Two-component mortar composition containing a temperature-responsive 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 hardening component, and a curing agent component (B) containing a curing agent for the radical-curable resin of the 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, 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. 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-responsive 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 drilled holes made in a mineral substrate.

[0002] In order to firmly fix fixing elements such as threaded anchor rods, reinforcing bars, threaded sleeves, and screws to a mineral substrate such as concrete, natural stone, or plaster, a drilled hole for receiving the fixing element to be fixed is first drilled in the mineral substrate with appropriate dimensions. Next, the drilling dust is removed from the drilled hole, and after mixing the resin component with the curing agent component, the two-component mortar composition is introduced into the drilled hole. Then, the fixing element to be fixed is inserted into the drilled hole filled with the mortar composition and adjusted. After the mortar composition is hardened by the reaction of the resin component and the curing agent component, the fixing element is firmly held in the mineral substrate.

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

[0004] External variable factors that have an impact include the type of cleaning of the drilled hole, for example the quality of the mineral base material such as concrete, its moisture and temperature, and the type of generation of the drilled hole.

[0005] Two-component mortar compositions based on urethane (meth)acrylate resins that cure 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, which are known in the prior art and used as chemical bond anchors, usually contain a polymerization inhibitor. Such conventional polymerization inhibitors are selected from phenolic polymerization inhibitors, phenothiazine and / or its derivatives, stable organic radicals, oximes, and pyrimidinol or pyridinol compounds substituted in the para position with respect to the hydroxyl group. The polymerization inhibitor can be used, on the one hand, to ensure a certain storage stability of the mortar composition and, on the other hand, to set the desired working time. The working time is understood to be the time during which the mortar composition is still liquid and a fixing element can be inserted. The working time should not be too short so that a fixing element fixed in a drilled hole filled with the mortar composition can be inserted and properly aligned. On the other hand, the working time should not be too long, otherwise the work flow at the construction site will be unnecessarily delayed.

[0007] However, the working time is strongly dependent on temperature. The temperature found at the construction site is an external variable factor that has an impact and cannot be influenced or controlled. At high temperatures, the reactivity of the components in the mortar composition increases, so the working time decreases as the temperature rises. For a mortar composition having a suitable working time at room temperature (about 20 °C), for example, the working time obtained at 40 °C is too short. By increasing the amount of polymerization inhibitor, a suitable working time at 40 °C can be obtained. However, in such a mortar composition provided with a larger amount of polymerization inhibitor, the working time at a lower temperature is clearly too long.

[0008] Therefore, there is a need for a chemical mortar that is stable under storage and has a working time suitable for practical use over a wider temperature range. That is, an object of the present invention is to provide a chemical mortar that exhibits suppression of the polymerization reaction 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 are solved by the two-component mortar composition according to 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 optionally be combined with each other.

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

[0012] The present invention is based on the idea of additionally providing a temperature-responsive polymerization inhibitor to a conventional mortar composition in other respects. According to the present invention, the "temperature-responsive polymerization inhibitor" is understood to be an inhibitor that shows no or almost no inhibitory effect at low temperature or room temperature, but significantly contributes to inhibition at high temperature. In the interaction with conventional polymerization inhibitors already established in the mortar system, such a temperature-responsive polymerization inhibitor can have the effect of obtaining a storage-stable mortar composition having a working time suitable for practical use at both low and high temperatures. Therefore, a specific object of the present invention is typically compatible with specific chemical properties in a composite mortar composition having many different components, and shows no or almost no inhibitory effect on the radical curing reaction at low temperature (such as room temperature), but shows a significant inhibitory effect at high temperature (such as 40 °C or higher). The object is to find a compound.

[0013] In a general embodiment, the present invention is 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) is selected from a phenolic polymerization inhibitor, 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 two-component mortar composition containing one or more polymerization inhibitors, the resin component (A) 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 and further contains an alkoxyamine compound (I). The two-component mortar composition is characterized by this.

[0014] An alkoxyamine is a compound containing the structural element R-O-N(R’R”) (wherein 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 in 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, since homolysis hardly occurs at room temperature, it was found that there are hardly any radicals that can suppress the radical curing reaction of the radical curable resin of the resin component (A) at room temperature. As a result, the radical curing reaction of the radical curable resin of the resin component (A) proceeds without being affected by the additional presence of the alkoxyamine compound (I) at room temperature. However, at a higher temperature, for example, a temperature of 40 °C or higher, the activation energy E for the homolysis of the R-O bond a When it is within the range of 100 kJ / mol to 120 kJ / mol, homolysis already occurs significantly. As a result, there are sufficient radicals to sufficiently suppress the additional radical curing reaction of the radical curable resin of the resin component (A). Therefore, at a higher temperature, the additional presence of the alkoxyamine compound (I) has a significant inhibitory effect on the radical curing reaction of the radical curable resin of the resin component (A), that is, the working time is extended at a higher temperature compared to the case where the alkoxyamine compound (I) is not present. Thus, according to the present invention, it is possible to provide a mortar composition that exhibits a practical working time both at low temperature and high temperature.

[0017] In a preferred embodiment, the activation energy E for the homolysis of the R-O bond in the alkoxyamine compound (I) a is within the range of 100 kJ / mol to 110 kJ / mol. In a more preferred embodiment, the activation energy E for the homolysis of the R-O bond in the alkoxyamine compound (I) a is within the range of 100 kJ / mol to 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 radically curable resin as a curable component and a curing agent 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, 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 two-component mortar composition, the resin component (A) has the following formula (II) [Chemical formula] (wherein R 1 is a C 3~10 alkyl group, R 2 is a C 2~10 alkyl group, where R 1 and R 2 may together with the N atom to which they are attached form an optionally substituted, optionally unsaturated heteroalkyl ring, R 3 is H or a C1-4 alkyl group, R4 is a C 1~4 alkyl group, R 5 is an aryl or heteroaryl group) and further contains an alkoxyamine compound of the formula (II). The two-component mortar composition is characterized by this.

[0019] In the alkoxyamine compound of the formula (II), the R 3 R 4 R 5 C-O bond undergoes thermoreversible homolysis according to the following reaction formula [Chemical formula]

[0020] From the alkoxyamine compound of the formula (II), R 3R 4 R 5 By homolysis of the C-O bond, a nitroxyl radical of the formula ·O-N(R 1 R 2 ) and an alkyl radical of the formula (R 3 R 4 R 5 )C· are formed. According to the present invention, at least one of the radicals formed in this process should be a good inhibitor for the radical polymerization of the radically curable resin of the 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 suitable substitution in the alkoxyamine compound of formula (II).

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

[0022] R in the alkoxyamine compound of formula (II) 2 represents a C 2~10 alkyl group, for example a C 4~8 alkyl group. R 2 may be linear or branched. Preferably, R 2 is branched at the β-position with respect to the nitrogen atom to which it is attached. Additionally or alternatively, R 2 may optionally be branched at the α-position with respect to the nitrogen atom as well. Further, R 2 may be substituted or unsubstituted. For example, R 2It may be substituted at the α-position relative to the nitrogen atom.

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

[0024] In the alkoxyamine compound of formula (II), R 3 represents H or a C 1~4 alkyl group. R 3 may be substituted or unsubstituted. Further, R 3 may be linear or branched. In one embodiment, R 3 is a hydrogen atom.

[0025] In the alkoxyamine compound of formula (II), R 4 is a C 1~4 alkyl group. This means that the unpaired electron in the alkyl radical of the formula (R 3 R 4 R 5 )C· is located at a (at least) secondary or tertiary C atom. R 4 may be substituted or unsubstituted. Further, R 4 may be linear or branched. In one embodiment, R 4 is a methyl group.

[0026] In the alkoxyamine compound of formula (II), R 5 is an aryl or heteroaryl group, for example, a C 6~20 aryl group such as phenyl, naphthyl, anthracenyl or pyrenyl. That is, the unpaired electron in the alkyl radical of the formula (R 3 R 4 R 5 )C· is in the α-position relative to the conjugated π-system. R 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 may be selected, for example, from an alkyl substituent (such as C 1~4 alkyl) 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 optionally protonatable substituent in R 1 , R 2 , R 3 , R 4 or R 5 include, but are not limited to, an amine group such as a dialkylamine (e.g., di-C 1~4 alkylamine). Examples of the optionally deprotonatable substituent in R 1 , R 2 , R 3 , R 4 or R 5 include, but are not limited to, a carboxylic acid group, a sulfonic acid group, a sulfinic acid group, or a phosphonic acid group. Examples of the optionally hydrolyzable substituent in R 1 , R 2 , R 3 , R 4 or R 5 include, but are not limited to, an alkyl ester of a carboxylic acid, a sulfonic acid, a sulfinic acid, or a phosphonic acid (e.g., C 1~4 alkyl ester). In one embodiment, R 2is substituted at the α-position with respect to the nitrogen atom, and the substituent is preferably selected from a carboxylic acid alkyl ester group, a sulfinic acid ester group, a sulfonic acid ester group, and a phosphonic acid ester group.

[0028] In one embodiment, R in the alkoxyamine compound of formula (II) 3 R 4 R 5 The activation energy E for the homolysis of the C-O bond a 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 The activation energy E for the homolysis of the C-O bond a 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 The activation energy E for the homolysis of the C-O bond a is in the range of 100 kJ / mol to 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 a phenolic polymerization inhibitor, phenothiazine and / or its derivative, a stable organic radical, an oxime, and a pyrimidinol or pyridinol compound substituted at the para-position with respect to the hydroxyl group. Such a polymerization inhibitor is usually present in an amount of 0.1% by weight to 1.0% by weight based on the amount of the radically curable resin of the resin component (A).

[0030] Examples of such polymerization inhibitors are, in particular, hydroquinone, substituted hydroquinones, such as those described in European Patent No. 1935860 (A1) or European Patent No. 0965619 (A1), for example, 4-methoxyphenol, phenothiazine, benzoquinone or tert-butylpyrocatechol, nitroxyl compounds, in particular stable nitroxyl radicals also called N-oxyl radicals, such as those described in German Patent Application Publication No. 19531649 (A1), piperidinyl-N-oxyl or tetrahydropyrrole-N-oxyl. Particularly preferably, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (hereinafter referred to as tempol) is 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, 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'-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 a mixture of two or more thereof, can be used as phenolic polymerization inhibitors and are often components of commercially available radically curable resins.

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

[0034] Suitable stable N-oxyl radicals (nitroxyl radicals) are 1-oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol (also called TEMPOL), 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one (also called 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 called 3-carboxy-PROXYL), aluminum-N-nitrosophenylhydroxylamine, and diethylhydroxylamine, as described in German Patent Application Publication No. 19956509. Even more suitable N-oxyl compounds are oximes such as acetaldoxime, acetone oxime, methyl ethyl ketoxime, salicyl oxime, benzoxime, glyoxime, dimethylglyoxime, acetone-O-(benzyloxycarbonyl)oxime. Further, pyrimidinol or pyridinol compounds substituted at the para position with respect to the hydroxyl group, as described in German Patent Application Publication No. 102011077248 (B1), can be used as polymerization inhibitors.

[0035] The polymerization inhibitors can be used alone or in combinations of two or more thereof, depending on the desired properties and use of the resin mixture. The combination of phenolic polymerization inhibitors and non-phenolic polymerization inhibitors enables a synergistic effect, as shown by setting the gelation time of the reactive resin composition in a substantially drift-free setting.

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

[0037] The fixing of the fixing element using the two-component mortar composition according to the present invention provides a practical working time both at low temperature and high temperature. According to the present invention, this is achieved by including, in addition to a conventional polymerization initiator, 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 composition.

[0038] A further advantage of the present invention can be found in the description of the following preferred embodiments.

[0039] For the purposes of the present invention, the "two-component mortar composition" is understood to mean a mortar composition consisting of a curable resin component and a curing agent component for the resin component, and the resin component and the curing agent component are stored separately from each other so that the reaction between the curing agent component and the resin component does not occur during storage. When the curing agent component is mixed with the reactive resin immediately before application of the mortar composition, the curing of the reactive resin is initiated.

[0040] The mortar composition according to the present invention may further contain at least one inorganic additive as a further constituent in the resin component (A) and / or the curing agent component (B). The term "inorganic additive" refers to all inorganic constituents 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 additives. For example, the amount of the inorganic additive is in the range of 40% to 75% by weight based on the total weight of the mortar composition. In one embodiment, the amount of the inorganic additive is in the range of 15% to 65% by weight, for example 30% to 60% by weight, based on the total weight of the mortar composition.

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

[0042] Preferably, the inorganic additive includes a filler that can be contained in the resin component (A) and / or the curing agent component (B). Examples of suitable fillers are BaSO4, quartz, glass, corundum, porcelain, stoneware, barite, lightweight spar, gypsum, talc, fly ash and / or chalk, and mixtures thereof, for example in the form of sand, powder or shaped articles, preferably in the form of fibers or spheres.

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

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

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

[0046] Among these compounds, a 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 them, unsaturated polyester resins and vinyl ester resins are particularly suitable, and are described, for example, in the applications of European Patent No. 1935860 (A1), German Patent Application Publication No. 19531649 (A1), and International Publication No. 10 / 108939 (A1). In this case, due to its hydrolysis resistance and excellent mechanical properties, vinyl ester resin is most preferred.

[0047] Examples of 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 glycols. These resins may contain a higher proportion of reactive diluents than ortho resins. (3) Bisphenol A fumarate esters: These are based on ethoxylated bisphenol A and fumaric acid. (4) HET acid resins (hexachlorendomethylene tetrahydrophthalic 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, those referred to as dicyclopentadiene resins (DCPD resins) can also be distinguished as unsaturated polyester resins. The class of DCPD resins can be obtained by modifying one of the above resin types by a Diels-Alder reaction with cyclopentadiene, or alternatively, this resin can be obtained by a first reaction of a diacid, such as maleic acid, with dicyclopentadiene, followed by a second reaction of the normal preparation of an unsaturated polyester resin, the latter being called a 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 5000, and even more preferably in the range of 750 to 4000 (in accordance with ISO 13885-1). n 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 using a DCPD resin 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, the vinyl ester resin is an oligomer or polymer having at least one (meth)acrylate end group, called a (meth)acrylate-functionalized resin, which also includes urethane (meth)acrylate resins and epoxy (meth)acrylates.

[0051] Vinyl ester resins having unsaturated groups only at the terminal positions can be obtained, for example, by reacting an epoxy oligomer or polymer (e.g., bisphenol A diglycidyl ether, phenol novolak type epoxy, or an epoxy oligomer based on tetrabromobisphenol A) with, for example, (meth)acrylic acid or (meth)acrylamide. Preferred vinyl ester resins are (meth)acrylate-functionalized resins and resins obtained by reacting an epoxy oligomer or epoxy polymer with methacrylic acid or methacrylamide, preferably methacrylic acid. Examples of this type of compound are known from the applications of U.S. Patent No. 3,297,745(A), U.S. Patent No. 3,772,404(A), U.S. Patent No. 4,618,658(A), British Patent Application Publication No. 2,217,722(A1), German Patent No. 3,744,390(A1), and German Patent No. 4,131,457(A1). In this context, reference is made to the application of U.S. Patent Application Publication No. 2011 / 071234.

[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 (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, difunctional, trifunctional or higher-functional urethane (meth)acrylate oligomers, or mixtures of these curable components are particularly suitable as vinyl ester resins.

[0054] Examples of this type of epoxy (meth)acrylate are those of formula (A),

Chemical formula

[0055] Further examples of propoxylated or especially ethoxylated aromatic diols, such as bisphenol A, bisphenol F or novolac (especially di -)(meth)acrylates are those of the formula (B), [Chemical formula] In the formula, a and b each independently represent a number of 0 or more, provided that preferably at least one of these values is greater than 0, preferably both are 1 or more (when there is a mixture of different molecules having different (a and b) values and is represented by the formula (B), non-integer values are also possible as an average).

[0056] For example, known reaction products of di - or polyisocyanates and hydroxyalkyl methyl acrylates described in German Patent No. 2312559 (A1), adducts of (di)isocyanates and 2,2 - propanebis[3 - (4 - phenoxy)-1,2 - hydroxypropane - 1 - methacrylate] according to U.S. Patent No. 3629187, and adducts of isocyanates and methacryloyl alkyl ethers, alkoxybenzenes or alkoxycycloalkanes described in European Patent No. 44352 (A1) are very particularly suitable. 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, mixtures of suitable monomers can also be used.

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

[0059] Furthermore, the resin may contain other reactive groups that can be polymerized with a radical initiator such as a peroxide, for example, (itaconic acid esters) described in WO 2010 / 108939, for example, reactive groups derived from itaconic acid, citraconic acid and allyl groups.

[0060] The percentage ratio (by weight of the reactive resin) of the radical curable resin in the resin component (A) is preferably greater than about 5%, preferably greater than about 15%, particularly preferably greater than about 20%. The percentage ratio (by weight of the resin component) of the radical curable resin in the resin component is preferably 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%, very particularly preferably from about 32% to about 45%.

[0061] The radical curable resin in the 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 for preparing urethane (meth)acrylate resins may be aromatic isocyanates, aliphatic isocyanates, particularly alicyclic isocyanates, and isocyanate group-containing prepolymers, and these may also be used by mixing them with each other.

[0064] Examples of suitable aliphatic and aromatic isocyanates include m-phenylene diisocyanate, toluylene-2,4-diisocyanate, toluylene-2,6-diisocyanate, hexamethylene-1,6-diisocyanate, tetramethylene-1,4-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrotoluylene diisocyanate, naphthylene-1,5-diisocyanate, methoxyphenyl-2,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, 4,4'-biphenylene 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), toluylene-2,4,6-triisocyanate, and 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate.

[0065] Diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, and their mixtures are collectively called MDI, and all of them can be used. Toluylene-2,4-diisocyanate, toluylene-2,6-diisocyanate, and their mixtures are usually called TDI, and all of these can also be used.

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

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

[0068] Examples of such chain extenders are 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, further 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 higher-membered 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 hydroxyl group-containing polyesters based on the above alcohols and polyethers and dicarboxylic acids or their anhydrides such as adipic acid, phthalic acid, tetra- or hexahydrophthalic acid, heteric acid, maleic acid, fumaric acid, itaconic acid, sebacic acid.

[0069] The chain extender having an aromatic structural unit functions to harden the resin chains. By using a hydroxyl compound having an unsaturated structural unit, for example, fumaric acid, the crosslink density during curing can be increased. Branched or star-shaped hydroxyl compounds as chain extenders, particularly alcohols having a trivalent or higher valence, and polyethers and / or polyesters containing the structural units thereof result in branched or star-shaped urethane (meth)acrylates that exhibit a lower resin viscosity and improved solubility in reactive diluents.

[0070] The hydroxy-functional (meth)acrylic compound for preparing the urethane (meth)acrylate resin of the 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 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 hereinafter, the designation “(meth)acrylic...” or “...(meth)acrylic...” means that this designation is intended to include both acrylic groups and methacrylic groups.

[0072] The reaction of at least a bifunctional isocyanate with a hydroxy-functional ethylenically unsaturated compound is carried out such that the resulting free radical 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%, 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.

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

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

[0075] Epoxy (meth) acrylate is usually a condensate of (meth) acrylic acid and glycidyl ether of bisphenol A, bisphenol F or novolac.

[0076] The radically curable resin is present, for example, in a proportion of 10 to 40 weight percent in the mortar composition.

[0077] According to a preferred embodiment of the present invention, the resin component (A) in all of the above embodiments contains, as a further constituent, at least one reactive diluent having at least one ethylenically unsaturated group. Suitable reactive diluents are, in particular, (meth) acrylate compounds and 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 (meth) acrylate ester as a reactive diluent, and particularly preferably, aliphatic or aromatic C5-C 15(Meth)acrylate is selected. Suitable 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, 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, dicyclopentenyl oxyethyl (meth)acrylate and / or tricyclopentadienyl di(meth)acrylate, bisphenol-A-(meth)acrylate, novolac epoxy di(meth)acrylate, di-[(meth)acryloyl-maleoyl]-tricyclo-5.2.1.0.2.6-decane, dicyclopentenyl oxyethyl crotonate, 3-(meth)acryloyl-oxymethyl-tricyclo-5.2.1.0.2.6-decane, 3-(meth)cyclopentadienyl (meth)acrylate, isobornyl (meth)acrylate and decaryl-2-(meth)acrylate; PEG-di(meth)acrylate, for example, PEG200 di(meth)acrylate, tetraethylene glycol di(meth)acrylate, sor ketal (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl di(meth)acrylate, methoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, tert-butyl (meth)acrylate and norbornyl (meth)acrylate.

[0079] As a rule, other conventional radically curable compounds, such as styrene, α-methylstyrene, alkylated styrenes such as tert-butylstyrene, divinylbenzene and allyl compounds, can also be used alone or as a mixture with (meth)acrylate esters. Among them, representative ones that are not subject to mandatory labeling are 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 reactive diluent acts, on the one hand, as a solvent for the radically curable resin and, on the other hand, as a comonomer involved in the radical polymerization of the resin components. The use of the reactive diluent brings about a further improvement in the adhesion of the cured mortar composition to the mineral substrate and / or the surface of the fixing elements to be fixed.

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

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

[0084] Suitable amines are, for example, the following compounds described in the application of US 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, di-isopentylamine, 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, dialkylamine, ethylenediamine, N,N'-dimethylethylenediamine, tetramethylethylenediamine, diethylenetriamine, permethyldiethylenetriamine, 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, 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, ethyl 6-aminohexanoate, isopropyl 11-aminoundecanoate, cyclohexylamine, N-methylcyclohexylamine, N,N-dimethylcyclohexylamine, dicyclohexylamine, N-ethylcyclohexylamine, N-(2-hydroxyethyl)cyclohexylamine, N,N-bis(2-hydroxyethyl)cyclohexylamine, N-(3-aminopropyl)cyclohexylamine, aminomethylcyclohexane, hexahydrotoluene, hexahydrobenzylamine, aniline, N-methylaniline, N,N-dimethylaniline, N,N-diethylaniline, N,N-di-propylaniline, isobutylaniline, toluidine, diphenylamine, hydroxyethylaniline, bis(hydroxyethyl)aniline, chloroaniline, aminophenol, aminobenzoic acid and its esters, benzylamine, dibenzylamine, tribenzylamine, methyldibenzylamine, α-phenylethylamine, xylylamine, di-isopropylaniline, 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,It is 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, indolenine, carbazole, pyrazole, imidazole, thiazole, pyrimidine, quinoxaline, aminomorpholine, dimorpholineethane, [2,2,2]-diazabicyclooctane, and N,N-dimethyl-p-toluidine.,

[0085] 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)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] Polymeric amines, such as those obtained by polycondensation of N,N-bis(hydroxyalkyl)aniline with dicarboxylic acids or by polyaddition of ethylene oxide with these amines, are also suitable as accelerators.,

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

[0088] The resin mixture may also contain a co-accelerator, especially when a transition metal compound is used as the accelerator. Depending on the selected transition metal compound, one skilled in the art can select a co-accelerator suitable for achieving the desired curing properties. When a cobalt compound is used as the accelerator, the co-accelerator is preferably an amine and / or a 1,3-dioxo compound. When a copper compound is used as the accelerator, the co-accelerator is preferably an amine, acetoacetamide, a potassium salt, imidazole and / or a gallate, or a mixture thereof. When a manganese compound is used as the accelerator, the co-accelerator is preferably a 1,3-dioxo compound, a thiol, and / or a potassium or lithium salt, or a mixture thereof. When an iron compound is used as the accelerator, the co-accelerator is preferably a 1,3-dioxo compound and / or a thiol, and is preferably combined with an alkali metal salt. Suitable 1,3-dioxo compounds are acetylacetone, acetoacetate and acetoacetamide.

[0089] For example, the accelerator and / or co-accelerator is present in the mortar composition in a proportion of 0 wt% to 1 wt%, for example 0.01 wt% to 0.7 wt%.

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

[0091] The curing agent for the radically curable resin of the resin component (A) contained in the curing agent component (B) of the two-component mortar composition according to the present invention is preferably 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.

[0092] The organic peroxide is preferably liquefied by adding water, especially as a liquefying agent and / or a solvent. Suitable curing agent components are known to those skilled in the art and are commercially available.

[0093] Alternatively, a peroxide-free curing agent system can be used for curing, and this system has the following components: at least one manganese compound as an accelerator, and a 1,3-dioxo compound as an initiator and contains. For this purpose, German Patent Application Publication No. 102011078785 (A1) is referred to.

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

[0095] As a result of the combination or mixing of the two components, instead of the radical formers that have been customary heretofore, radicals can be formed that can cause the polymerization of non-aromatic double bonds, such as olefin double bonds, such as acrylates or methacrylates.

[0096] As a further alternative, the following components: at least one metal salt as an accelerator As an initiator, at least one formula

Chemical formula

[0097] In both cases, the component used as an accelerator in the form of a metal salt, which also includes metal complexes and metal oxides, is preferably one or more metal salts, or in particular, a salt of an organic acid and / or an inorganic acid with a metal selected from, for example, cobalt, zirconium, zinc, cerium, tin, bismuth, or preferably vanadium, manganese, copper or iron, or a mixture of two or more of them, 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 above group of metals, in particular, an inorganic acid and / or a carboxylate functional group, for example, CH3, C2-C 20 alkyl, C6-C 24 aryl functional group or C7-C 30 carboxylates having an aralkyl functional group, such as octanoate, such as 2-ethylhexanoate (isooctanoate), and further neodecanoate or acetylacetonate, and in the form of salts and complexes, vanadium and iron, or in particular manganese and copper are preferred. Particularly preferred are manganese carbonate or manganese carboxylate, such as Mn acetate or Mn octanoate, copper carboxylate, such as copper octanoate or copper naphthenate, copper quinolate, iron carboxylate, such as iron octanoate, and / or vanadium carboxylate, and / or the group of metal salts having an inorganic acid, such as the group containing iron chloride, iron sulfate and copper chloride.

[0098] In a further alternative, the following components: at least one metal salt as an accelerator, at least one aldehyde and / or ketone as an initiator and at least one primary amine, and / or b2) formula

Chemical formula

[0099] In order to set a suitable viscosity, the curing agent component may contain a certain proportion of inorganic fillers and modifiers, such as thixotropic agents.

[0100] The two-component mortar composition according to the present invention is preferably present in a capsule, cartridge or film pouch, characterized by comprising two or more separate chambers in which the resin component (A) and the curing agent component (B) of the mortar composition are separately arranged to prevent reaction.

[0101] For the intended use, the resin component (A) and the curing agent component (B) are discharged from separate chambers and mixed in a suitable device, such as a static mixer. Then, the mixture of the resin component (A) and the curing agent component (B) is introduced into a previously cleaned drilling hole by means of a known injection device. Then, the fixing element to be fixed is inserted into and aligned in the mortar composition. The curing agent of the curing agent component (B) initiates the radical polymerization of the resin component (A), so the mortar composition cures within a few hours under ambient conditions.

[0102] Accordingly, the present invention also relates to the use of the two-component mortar composition according to the present invention for chemically fixing fixing elements, in particular threaded rods with anchor threads, reinforcing bars, threaded sleeves and screws, in drilling 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 being limited in any way.

Examples

[0104] Generation of Components The compositions of the resin components used in Comparative Example V1 and Application Example A1 below are 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 in each case. In Application Example A1, the following compound (AV1) was used as the alkoxyamine compound of formula (I).

Chemical Formula

[0106] The alkoxyamine compound AV1 (diethyl (1-(tert-butyl(1-(pyren-1-yl)ethoxy)amino)-2,2-dimethylpropyl)phosphonate, MW: 523.6 g / mol) has an activation energy E for the homolysis of the R-O bond of 105.32 kJ / mol. a The amount of AV1 used in Application Example A1 corresponds to 4 equivalents relative to 1 equivalent of the polymerization inhibitor (Tempol).

Table 2

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

[0108] At this time, subsequently, isothermal measurements of the curing curves at 20 °C, 40 °C, and 60 °C were carried out. The crucible tempered at 5 °C was placed in a DSC cell tempered at the measurement temperature, and the measurement was started. The gelation time (time to peak) was measured from the mixing time. The measurement (duration: 120 minutes) was carried out under N2. The results ([min]) obtained here are shown in Table 3.

Table 3

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

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 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′ and R″ are each an organic group), and the activation energy E for the homolysis of the R—O bond is in the range of 100 kJ / mol to 120 kJ / mol ａ A mortar composition, characterized by having the same.

2. The alkoxyamine compound (I) has an activation energy E for the homolysis of the R—O bond in the range of 100 kJ / mol to 110 kJ / mol, preferably 100 kJ / mol to 108 kJ / mol ａ The mortar composition according to Claim 1.

3. 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) has the following formula (II) 【Chemical Formula 1】 (wherein, R １ is a C ３～１０ alkyl group, R ２ is a C ２～１０ alkyl group, where R １ and R ２ may, together with the N atom to which they are attached, form an optionally substituted, optionally unsaturated heteroalkyl ring. R ３ is H or a C １ - ４ alkyl group. R ４ is a C １～４ alkyl group. R ５ is an aryl or heteroaryl group). A mortar composition, further comprising an alkoxyamine compound of ).

4. In the alkoxyamine compound of formula (II), R １ is branched at the α-position relative to the nitrogen atom, preferably a C ４～８ alkyl group branched at the α-position relative to the nitrogen atom. R ２ is branched at the β-position relative to the nitrogen atom, optionally branched or substituted at the α-position relative to the nitrogen atom, and the substituent is preferably selected from a carboxylic acid alkyl ester group, a sulfinic acid ester group, a sulfonic acid ester group, and a phosphonic acid ester group. R ５ is an unsubstituted or substituted C ６～２０ aryl group. In the formula, R １ , R ２ , R ３ , R ４ or R ５ optionally further contains a protonatable group, a deprotonatable group, or a hydrolyzable group. The mortar composition according to claim 3.

5. The alkoxyamine compound of formula (II) has an R within 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 Activation energy E for the homolysis of the C−O bond ａ The mortar composition according to claim 3 or 4, which has.

6. The mortar composition according to any one of claims 1 to 5, wherein the alkoxyamine compound (I) or the alkoxyamine compound of formula (II) is present in an amount of 0.5 equivalent to 100 equivalents, preferably 1 equivalent to 10 equivalents, per 1 equivalent of the polymerization inhibitor.

7. The mortar composition according to any one of claims 1 to 6, wherein the resin component (A) and / or the curing agent component (B) contains at least one inorganic additive selected from the group consisting of an inorganic filler, a hydraulic or polycondensable inorganic compound, a modifier, and mixtures thereof.

8. The inorganic additive is BaSO ４ The mortar composition according to claim 7, which contains a filler selected from the group consisting of, quartz, glass, corundum, porcelain, stoneware, barite, lightweight spar, gypsum, talc, fly ash, chalk, and mixtures thereof.

9. The mortar composition according to claim 7 or 8, wherein the inorganic additive is a hydraulic or polycondensable inorganic compound selected from the group consisting of cement and gypsum, and mixtures thereof, preferably aluminate cement.

10. The mortar composition according to any one of claims 7 to 9, wherein the inorganic additive is a modifier selected from the group consisting of a thickener, a plasticizer, a thixotropic agent, and mixtures thereof, preferably precipitated or fumed silica, bentonite, and / or kaolin.

11. The radical curable resin is selected from a compound based on urethane (meth) acrylate, a compound based on epoxy (meth) acrylate, a methacrylic acid ester of alkoxylated bisphenol, and a compound based on a further ethylenically unsaturated compound. The radical curable resin is preferably selected from a compound based on urethane (meth) acrylate, a compound based on epoxy (meth) acrylate, and a methacrylic acid ester of alkoxylated bisphenol. More preferably, the radical curable resin contains a urethane (meth) acrylate resin. The mortar composition according to any one of claims 1 to 10.

12. The mortar composition according to any one of claims 1 to 11, wherein the resin component (A) contains at least one reactive diluent as a further constituent component.

13. The mortar composition according to any one of claims 1 to 12, wherein the resin component (A) contains at least one accelerator as a further component.

14. The mortar composition according to any one of claims 1 to 13, wherein the curing agent component (B) contains, as a curing agent, at least one organic peroxide, particularly dibenzoyl peroxide, methyl ethyl ketone peroxide, tert-butyl perbenzoate, cyclohexanone peroxide, lauryl peroxide, cumene hydroperoxide and / or tert-butyl peroxy-2-ethylhexanoate.

15. The mortar composition according to any one of claims 1 to 14, which is in a capsule, cartridge or film pouch, and the resin component (A) and the curing agent component (B) are arranged in separate chambers.

16. Use of the two-component mortar composition according to any one of claims 1 to 15 for chemically fixing fixing elements such as threaded anchor rods, reinforcing bars, threaded sleeves and screws in drilled holes of building materials such as wood or mineral substrates.

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