polymerization inhibitors selected from phenolic polymerization inhibitors, phenothiazines and / or derivatives thereof, stable organic radicals, oximes, and pyrimidinol or pyridinol compounds substituted at the para position relative to a hydroxyl group, wherein resin component (A) has an activation energy E for homolysis of RO bonds in the range of 100 kJ / mol to 120 kJ / mol a The present invention relates to a two-component mortar composition characterized by further containing an alkoxyamine compound (I) having the above properties.

[0014] An alkoxyamine is a compound containing a structural element R - O - N(R’R”) (where R is an alkyl group and R’ or R” is an organic group). The N - O - R group in the alkoxyamine undergoes homolysis of the R - O bond. That is, a thermally reversible equilibrium is established between one alkoxyamine compound and the other alkyl radical R· and nitroxyl radical ·O - N(R’R”). For a given alkoxyamine compound, the homolysis has a specific activation energy E a which can be measured (or calculated). The determination of the activation energy is generally well - 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 using electron spin resonance (ESR, electron paramagnetic resonance, EPR) at a temperature of 50 °C. Then, the activation energy E a is calculated from the measured reaction rate constant k via the Arrhenius equation.

Equation

[0016] According to the present invention, an alkoxyamine having an activation energy E a for the homolysis of the R - O bond within the range of 100 kJ / mol to 120 kJ / mol is selected as the alkoxyamine compound (I). The inventors have found that the activation energy E aIn the range of 100 kJ / mol to 120 kJ / mol, homolysis hardly occurs at room temperature, and we found that at room temperature, there are hardly any radicals that could suppress the radical curing reaction of the radical curable resin of resin component (A). As a result, the radical curing reaction of the radical curable resin of resin component (A) proceeds at room temperature without being affected by the additional presence of alkoxyamine compound (I). However, at higher temperatures, for example above 40°C, the activation energy E for homolysis of RO bonds a When the concentration is in the range of 100 kJ / mol to 120 kJ / mol, significant homolysis has already occurred, resulting in sufficient radicals to further suppress the radical curing reaction of the radical-curable resin component (A). Therefore, at higher temperatures, the additional presence of alkoxyamine compound (I) has a significant inhibitory effect on the radical curing reaction of the radical-curable resin component (A), meaning that the working time is extended at higher temperatures compared to the case where alkoxyamine compound (I) is absent. Thus, according to the present invention, it is possible to provide a mortar composition that exhibits a practical working time simultaneously at both low and high temperatures.

[0017] In a preferred embodiment, the activation energy E for homolysis of RO bonds in alkoxyamine compound (I) is a The activation energy E for homolysis of RO bonds in alkoxyamine compound (I) is in the range of 100 kJ / mol to 110 kJ / mol. In a more preferred embodiment, the activation energy E for homolysis of RO bonds in alkoxyamine compound (I) is a The range is between 100 kJ / mol and 108 kJ / mol.

[0018] In another general embodiment, the present invention relates to a two-component mortar composition comprising a resin component (A) containing at least one radical-curable resin as a curable component, and a solidifying agent component (B) containing a curing agent for the radical-curable resin of resin component (A), wherein resin component (A) contains one or more polymerization inhibitors selected from phenolic polymerization inhibitors, phenothiazines and / or derivatives thereof, stable organic radicals, oximes, and pyrimidinol or pyridinol compounds substituted at the para position relative to a hydroxyl group, wherein resin component (A) is of the following formula (II) [ka] (In the formula, R 1 C 3~10 It is an alkyl group, R 2 C 2~10 It is an alkyl group, where R 1 and R 2 These may, together with the N atoms to which they are bonded, form optionally substituted, optionally unsaturated heteroalkyl rings. R 3 is H or C1-4 alkyl group, R4 is C 1~4 It is an alkyl group, R 5 (This is an aryl or heteroaryl group.) The present invention comprises a two-component mortar composition characterized by further containing an alkoxyamine compound.

[0019] R in the alkoxyamine compound of formula (II) 3 R 4 R 5 The CO bond undergoes thermally reversible homolysis according to the following reaction equation. [ka]

[0020] From the alkoxyamine compound of formula (II), R 3R 4 R 5 Homosis of the CO bond results in the formula ·ON(R 1 R 2 Nitroxyl radical of formula (R 3 R 4 R 5 )C· alkyl radicals are formed. According to the present invention, at least one of the radicals formed in this process should be a good inhibitor of the radical polymerization of the radical-curable resin of resin component (A). Otherwise, the radicals formed should not interfere with the partially complex chemistry in the mortar system. According to the present invention, this is achieved by a suitable substitution in the alkoxyamine compound of formula (II).

[0021] Therefore, R in the alkoxyamine compound of formula (II) 1 C 3~10 Represents an alkyl group. Preferably, R 1 C 4~8 It is an alkyl group. 1 It may be linear or branched. Preferably, R 1 It is branched at the α-position with respect to the nitrogen atom to which it is bonded. In a preferred embodiment, R 1 This is a C that is branched at the α position relative to the nitrogen atom. 4~8 Represents an alkyl group. 1 This can be further substituted or unsubstituted.

[0022] R in the alkoxyamine compound of formula (II) 2 C 2~10 Alkyl alkyl groups, for example, C 4~8 Represents an alkyl group. 2 It may be linear or branched. Preferably, R 2 It is branched at the β position relative to the nitrogen atom to which it is bonded. Additionally or alternatively, R 2 The branching is optional and may occur at the α-position relative to the nitrogen atom. Furthermore, R 2 It may be substituted or not substituted. For example, R 2The nitrogen atom may be substituted at the α-position.

[0023] Alternatively, R 1 and R 2 These atoms may optionally form a heteroalkyl ring together with the N atom to which they are bonded. This heteroalkyl ring may be unsubstituted or optionally substituted. Furthermore, the heteroalkyl ring may be saturated or optionally partially unsaturated.

[0024] R in the alkoxyamine compound of formula (II) 3 is H or C 1~4 Represents an alkyl group. 3 It may be substituted or not substituted. Furthermore, R 3 It may be linear or branched. In one embodiment, R 3 It is a hydrogen atom.

[0025] R in the alkoxyamine compound of formula (II) 4 C 1~4 It is an alkyl group. This is given by formula (R 3 R 4 R 5 ) This means that the unpaired electrons in the alkyl radical of C· are located (at least) on a secondary or tertiary carbon atom. 4 It may be substituted or not substituted. Furthermore, R 4 It may be linear or branched. In one embodiment, R 4 It is a methyl group.

[0026] R in the alkoxyamine compound of formula (II) 5 This refers to an aryl or heteroaryl group, such as phenyl, naphthyl, anthracenyl, or pyrenyl. 6~20 It is an aryl group. That is, formula (R 3 R 4 R 5 The unpaired electrons in the alkyl radical of )C· are located at the α-position relative to the conjugated π system. 5may be substituted or unsubstituted. In one embodiment, R 5 is naphthyl or pyrenyl, preferably pyrenyl.

[0027] The optional substituent R 1 , R 2 , R 3 , R 4 or R 5 is not particularly limited and can be selected from, for example, an alkyl substituent (such as C 1~4 alkyl, etc.) or a halogen atom. In one embodiment, R 1 , R 2 , R 3 , R 4 or R 5 optionally further contains a protonatable group, a deprotonatable group, or a hydrolyzable group. Examples of the optional protonatable substituent in R 1 , R 2 , R 3 , R 4 or R 5 include, but are not limited to, amine groups such as dialkylamine (e.g., di-C 1~4 alkylamine). Examples of the optional deprotonatable substituent in R 1 , R 2 , R 3 , R 4 or R 5 include, but are not limited to, carboxylic acid groups, sulfonic acid groups, sulfinic acid groups, or phosphonic acid groups. Examples of the optional hydrolyzable substituent in R 1 , R 2 , R 3 , R 4 or R 5 include, but are not limited to, alkyl esters of carboxylic acid, sulfonic acid, sulfinic acid, or phosphonic acid (e.g., C 1~4 alkyl ester). In one embodiment, R 2The substituent is substituted at the α-position relative to the nitrogen atom, and the substituent is preferably selected from alkyl carboxylate groups, sulfinic acid groups, sulfonic acid groups, and phosphonic acid groups.

[0028] In one embodiment, R in the alkoxyamine compound of formula (II) 3 R 4 R 5 Activation energy E for homolysis of CO bond a The R is in the range of 100 kJ / mol to 120 kJ / mol. In a preferred embodiment, R in the alkoxyamine compound of formula (II) 3 R 4 R 5 Activation energy E for homolysis of CO bond a The R in the alkoxyamine compound of formula (II) is in the range of 100 kJ / mol to 110 kJ / mol. In a more preferred embodiment, R in the alkoxyamine compound of formula (II) 3 R 4 R 5 Activation energy E for homolysis of CO bond a The range is between 100 kJ / mol and 108 kJ / mol.

[0029] As described 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 derivatives thereof, stable organic radicals, oximes, and pyrimidinol or pyridinol compounds substituted at the para position with respect to the hydroxyl group. Such polymerization inhibitors are usually present in an amount of 0.1% to 1.0% by weight relative to the amount of radical-curable resin in the resin component (A).

[0030] Examples of such polymerization inhibitors include, in particular, hydroquinones, substituted hydroquinones, such as 4-methoxyphenol, phenothiazine, benzoquinone, or tert-butylpyrocatechol, as described in European Patent No. 1935860(A1) or European Patent No. 0965619(A1), and nitroxyl compounds, in particular stable nitroxyl radicals, also called N-oxyl radicals, such as piperidinyl-N-oxyl or tetrahydropyrrole-N-oxyl, as described in German Patent Application Publication No. 19531649(A1). Particularly preferred is 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (hereinafter referred to as tempol) used for stabilization.

[0031] The polymerization inhibitor is preferably selected from phenolic compounds and non-phenolic compounds, such as stable radicals and / or phenothiazines.

[0032] Phenols, for example, 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'-thio-bis(3-methyl-6-tert-butylphenol), 4,4'-isopropylidenediphenol, 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 Pyrocatechol and butylpyrocatechols, such as 4-tert-butylpyrocatechol, 4,6-di-tert-butylpyrocatechol, 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 mixtures of two or more thereof, can be used as phenolic polymerization inhibitors and are often components of commercially available radical-curing reactive resins.

[0033] Phenothiazines, such as phenothiazines and / or their derivatives, or combinations thereof, or stable organic radicals such as garbinoxyl radicals and N-oxyl radicals, are preferably considered as non-phenolic polymerization inhibitors.

[0034] Suitable stable N-oxyl radicals (nitroxyl radicals) can be selected from 1-oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidine-4-ol (also known as TEMPOL), 1-oxyl-2,2,6,6-tetramethylpiperidine-4-one (also known as TEMPON), 1-oxyl-2,2,6,6-tetramethyl-4-carboxy-piperidine (also known as 4-carboxy-TEMPO), 1-oxyl-2,2,5,5-tetramethylpyrrolidine, 1-oxyl-2,2,5,5-tetramethyl-3-carboxylpyrrolidine (also known as 3-carboxy-PROXYL), aluminum-N-nitrosophenylhydroxylamine, and diethylhydroxylamine, as described in German Patent Application Publication No. 19956509. Further preferred N-oxyl compounds are oximes such as acetaldehyde, acetone oxime, methyl ethyl ketoxime, salicyl oxime, benzoxime, glyoxime, dimethyl glyoxime, and acetone-O-(benzyloxycarbonyl)oxime. In addition, pyrimidinol or pyridinol compounds substituted at the para position relative to the hydroxyl group, as described in German Patent Application Publication No. 102011077248(B1), can be used as polymerization inhibitors.

[0035] Polymerization inhibitors can be used alone or in combination of two or more, depending on the desired properties and use of the resin mixture. Combinations of phenolic and non-phenolic polymerization inhibitors enable synergistic effects, as can also be shown by setting the gelation time of the reactive resin composition in a substantially drift-free manner.

[0036] In one embodiment, the mortar composition contains alkoxyamine compound (I) or alkoxyamine compound of formula (II) in an amount of 0.5 to 100 equivalents, preferably 1 to 10 equivalents of alkoxyamine compound (I) or alkoxyamine compound of formula (II) per equivalent of the above (conventional) polymerization inhibitor.

[0037] The fixation of fixed elements using the two-component mortar composition according to the present invention provides a practical working time at both low and high 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 addition to a conventional polymerization initiator, in the resin component (A) of the mortar composition.

[0038] Further advantages of the present invention can be found in the following description of preferred embodiments.

[0039] For the purposes of this invention, "two-component mortar composition" is understood to mean a mortar composition comprising a curable resin component and a solidifying agent component for the resin component, and the resin component and the solidifying agent component are stored separately from each other to prevent reaction between the solidifying agent component and the resin component during storage. When the solidifying agent component is mixed with the reactive resin immediately before application of the mortar composition, the curing of the reactive resin begins.

[0040] The mortar composition according to the present invention may further contain at least one inorganic additive as a further component in the resin component (A) and / or the solidifying agent component (B). The term "inorganic additive" refers to all inorganic components of the mortar composition. The use of inorganic additives in mortar compositions is known in the prior art. In this context, the mortar composition according to the present invention may contain a large amount of inorganic additive. For example, the amount of inorganic additive is in the range of 40% to 75% by weight of the total weight of the mortar composition. In one embodiment, the amount of inorganic additive is in the range of 15% to 65% by weight, for example, 30% to 60% by weight of the total weight of the mortar composition.

[0041] Inorganic additives can be selected from, for example, inorganic fillers, hydraulic or polycondensable inorganic compounds, modifiers, and mixtures thereof.

[0042] Preferably, the inorganic additive includes fillers that may be contained in the resin component (A) and / or the solidifying agent component (B). Suitable examples of fillers are BaSO4, quartz, glass, corundum, porcelain, stoneware, barite, light spar, gypsum, talc, fly ash and / or chalk, and mixtures thereof, for example, in the form of sand, powder or molded articles, preferably in the form of fibers or spheres.

[0043] According to one embodiment of the present invention, the inorganic additive further comprises a hydraulic or polycondensing inorganic compound, such as cement and / or gypsum, preferably a cement that is iron oxide-free or contains only a small amount of iron oxide, such as aluminate cement. The hydraulic or polycondensing inorganic compound is preferably contained in the solidifying agent component (A). In this case, the solidifying agent component (B) comprises a hardening agent and water optionally included to viscous the hardening agent, in addition to additional water for hardening the hydraulic or polycondensing inorganic compound.

[0044] Finally, the inorganic additive in the resin component (A) and / or the solidifying agent component (B) may also contain other inorganic modifiers, such as thickeners and thixotropes, such as precipitated or fumed silica, bentonite and / or kaolin.

[0045] The two-component mortar composition of the present invention further comprises at least one radical-curable resin as a curable component in the resin component (A). Radical-curable resins for use in mortar compositions are known in the prior art. Suitable radical-curable compounds according to the present invention include, as known to those skilled in the art, for example, ethylenically unsaturated compounds, compounds having carbon-carbon triple bonds, and thiol-yen / ene resins.

[0046] Of these compounds, the group of ethylenically unsaturated compounds is preferred, and this group includes styrene and its derivatives, (meth)acrylates, vinyl esters, unsaturated polyesters, vinyl ethers, allyl ethers, itaconates, dicyclopentadiene compounds, and unsaturated fats, among which unsaturated polyester resins and vinyl ester resins are particularly preferred, as described, for example, in European Patent No. 1935860(A1), German Patent Application Publication No. 19531649(A1), and International Publication No. 10 / 108939(A1). In this case, vinyl ester resins are most preferred due to their hydrolysis resistance and excellent mechanical properties.

[0047] Suitable unsaturated polyesters that can be used in the two-component mortar composition according to the present invention are classified as follows: (1) Ortho resins: These 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. (2) Iso resins: These are prepared from isophthalic acid, maleic anhydride or fumaric acid and glycol. These resins may contain a higher proportion of reactive diluent than ortho resins. (3) Bisphenol A fumarate esters: These are based on ethoxylated bisphenol A and fumarate. (4) HET acid resins (hexachloroendomethylenetetrahydrophthalic acid resins): These are resins obtained from chlorine / bromine-containing anhydrides or phenols during the preparation of unsaturated polyester resins.

[0048] In addition to these resin classes, dicyclopentadiene resins (DCPD resins) can also be distinguished as unsaturated polyester resins. The DCPD resin class is obtained by modifying one of the above resin types by a Diels-Alder reaction with cyclopentadiene, or alternatively, by a first reaction of dicyclopentadiene with a diacid, such as maleic acid, followed by a second reaction in the usual preparation of unsaturated polyester resins, the latter of which is called DCPD maleic acid ester resin.

[0049] The unsaturated polyester resin preferably has a molecular weight M in the range of 500 Daltons to 10,000 Daltons, more preferably in the range of 500 to 5,000, and even more preferably in the range of 750 to 4,000. n It has (in accordance with 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 (in accordance with ISO 2114-2000). When 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.

[0050] Within the scope of the present invention, vinyl ester resin is an oligomer or polymer having at least one (meth)acrylate end group, which is called a (meth)acrylate-functionalized resin, also including urethane (meth)acrylate resin and epoxy (meth)acrylate.

[0051] Vinyl ester resins having unsaturated groups only at terminal positions can be obtained, for example, by reacting epoxy oligomers or polymers (e.g., bisphenol A diglycidyl ether, phenol novolac type epoxy, or tetrabromobisphenol A-based epoxy oligomers) with, for example, (meth)acrylic acid or (meth)acrylamide. Preferred vinyl ester resins are resins obtained by reacting (meth)acrylate-functionalized resins and epoxy oligomers or epoxy polymers with methacrylic acid or methacrylamide, preferably methacrylic acid. Examples of such compounds are known from U.S. Patent Nos. 3,297,745(A), 3,772,404(A), 4,618,658(A), UK Patent Application Publication No. 2217,722(A1), German Patent Nos. 3,744,390(A1) and 4131,457(A1). In this context, the application in U.S. Patent Application Publication No. 2011 / 071234 is referred to.

[0052] The vinyl ester resin preferably has a molecular weight M in the range of 500 Daltons to 3,000 Daltons, more preferably 500 Daltons to 1,500 Daltons. n It has (in accordance with ISO 13885-1). The vinyl ester resin has an acid value 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 (in accordance with ISO 2114-2000).

[0053] Ethoxylated bisphenol A di(meth)acrylate having an ethoxylation degree of 2 to 10, preferably 2 to 4, bifunctional, trifunctional, or more highly functional urethane(meth)acrylate oligomers, or mixtures thereof of curable components are particularly suitable as vinyl ester resins.

[0054] An example of this type of epoxy (meth)acrylate is that of formula (A), [ka] In the formula, n represents a number greater than or equal to 1 (a non-integer as the average is also possible if there is a mixture of different molecules with different values ​​of n and it is represented by formula (A)).

[0055] Further examples of propoxylated or especially ethoxylated aromatic diols, such as bisphenol A, bisphenol F, or novolac (especially di-)(meth)acrylates, are of formula (B), [ka] In the formula, a and b each independently represent a number greater than or equal to 0, but preferably at least one of these values ​​is greater than 0, and preferably both are 1 or greater (if there is a mixture of different molecules with different (a and b) values ​​and is represented by formula (B), then non-integers as the average value are also possible).

[0056] For example, known reaction products of di- or polyisocyanates and hydroxyalkylmethyl acrylates described in German Patent No. 2312559(A1), adducts of (di)isocyanate and 2,2-propanebis[3-(4-phenoxy)-1,2-hydroxypropane-1-methacrylate] according to U.S. Patent No. 3,629187, and adducts of isocyanates and methacryloylalkyl ethers, alkoxybenzenes, or alkoxycycloalkanes described in European Patent No. 44352(A1) are particularly preferred. In this context, reference is made to German Patent No. 2312559(A1), German Patent Application Publication No. 19902685(A1), European Patent No. 0684906(A1), German Patent No. 4111828(A1), and German Patent Application Publication No. 19961342(A1).

[0057] Of course, suitable monomer mixtures can also be used.

[0058] All of these resins that can be used in this invention can be modified, for example, by methods known to those skilled in the art to achieve a lower acid value, hydroxyl value, or anhydrous value, or they can be made more flexible by introducing flexible units into the skeleton or the like.

[0059] Furthermore, the resin may contain other reactive groups that can be polymerized with radical initiators such as peroxides, such as the (itaconic acid esters) described in International Publication No. 2010 / 108939, for example, reactive groups derived from itaconic acid, citraconic acid, and allyl groups.

[0060] The percentage ratio of radical-curable resin in resin component (A) (in weight %) is advantageously greater than about 5%, preferably greater than about 15%, and particularly preferably greater than about 20%. The percentage ratio of radical-curable resin in resin component (in weight %) is advantageously about 10% to about 90%, preferably about 15% to about 80%, more preferably about 20% to about 60%, more preferably about 25% to about 55%, even more preferably about 30% to about 55%, particularly preferably about 30% to about 50%, and very particularly preferably about 32% to about 45%.

[0061] The radical-curable resin in component (A) of the mortar composition 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.

[0062] To prepare a suitable urethane (meth)acrylate resin, at least a bifunctional isocyanate can be reacted with one or more hydroxy-functional ethylenically unsaturated compounds, particularly a hydroxy-functional (meth)acrylic compound.

[0063] The at least bifunctional isocyanates used to prepare the urethane (meth)acrylate resin may be aromatic isocyanates, aliphatic isocyanates, particularly alicyclic isocyanates, and isocyanate group-containing prepolymers, which can be used in combination with each other.

[0064] Suitable examples of aliphatic and aromatic isocyanates include m-phenylenediisocyanate, toluene-2-4-diisocyanate, toluene-2-6-diisocyanate, hexamethylene-1,6-diisocyanate, tetramethylene-1,4-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrotoluylenediisocyanate, naphthylene-1,5-diisocyanate, methoxyphenyl-2,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, and 4,4 Examples include '-biphenyl diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl 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.

[0065] Diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, and mixtures thereof are collectively called MDI and can all be used. Toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, and mixtures thereof are commonly called TDI and can all also be used.

[0066] Preferably, the polyisocyanate is selected from the group consisting of diphenylmethane diisocyanate (MDI), polymeric diphenylmethane diisocyanate (PMDI), toluene diisocyanate (TDI), hexane diisocyanate (HDI), isophorone diisocyanate (IPDI), and mixtures thereof.

[0067] Isocyanate prepolymers, prepared by reacting a stoichiometrically excess of any polyisocyanate with an isocyanate-reactive compound as a chain extender, can also be optionally used in the above-mentioned mixtures of aromatic isocyanates and aliphatic isocyanates.

[0068] Examples of such chain extenders include dihydric alcohols, such as ethanediol, diethylene glycol, triethylene glycol and polyethylene glycol, propanediol, dipropylene glycol, tripropylene glycol and polypropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and diethanolamine, as well as aromatic alcohols, such as bisphenol A and bisphenol F, or their ethoxylated, hydrogenated and / or halogenated products, higher alcohols, such as glycerol, trimethylolpropane, hexanetriol and pentaerythritol, hydroxyl group-containing polyethers, such as oligomers of aliphatic or aromatic oxiranes, and / or high-membered ring 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 or F, and the above alcohols and polyethers with dicarboxylic acids or their anhydrides, such as adipic acid, phthalic acid, tetrahydrophthalic acid or hexahydrophthalic acid, heteric acid. It is a hydroxyl group-containing polyester based on acid, maleic acid, fumaric acid, itaconic acid, and sebacic acid.

[0069] Chain extenders containing aromatic structural units harden the resin chains. Hydroxyl compounds containing unsaturated structural units, such as fumaric acid, can be used to increase the crosslinking density during curing. Branched or star-shaped hydroxyl compounds as chain extenders, particularly trivalent or higher alcohols, and polyethers and / or polyesters containing these structural units, result in branched or star-shaped urethane (meth)acrylates that exhibit lower resin viscosity and improved solubility in reactive diluents.

[0070] The hydroxy-functional (meth)acrylic compound for preparing the urethane (meth)acrylate resin of resin component (A) is preferably a hydroxyalkyl (meth)acrylate ester such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, polyoxyethylene (meth)acrylate, polyoxypropylene (meth)acrylate, or a hydroxyl group-containing (meth)acrylic acid ester of a polyhydric alcohol such as pentaerythritol tri(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane di(meth)acrylate, and neopentyl glycol mono(meth)acrylate.

[0071] As used herein and hereafter, the designations "(meth)acrylic..." or "...(meth)acrylic..." are intended to include both acrylic and methacrylic groups.

[0072] The reaction between at least a bifunctional isocyanate and a hydroxy-functional ethylenically unsaturated compound is carried out such that the free-radical curable resin of the resulting 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 stoichiometric excess relative to the isocyanate groups.

[0073] Other radical-curable resins that can be used include, for example, vinyl esters, epoxy (meth)acrylates, unsaturated polyester resins, and mixtures thereof, which can be used alone or in combination with the (poly)urethane (meth)acrylates mentioned above.

[0074] Unsaturated polyester resins are obtained by reacting unsaturated dicarboxylic acids, such as o- and / or isophthalic acid, maleic acid, and fumaric acid, with dialcohols.

[0075] Epoxy (meth)acrylates are typically condensates of (meth)acrylic acid and glycidyl ethers of bisphenol A, bisphenol F, or novolac.

[0076] Radical-curable resins are present in mortar compositions, for example, at a concentration of 10% to 40% by weight.

[0077] According to preferred embodiments of the present invention, the resin component (A) in all of the above embodiments further contains, as a constituent component, at least one reactive diluent having at least one ethylenically unsaturated group. Preferred reactive diluents are, in particular, (meth)acrylate compounds, as well as allyl and vinyl compounds.

[0078] Suitable reactive diluents are described in European Patent No. 1935860(A1) and German Patent Application Publication No. 19531649(A1). Preferably, the resin mixture contains a (meth)acrylic acid ester as a reactive diluent, and is particularly preferably an aliphatic or aromatic C5-C5 ester. 15(Meth)acrylates are selected. Preferred examples include hydroxypropyl (meth)acrylate, 1,2-ethanediol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,2-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate (BBDMA), trimethylolpropane tri(meth)acrylate, phenethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethyl triglycol (meth)acrylate, and N,N-dimethylaminoethyl Di(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 tricyclo Pentadienyl di(meth)acrylate, bisphenol-A-(meth)acrylate, novolac epoxy di(meth)acrylate, di-[(meth)acryloyl-maleoil]-tricyclo-5,2.1.0.2.6-decane, dicyclopentenyloxyethyl crotonate (crotonat), 3-(meth)acryloyl-oxymethyl-tricyclo(tricylo)-5,2.1.0.2.6-decane, 3-(meth)cyclopentadienyl(meth)acrylate, isobornyl(meth) Examples include acrylates and decalyl-2-(meth)acrylate; PEG-di(meth)acrylates, such as PEG200 di(meth)acrylate, tetraethylene glycol di(meth)acrylate, solketal (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl di(meth)acrylate, methoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, tert-butyl (meth)acrylate, and norbornyl (meth)acrylate.

[0079] In principle, other conventional radical-curable compounds, such as styrene, α-methylstyrene, alkylated styrene, such as tert-butylstyrene, divinylbenzene, and allyl compounds, can also be used alone or in mixtures with (meth)acrylic acid esters, with representative examples that are not subject to mandatory labeling being preferred.

[0080] Particularly preferred reactive diluents are hydroxypropyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, and butanediol-1,2-di(meth)acrylate.

[0081] The reaction diluent acts, on the one hand, as a solvent for the radical-curable resin, and on the other hand, as a comonomer involved in the radical polymerization of the resin components. The use of the reaction diluent provides further improvement in the adhesion of the cured mortar composition to the surface of the mineral substrate and / or the fixed element to be fixed.

[0082] The reactive diluent is present in the mortar composition in proportions of, for example, 0 to 25 percent by weight, 4 to 25 percent by weight, or 8 to 15 percent by weight. All radical-curable compounds are preferably present in the mortar composition in proportions of up to 30 percent by weight.

[0083] According to a more preferred embodiment of the present invention, the resin component (A) contains at least one accelerator for curing. Suitable accelerators commonly added to resin mixtures are known to those skilled in the art. These are, for example, amines, preferably tertiary amines and / or metal salts.

[0084] Suitable amines include, for example, the following compounds described in U.S. Patent Application Publication No. 2011071234(A1): dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-propylamine, isopropylamine, di-isopropylamine, tri-isopropylamine, n-butylamine, isobutylamine, tert-butylamine, di-n-butylamine, di-isobutylamine, tri-isobutylamine, pentylamine, isopentylamine, diisopentylamine, hexylamine, octylamine, dodecylamine, laurylamine, stearylamine, aminoethanol, diethanolamine, triethanolamine, aminohexanol, ethoxyaminoethane, dimethyl(2-chloroethyl)amine, 2-ethylhexylamine, bis(2-chloroethyl)amine, 2-ethylhexyl Diamine, bis(2-ethylhexyl)amine, N-methylstearylamine, dialkylamine, ethylenediamine, N,N'-dimethylethylenediamine, tetramethylethylenediamine, diethylenetriamine, permethyldiethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,2-diaminopropane, dipropylenetriamine, tripylenetetramine, 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, di-isopropanolamine, 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-Aminohexanoic acid, 11-Aminoundecanoic acid, 6-Aminohexanoic acid ethyl ester, 11-Aminohexanoic acid isopropyl ester, Cyclohexylamine, N-Methylcyclohexylamine, N,N-Dimethylcyclohexylamine, Dicyclohexylamine, N-Ethylcyclohexylamine, N-(2-Hydroxyethyl)cyclohexylamine, N,N-Bis(2-Hydroxyethyl)cyclohexylamine, N-(3-A Minopropyl)cyclohexylamine, aminomethylcyclohexane, hexahydrotoluidine, 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 their esters, benzylamine, dibenzylamine, tribe Didiamine, methyldibenzylamine, α-phenylethylamine, xylidine, diisopropylaniline, dodecylaniline, aminonaphthalene, N-methylaminonaphthalene, N,N-dimethylaminonaphthalene, N,N-dibenzylnaphthalene, diaminocyclohexane, 4,4'-diamino-dicyclohexylmethane, diamino-dimethyl-dicyclohexylmethane, phenylenediamine, xylylenediamine, diaminobiphenyl, naphthalenediamine, toluidine, benzidine, 2,Selected from 2-bis(aminophenyl)propane, aminoanisole, aminothiophenol, aminodiphenyl ether, aminocresol, morpholine, N-methylmorpholine, N-phenylmorpholine, hydroxyethylmorpholine, N-methylpyrrolidine, pyrrolidine, piperidine, hydroxyethylpiperidine, pyrrole, pyridine, quinoline, indole, indorenine, carbazole, pyrazole, imidazole, thiazole, pyrimidine, quinoxaline, aminomorpholine, dimorpholineethane, [2,2,2]-diazabicyclooctane, and N,N-dimethyl-p-toluidine.

[0085] Preferred amines include aniline derivatives and N,N-bisalkylarylamines, such as N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-toluidine, N,N-bis(hydroxyalkyl)arylamines, 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.

[0086] High molecular weight amines, such as those obtained by polycondensation of N,N-bis(hydroxyalkyl)aniline with a dicarboxylic acid, or by polyaddition of ethylene oxide with these amines, are also suitable as accelerators.

[0087] Suitable metal salts include, for example, cobalt octanoate or cobalt naphthenate, and vanadium carboxylate, potassium carboxylate, calcium carboxylate, copper carboxylate, manganese carboxylate, or zirconium carboxylate.

[0088] Resin mixtures may also contain co-promoters, especially when transition metal compounds are used as accelerators. Depending on the selected transition metal compound, those skilled in the art can select a co-promoter suitable for achieving the desired curing properties. When cobalt compounds are used as accelerators, the co-promoters are preferably amines and / or 1,3-dioxo compounds. When copper compounds are used as accelerators, the co-promoters are preferably amines, acetacetamides, potassium salts, imidazoles and / or gallates, or mixtures thereof. When manganese compounds are used as accelerators, the co-promoters are preferably 1,3-dioxo compounds, thiols, and / or potassium or lithium salts, or mixtures thereof. When iron compounds are used as accelerators, the co-promoters are preferably 1,3-dioxo compounds and / or thiols, preferably in combination with alkali metal salts. Suitable 1,3-dioxo compounds are acetylacetone, acetacetate, and acetacetamide.

[0089] For example, accelerators and / or co-accelerators are present in the mortar composition in a proportion of 0% to 1% by weight, for example, 0.01% to 0.7% by weight.

[0090] Finally, the mortar composition may contain other organic additives, such as silane compound-based adhesion improvers, which are known to those skilled in the art, for example, from European Patent No. 2371782(A2) and International Publication No. 2011 / 072789(A1).

[0091] The curing agent for the radical-curable resin of the resin component (A) contained in the solidifying agent component (B) of the two-component mortar composition according to the present invention preferably comprises at least one organic peroxide, such as dibenzoyl peroxide, methyl ethyl ketone peroxide, tert-butyl perbenzoate, cyclohexanone peroxide, lauryl peroxide, cumene hydroperoxide and / or tert-butyl peroxy-2-ethylhexanoate.

[0092] The organic peroxide is preferably liquefied by adding water, particularly as a liquefaction agent and / or solvent. Suitable solidifying agent components are known to those skilled in the art and are available on the market.

[0093] Alternatively, a peroxide-free solidifying agent system can be used for curing, and this system consists of the following components: At least one manganese compound as an accelerator, 1,3-dioxo compounds as initiators and It contains. For this purpose, German Patent Application Publication No. 102011078785(A1) is referenced.

[0094] Similarly, alternatively, the following components: At least one metal salt as an accelerator, A compound containing a thiol and / or thiol ester group as an initiator and A solidifying agent system containing [the specified ingredient] can be used for curing. For this purpose, German Patent Application Publication No. 102013114061(A1) is referenced.

[0095] As a result of the combination or mixing of two components, radicals can be formed that can cause polymerization of non-aromatic double bonds, such as olefin double bonds, such as acrylates or methacrylates, instead of conventionally used radical-forming agents.

[0096] As further alternatives, the following components: At least one metal salt as an accelerator and As an initiator, at least one formula [ka] (In the formula, (i) -A- is -C(R 1 )(R 2 )- represents, -X- is -NR 3-or-(CR 4 R 5 ) p - or -O- represents a bond, Y is NR 6 Or (CR 7 R 8 ) q , or represents O, Here, if X represents O, then Y also represents O; Here, preferably, X is (CR 4 R 5 ) p Y represents CR 7 R 8 This represents, Or X is NR 3 This represents Y, where Y is NR 6 It represents; Z 1 This represents O, S, S=O, or S(=O)², Z 2 This represents O, S, S=O, or S(=O)², Z 3 is O, S, S=O or S(=O)2, or R 9 and R 10 This represents, p represents 1, 2, or 3, preferably 1 or 2. q represents 1, 2, or 3, preferably 1; Functional group R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 Each of these independently represents hydrogen, alkyl, aryl, aralkyl, cycloalkyl, or cycloalkylalkyl, and each is unsubstituted, substituted, and / or a heteroatom (in place of a C atom; Preferably, selected from O, N, for example NH or N-alkyl, and S, provided that the functional group R 1 and R 2 At least one of them represents hydrogen. or (ii) Crosslinked-C(=Z 3 It is an open-chain compound lacking the bond that forms )-, -A- is -C(R 1 )(R 2 )- represents, where X and Y each independently represent, in each case, an unbranched or branched, unsubstituted or substituted C1-C4 alkyl group or C1-C4 alkoxy group, which optionally have a heteroatom (in place of a C atom; in particular selected from O, N, e.g., NH or N-alkyl, and S), or preferably, in each case, an unsubstituted or substituted C1-C4 alkoxycarbonylmethyl group or C1-C4 alkylcarbonylmethyl group, which optionally have a heteroatom (in place of a C atom; in particular selected from O, N, e.g., NH or N-alkyl, and S), R 1 and R 2 Both are hydrogen. Z 1 and Z 2 It has the meaning described above; Alternatively, X represents, in each case, 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 a heteroatom (in place of a C atom; in particular selected from O, N, e.g., NH or N-alkyl, and S), Y and Z 2 It, together with the bonded carbon atom, is -CN, Z 1 It has the above meaning, R 1 and R 2 In each case, the definition is as described above, except that at least one of the functional groups is hydrogen. CH-acidic compounds and / or salts thereof A solidification system containing the above can be used for curing. For this purpose, refer to German Patent Application Publication No. 102015003221(A1).

[0097] In both cases, the components used as accelerators, including metal complexes and metal oxides, in the form of metal salts, are preferably one or more metal salts, or in particular, salts of organic acids and / or inorganic acids with metals selected from, for example, cobalt, zirconium, zinc, cerium, tin, bismuth, or preferably vanadium, manganese, copper, or iron, or mixtures of two or more thereof, where the organic acid is preferably saturated, and where optionally, in the presence of one or two co-accelerators having a metal content from the group of metals, in particular, inorganic acids and / or carboxylate functional groups, for example, CH3, C2~C 20 Alkyl, C6~C 24 Aryl functional group or C7~C 30 Preferred are salts and complexes having carboxylates with aralkyl functional groups, such as octanoates, such as 2-ethylhexanoate (isooctanoate), and even more specifically, neodecanoates or acetylacetonates, with vanadium and iron, or particularly manganese and copper. Particularly preferred are the group of metal salts having manganese carbonate or manganese carboxylate, such as Mn acetate or Mn octanoate, copper carboxylate, such as copper octanoate or copper naphthenate, copper quinolinate, iron carboxylate, such as iron octanoate, and / or vanadium carboxylate, and / or inorganic acids, such as iron chloride, iron sulfate, and copper chloride.

[0098] Further alternatives include the following components: At least one metal salt as an accelerator, At least one aldehyde and / or ketone and at least one primary amine as initiators, and / or b2) formula [ka] (Each in the formula is independent of the others, Q represents the organic functional group of the amine used (in each case), or represents hydrogen. R 2 and R 3Each of these is independently a hydrogen and / or unsubstituted or substituted, single-branched, multi-branched or linear organic functional group, optionally having a double bond and / or a heteroatom, and comprising at least one aliphatic, heteroaliphatic, alicyclic or heterocyclic molecular structure, or a combination of two or more of the above molecular structures. At least one imine and / or salt thereof containing one or more imine structural increments. A solidification system containing [the specified element] can be used for curing. For this purpose, German Patent Application Publication No. 102016124075(A1) is referenced.

[0099] To set a suitable viscosity, the solidifying agent component may contain a certain proportion of inorganic fillers and modifiers, such as thixotropes.

[0100] The two-component mortar composition according to the present invention is preferably contained within a capsule, cartridge, or film pouch, characterized by having two or more separate chambers that separately arrange the resin component (A) and the solidifying agent component (B) of the mortar composition to prevent reaction.

[0101] For intended use, the resin component (A) and the solidifying agent component (B) are discharged from separate chambers and mixed in a suitable apparatus, such as a static mixer. The mixture of resin component (A) and solidifying agent component (B) is then introduced into a pre-cleaned borehole by means of a known injection apparatus. The fixing elements to be fixed are then inserted into the mortar composition and aligned. The hardening agent of the solidifying agent component (B) initiates the radical polymerization of the resin component (A), so the mortar composition hardens within a few hours under ambient conditions.

[0102] Accordingly, the present invention also relates to the use of a two-component mortar composition according to the present invention for chemically fixing fastening elements, particularly anchor threaded rods, reinforcing bars, threaded sleeves and screws, in drilled holes in building materials such as wood or mineral substrates, preferably concrete.

[0103] The present invention is described below based on preferred exemplary embodiments, but should not be understood as limiting. [Examples]

[0104] Component generation The composition of the resin components used in Comparative Example V1 and Application Example A1 is shown in Table 1 below. [Table 1]

[0105] Table 2 below shows the compositions of Comparative Example V1 and Application Example A1 in parts by weight for each case. In Application Example A1, the following compound (AV1) was used as the alkoxyamine compound of formula (I). [ka]

[0106] 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 of 105.32 kJ / mol for homolysis of RO bonds. a It has the following properties. The amount of AV1 used in application example A1 corresponds to 4 equivalents per 1 equivalent of polymerization inhibitor (Tempol). [Table 2]

[0107] In each case, Perkadox 20S, available from Akzo Nobel, i.e., a mixture containing 20% ​​by weight of dibenzoyl peroxide on calcium sulfate / magnesium hydroxycarbonate, was used as component B. 3 g of each component A was heated in a small speed mixer at 5°C for at least 3 hours. Then, 900 mg of component B was mixed in a speed mixer (1500 rpm / 60 sec), and the sample was immediately weighed and placed in a DSC crucible (aluminum 40 μL-D).

[0108] At this point, isothermal measurements of the curing curves at 20°C, 40°C, and 60°C are performed. A crucible heated to 5°C is placed in a DSC cell heated to the measurement temperature, and the measurement is started. The gelation time (time to peak) is measured from the mixing time. The measurement (duration: 120 minutes) is performed under N2 conditions. The results obtained ([minutes]) are shown in Table 3. [Table 3]

[0109] At room temperature, the addition of alkoxyamine compound AV1 results in only a slight extension of gelation time of 25%. At 40°C, the extension of gelation time caused by the addition of alkoxyamine compound AV1 is already significant at 42%. The extension of gelation time achieved by the addition of alkoxyamine compound AV1 is particularly remarkable at 60°C, reaching 72%. [Table 4]

Claims

1. A two-component mortar composition comprising a resin component (A) containing at least one radical-curable resin as a curable component, and a solidifying agent component (B) containing a curing agent for the radical-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 derivatives thereof, stable organic radicals, oximes, and pyrimidinol or pyridinol compounds substituted at the para position with respect to a hydroxyl group, The aforementioned resin component (A) is given by the following formula (II) 【Chemistry 1】 (In the formula, R １ This is a C4-8 alkyl group that is branched at the α position relative to the nitrogen atom. R ２ This is a C that is branched at the β position relative to the nitrogen atom and substituted at the α position relative to the nitrogen atom. ２～１０ It is an alkyl group, where R2 is a substituent selected from an alkyl carboxylate group, a sulfinic acid ester group, a sulfonic acid ester group, and a phosphonic acid ester group. R ３ H is, R ４ C １～４ It is an alkyl group, R ５ (These are unsubstituted or substituted C6-20 aryl groups.) A mortar composition further containing an alkoxyamine compound of formula (II), wherein the alkoxyamine compound of formula (II) has an activation energy E a for homolysis of the R3 R4 R5 C-O bond in the range of 100 kJ / mol to 120 kJ / mol, and the alkoxyamine compound of formula (II) is present in an amount of 0.5 to 100 equivalents per equivalent of polymerization inhibitor.

2. The alkoxyamine compound of formula (II) has an R within the range of 100 kJ / mol to 110 kJ / mol ３ R ４ R ５ Activation energy E for homolysis of the C—O bond ａ The mortar composition according to claim 1, which has

3. The mortar composition according to claim 1, wherein the alkoxyamine compound of formula (II) is present in an amount of 1 to 10 equivalents per equivalent of the polymerization inhibitor.

4. The mortar composition according to claim 1, wherein the resin component (A) and / or the solidifying agent component (B) further contain, as constituent components, at least one inorganic additive selected from inorganic fillers, hydraulic or polycondensable inorganic compounds, modifiers and mixtures thereof.

5. The inorganic additive is BaSO ４ The mortar composition according to claim 4, comprising a filler selected from the group consisting of quartz, glass, corundum, porcelain, stoneware, barite, light spar, gypsum, talc, fly ash, chalk, and mixtures thereof.

6. The mortar composition according to claim 4, wherein the inorganic additive comprises a hydraulic or polycondensable inorganic compound selected from the group consisting of cement, gypsum, and mixtures thereof.

7. The mortar composition according to claim 4, wherein the inorganic additive comprises a modifier selected from the group consisting of thickeners, plasticizers, thixotropes, and mixtures thereof.

8. The mortar composition according to claim 1, wherein the radical-curable resin is selected from a urethane (meth)acrylate-based compound, an epoxy (meth)acrylate-based compound, a methacrylic acid ester of alkoxylated bisphenol, and a compound based on a further ethylenically unsaturated compound.

9. The mortar composition according to claim 1, wherein the resin component (A) contains at least one reactive diluent as a further constituent component.

10. The mortar composition according to claim 1, wherein the resin component (A) further comprises at least one accelerator as a component.

11. The mortar composition according to claim 1, wherein the solidifying agent component (B) contains at least one organic peroxide as a hardening agent.

12. The mortar composition according to claim 1, wherein the resin component (A) and the solidifying agent component (B) are contained within a capsule, cartridge, or film pouch, and are arranged in separate chambers.

13. Use of the two-component mortar composition according to claim 1 for chemically fixing a fixing element in an excavation hole for building materials.

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