Epoxy-based fixing mortar with CMR-free reactive diluent

Abstract

The invention relates to a fastening mortar system for mortaring anchoring means based on one or more epoxy-based curing reactive resins into holes or gaps, the fastening mortar system containing a CMR-free reactive diluent, in particular neopentyl glycol diglycidyl ether or glycerol triglycidyl ether; and further relates to associated embodiments of the invention.

Description

[0001] Epoxy-based fixing mortar with CMR-free reactive thinner

[0002] The invention relates to a fixing mortar system for mortaring anchoring means based on epoxy-based reactive resins that harden (after initiation and reaction with a hardener) into holes or gaps or for fixing fibers, non-woven fabrics, woven fabrics or composites for reinforcing structures, and its use for mortaring anchoring means into holes or gaps or for fixing fibers, non-woven fabrics, woven fabrics or composites for reinforcing structures; and related inventive subjects.

[0003] A number of (e.g. injection) fixing mortar systems based on a wide variety of polymer-forming components are known, which, sometimes as single-, sometimes as two- or multi-component systems, are used to mortar in anchoring elements, such as bolts or the like, into holes, such as drill holes, or gaps, in each case in solid substrates such as masonry or concrete. Other components can then be attached to the anchoring elements. The mortaring of the anchoring elements (synonymously referred to here as anchoring elements) is based on the one hand on adhesive effects in the sense of a material bond between the synthetic mortar and an anchoring element and / or the wetted surface of the hole or gap, and on the other hand, possibly on form fit, such as undercuts by surrounding with the synthetic mortar projecting or indented sections of the anchoring element and / or the hole or gap.

[0004] An example of particularly suitable systems are those based on epoxides, such as glycidyl compounds, and suitable (epoxy) hardeners.

[0005] WO 2011 / 113533 A1 shows the use of trimethylolpropane triglycidyl ether as a reactive diluent in fixing mortar systems.

[0006] FIS EM Plus 390 S® (fischerwerke GmbH & Co. KG, Waldachtal, Germany) is a highly successful, market-established example of a two-component injection mortar system for mortaring anchoring elements. It is based on an epoxy resin in component A and amines as a hardener in component B, along with additional components in each component. As mentioned in the examples below, the system contains trimethylolpropane triglycidyl ether, abbreviated to trimethylolpropane-TGE, as a reactive diluent.For the compound trimethylolpropane-TGE, originally labelled as "II" (no sensitising effect), it was surprisingly found that it actually falls into the potency category "HS" (high sensitising potency) with regard to allergenic effect, i.e. - see "Ranking of substances in epoxy resin systems based on their sensitising potencies (FP-0324), Research and Consulting Institute for Hazardous Substances GmbH, Klarastrasse 63, Freiburg, December 2012 - see https: / / www.dguv.de / medien / ifa / de / pro / pro1 / ff-fp0324 / gesamtbericht.pdf.

[0007] Worse still, it has been found that trimethylolpropane TGE (which is de facto a polymer) can impair fertility (hazard statement H360F) and thus has a so-called CMR effect (carcinogenic, mutagenic and toxic for reproduction) - see, for example, ECHA information at https: / / echa.europa.eu / de / substance-information / - / substanceinfo / 100.111.042

[0008] The known epoxy-based reaction systems already show very good adhesion failure loads, but the new test systems and procedures pose further challenges, so that one task is to achieve even better properties, such as further increased adhesion failure loads, even under these conditions - which are already quite unusual for real-life conditions.

[0009] Furthermore, it is important to avoid substances that are harmful to health, especially those that have CMR (in this disclosure, CMR effect), in order to best protect users and other persons who may come into contact with the components from health damage.

[0010] Surprisingly, it has now been found that when using glycerol triglycidyl ether and / or neopentyl glycol diglycidyl ether, on the one hand the health impairments to be feared with trimethylolpropane TGE can be avoided, and on the other hand - interestingly preferably with the same possible concentrations (mass fractions) of the reactive diluents due to the same epoxy equivalent numbers (particularly in the case of glycerol triglycidyl ether in comparison with trimethylolpropane TGE) - with an otherwise identical composition of the epoxy-based fixing mortar systems - improved properties such as a lower tendency to creep, better extrusion properties, in particular even at lower temperatures such as 5 °C, and increased strength, as can be proven for example by an increase in the glass transition temperature, are found.In addition, it exhibits increased chemical resistance to trimethylolpropane TGE, particularly with glycerol triglycidyl ether. It should be noted that glycerol triglycidyl ether is a technical product comprising various species and is only idealized as glycerol triglycidyl ether. This is also reflected in the fact that the substance, under CAS number 90529-77-4, is not subject to registration under Regulation (EC) No. 1907 / 2006 (REACH) (since it is a polymer).

[0011] Neopentyl glycol diglycidyl ether has the CAS number 17557-23-2.

[0012] By adding certain silanes, which may or may not have reactive groups capable of participating in the polymerization with a synthetic resin based on epoxy-based reactive resins and in any case have Si-bonded hydrolyzable groups, further advantages can be achieved, in particular higher adhesion failure loads.

[0013] The invention therefore relates, in a first embodiment, to a fixing mortar system for mortaring anchoring agents based on one or more curing (used synonymously with curable in the present disclosure) epoxy-based reactive resins into holes or gaps, which is characterized in that it is at least largely free of trimethylolpropane TGE (i.e. in particular < 1% by weight, in particular < 0.3% by weight), preferably completely free thereof, and contains glycerol triglycidyl ether and / or neopentyl glycol diglycidyl ether as a reactive diluent. In particular embodiments, silanes which may or may not have reactive groups capable of participating in the polymerization with a synthetic resin based on the curing epoxy-based reactive synthetic resin(s) (i.e., do not have such reactive groups) and in any case have Si-bonded hydrolyzable groups may be included.A fixing mortar system according to the invention therefore also comprises one or more curable epoxy-based reactive resins and a corresponding hardener, e.g. as defined below, in particular based on (poly)amines and / or (poly)thiols.

[0014] In a further embodiment (= embodiment), the invention relates to the use of a fixing mortar system for mortaring (fixing) anchoring means in holes or gaps, in particular in drill holes in a building substrate, such as masonry or concrete, wherein the fixing mortar system is based on curing reactive synthetic resins based on epoxy, is completely (preferably) or at least largely free of trimethylolpropane TGE (< 1 wt.%, in particular < 0.3 wt.%) and contains glycerol triglycidyl ether and / or neopentyl glycol diglycidyl ether as reactive diluent - and optionally in one or more components (already before the start of the curing reaction) in addition to the curable reactive resin(s) based on epoxy and one or more corresponding hardeners, e.g. as defined below or in particular based on (poly)amines and / or (poly)thiols, one or more no or at least one amino, sec.Amino, mercapto, epoxy, isocyanato, alkenyl, (meth)acryloyl, anhydrido and / or (in particular) epoxy group, and at the same time silanes containing at least one Si-bonded hydrolyzable group, as well as other customary additives, for filling holes or gaps in building substrates such as masonry, concrete or the like.

[0015] In a further embodiment, the invention relates to the use of a fixing mortar system, as defined above and below, for fixing fibers, scrims, fabrics or composites for reinforcing structures, in particular walls, ceilings or floors, in which the components of the fixing mortar system are mixed and applied to fibers, scrims, fabrics or composites and / or to the surfaces of structures to be fixed, in particular walls, ceilings or floors, and the fibers, scrims, fabrics or composites for reinforcing structures and the surfaces of the structures are brought into contact with one another and the fixing mortar system is caused to harden, so that the surfaces are bonded to one another; wherein the fixing mortar system is designed on the basis of hardening reactive synthetic resins based on epoxy, is completely or at least largely free from trimethylolpropane TGE (< 1 wt.%, in particular < 0.3 wt.-%) and contains glycerol triglycidyl ether and / or neopentyl glycol diglycidyl ether as reactive diluent - and optionally in one or more components (already before the start of the curing reaction) in addition to the curable epoxy-based reactive resin(s) and one or more corresponding hardeners, e.g. as defined below or in particular based on (poly)amines and / or (poly)thiols, one or more silanes containing no or at least one amino, sec. amino, mercapto, epoxy, isocyanato, alkenyl, (meth)acryloyl, anhydrido and / or (in particular) epoxy group, and at the same time at least one Si-bonded hydrolyzable group, as well as other customary additives.

[0016] The present invention also relates to corresponding processes and methods for mortaring anchoring elements and holes or gaps, in which a fixing mortar system as described in the last paragraph or below is used for mortaring anchoring means, or (further) for fixing fibers, fabrics, wovens or composites for reinforcing structures.In this case, such a fixing mortar system and an anchoring means are introduced one after the other, in particular first the fixing mortar system, then the anchoring means, or (at least substantially) simultaneously into a hole or a gap in a substrate (in particular a cracked substrate, as in a particular embodiment of the invention in cracked concrete), or (further) fibers, scrims, fabrics or composites and / or surfaces of structures which are to be reinforced, such as those of walls, ceilings or floors, are subjected to the fixing system under or after mixing the components of a fixing system according to the invention, and the corresponding surfaces are brought into contact with one another, the fixing system is allowed to cure and the said surfaces are thus bonded together.

[0017] A further embodiment of the invention relates to a use of glycerol triglycidyl ether and / or neopentyl glycol diglycidyl ether as a reactive diluent instead of a potentially harmful reactive diluent in a fixing mortar system for mortaring anchoring agents based on one or more curing reactive resins based on epoxy into holes or gaps to reduce or avoid health impairments during and after application and / or in particular to increase chemical resistance compared to trimethylolpropane triglycidyl ether;in particular the use of glycerol triglycidyl ether and / or neopentyl glycol diglycidyl ether as a reactive diluent in a fixing mortar system for mortaring anchoring agents or for fixing fibers, scrims, fabrics or composites for reinforcing structures, based on one or more curing epoxy-based reactive resins, for replacing a reactive diluent having a CMR and / or allergenic and / or skin-sensitizing effect and / or for avoiding CMR and / or allergenic or skin-sensitizing effects of a reactive diluent; in each case in particular instead of or avoiding the use of trimethylolpropane triglycidyl ether as a reactive diluent;Preferably, the percentage mass fractions of all other components of a fixing mortar system based on one or more curing epoxy-based reactive resins (which is otherwise identical in composition to the corresponding fixing mortar system with the replaced CMR and / or allergenic and / or skin-sensitizing reactive diluent) are maintained. A preferred embodiment of the invention relates to the use of glycerol triglycidyl ether as a reactive diluent in a fixing mortar system to increase chemical resistance compared to trimethylolpropane TGE (in particular added in the same mass fraction).

[0018] Increasing chemical resistance refers, in particular, to increasing resistance to polar organic solvents such as acetone or ethanol. This chemical resistance can be determined, in particular, by measuring swelling, as described in the examples.

[0019] Further embodiments of the invention are set forth in the claims, which are incorporated herein by reference, with dependent claims indicating preferred embodiments of the invention.

[0020] Regarding the optional silane additives, without wishing to be definitively bound by this attempt at explanation, these may potentially enable better contact with the wetted substrate surface in the hole or gap, whether in the form and / or in the bonding. It is also possible that there is improved internal cohesion of the resulting cured synthetic mortar (which tends to be thick layers when mortaring anchoring systems), which may also contribute to the high values ​​for adhesion failure. This is a particularly surprising aspect of the present invention.

[0021] Surprisingly, the fixing mortar systems according to the invention or usable according to the invention, when used in foil bags or two- or multi-chamber cartridges, exhibit easier extrusion even at lower temperatures (e.g., from 0 to 10 °C, in particular from 5 ± 2 °C), and / or generally higher glass transition temperatures compared to otherwise identically formulated products containing trimethylolpropane TGE. A reduced tendency to creep can also be observed. In particular, increased chemical resistance is also demonstrated.

[0022] In all embodiments of the invention, the viscosity of the silanes is preferably 10 Pa*s or lower, such as 1 Pa*s or lower. Extremely low-viscosity and low-molecular-weight silanes with viscosities of less than 100 mPa*s, in particular less than 10 mPa*s, are particularly preferred.

[0023] Unless otherwise stated, viscosities are measured according to DIN EN ISO 2555:2000-01 using a Brookfield DV-lll+ viscometer with a suitable spindle and rotation speed according to the standard, for glycidyl ethers, for example, with spindle 3 at 20 revolutions / minute (rpm) at 23 °C, and are given in Pa * s (or Pas).

[0024] Glass transition temperatures (Tg) are measured according to ISO 11357-2:2020-8 after 7 days of curing at 23 °C. The calorimetric analysis of the samples is carried out using a DSC Q200 from TA Instruments (with Universal Analysis software) according to ISO 11357 at a heating rate of 20 K / min.

[0025] In order to achieve high strengths and sophisticated mechanical properties, the use of elastomeric structural units, especially on the hardener side, is preferably largely or preferably completely avoided (particularly when using silanes carrying epoxy groups).

[0026] The following definitions serve to clarify certain terms or symbols and to describe particular embodiments of the invention, whereby in the embodiments (“embodiments”) of the invention mentioned above and below, individual, several or all terms or symbols can be replaced by more specific definitions, leading to special embodiments of the invention, which are hereby also all to be regarded as specifically disclosed. If, in particular, mass fractions (in wt. %) are stated, then for each constituent mentioned in an embodiment, the variants with the same position number, counted backwards from the most preferred variant, define preferred embodiments. For example, if component A has a proportion of x to y wt.%, preferably from x* to y* wt.%, in particular from x** to y** wt.% and component B has a proportion of v to w wt.%, preferably from v* to w* wt.-%, then, among other things, a preferred embodiment can be defined with a proportion of A of x* to y* wt.% and a proportion of B of v to w wt.%.

[0027] The term “fixing mortar system” in the present disclosure is synonymous with “fixing resin system”.

[0028] Where mass data are given in percent (given as wt. %), unless otherwise stated, these refer to the total mass of the reactants and additives of the fixing mortar system (i.e., the components present in the mass to be cured after mixing, excluding packaging and other possible parts such as static mixers or the like), or to the total mass of the formulations mentioned in the examples. Where such mass data are mentioned above and below, they can be used individually or in combination in preferred embodiments of the invention in each embodiment, resulting in preferred embodiments of the respective embodiment(s).

[0029] In particular embodiments of the invention, the silanes which carry one or more no or at least one amino, sec. amino, mercapto, isocyanate, alkenyl, (meth)acryloyl, anhydrido and / or (in particular) epoxy group, in particular containing amino, thiol (= mercapto) and / or (preferably) epoxy groups, and containing at least one Si-bonded hydrolyzable group are those of the formula I,

[0030] [Ri-X-(CH2)n-]p-Si(R B ) q (L)t (I) where

[0031] X stands for S (preferred) or NRi* (preferred) or O or NCO or nothing; where X is nothing (= absent) when Ri stands for anhydrido;

[0032] Ri and R1*, all independently of one another, represent hydrogen, cycloalkyl, alkyl, aminoalkyl, (meth)acryloyl, aryl, aralkyl, acyl, heterocyclyl (especially anhydrido) or a radical of the formula -[(CH2) n *]p*-Si(R B *)3-t*(L*) t* or (in particular) epoxyalkyl, wherein, in each case independently of the other radical, R B * the following for R B mentioned meanings, L* has the meanings given below for L and n*, p* and t* each have the meanings given below; where Ri is hydrogen when X is S; where X is O when Ri is epoxyalkyl or (meth)acryloyl; where Ri is nothing when X is NCO (= isocyanates);

[0033] R B independently of one another represents an alkyl, alkenyl, arylalkyl or aryl group, preferably alkyl and / or (further) alkenyl,

[0034] L represents a hydrolyzable radical, in particular alkoxy; n and, if present, n* independently represent a positive integer, in particular 1 to 10; p represents 0 to 3 and, if present, p* independently represents 1 to 3; q represents 0 to 2; and t stands for 1 to 4 and, if present, t* independently stands for 1 to 3, with the proviso that: p + q + t = 4 and, if present, p* + (3-t*) + t* = 4. Further silanes with hydrolyzable groups can be included, for example (based on the total weight of all silanes) up to 80 wt.%, up to 70 wt.%, up to 60 wt.%, up to 50 wt.%, up to 40 wt.%, up to 30 wt.%, up to 20 wt.% or up to 10 wt.% - this implies, for example, alkoxysilane compounds or silane crosslinkers, such as vinylalkoxysilanes, e.g. vinyltrimethoxysilane or vinyltriethoxysilane or (further or in particular) esters of (poly)silicic acid (such as e.g.Dynasilan® 40 (an ethyl polysilicate) or Dynasylan® A, Evonik GmbH, Frankfurt am Main, Germany), which allow control of the degree of crosslinking, or mixtures of two or more thereof.

[0035] Silanes may be present in all embodiments of the invention, based on the total mass of the reactants and additives of the fastening system, preferably in a proportion of 0.1 to 30 wt.%, in particular of 0.2 to 20 wt.%.

[0036] A particularly preferred silane is glycidyloxypropyltrimethoxysilane. Alternatively, another silane as defined above or below may be preferred instead of glycidyloxypropyltrimethoxysilane.

[0037] Within this disclosure, aryl is always preferably an unsubstituted or (e.g. by alkyl, alkoxy (= alkyloxy), alkenyl, hydroxy, or further halogen, such as fluorine, chlorine or bromine, or cyano) mono- or independently polysubstituted, e.g. 1- to 3-fold, aromatic radical having 6 to 18 ring carbon atoms, for example phenyl, naphthyl or toluyl.

[0038] Aralkyl within this disclosure is always aryl as defined above, which is bonded to alkyl as defined above, for example benzyl or phenylethyl, but can preferably be omitted from lists within this disclosure.

[0039] Cycloalkyl stands in particular for mono-, di- or tricyclic, preferably monocyclic, cycloalkyl having 3 to 20 carbon atoms, preferably having 3 to 10 carbon atoms, in the ring, in particular for cyclopentyl or cyclohexyl.

[0040] Epoxyalkyl preferably represents alkyl as defined above which is substituted by an epoxy group to form a ring.

[0041] Epoxyalkyl is in particular epoxy-Ci-C?-alkoxy, such as in particular (2,3-epoxy-propan-1-yl) of the formula

[0042] (the dashed line marks the end of the bond to the rest of the molecule).

[0043] Epoxyalkoxy is in particular epoxy-Ci-C?-alkoxy, such as in particular a radical of the formula

[0044] (the dashed line marks the end of the bond to the rest of the molecule).

[0045] Within this disclosure, acyl always represents a residue of a carboxylic acid or a sulfonic acid, for example an aryl, alkyl or aralkyl carboxylic acid or sulfonic acid residue, such as Ci-C?-alkanoyl, e.g. acetyl or propionyl, aroyl (aryl-C(=O)-), such as benzoyl, or the like.

[0046] Within this disclosure, alkyl always represents in particular an unbranched or singly or multiply branched alkyl radical having, for example, 1 to 20, preferably 1 to 10 carbon atoms, for example having 1 to 4 carbon atoms, in which one or more, for example 1 to 3, preferably not directly adjacent, in particular separated by 2 carbon atoms and not terminal, chain sections containing a C atom (such as -CH2- or -C(-)(H)-) can be replaced by a heteroatom, such as -N(-)-, -NH-, -O- or -S-, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.

[0047] Within this disclosure, alkenyl always represents an unbranched or singly or multiply branched mono- or polyunsaturated alkyl radical having 2 to 20, preferably 2 to 10, e.g. 2 to 4 carbon atoms, such as vinyl, allyl or buten-1- or -2-yl.

[0048] Aminoalkyl means alkyl substituted by one or more amino groups, as just defined.

[0049] Heterocyclyl means in particular an optionally substituted, e.g. as defined for aryl above, mono-, di- or tricyclic, in particular monocyclic radical having 3 to 20, preferably 3 to 8 ring atoms, of which one or more, in particular 2, are heteroatoms independently selected from N, O and S, and may be substituted by one or more oxo groups, in particular those bonded to ring carbon atoms bonded via an O heteroatom (leading to anhydrido). Heterocyclyl therefore also includes in particular anhydrido, which is a cyclic radical containing the following ring-closing bridge element: -C(=O)-O- C(=O)-. The ring therefore contains a carboxylic anhydride group.A possible preferred example is 2,5-dioxo-oxolan-3-yl, another the corresponding unsaturated variant 2,5-dioxo-oxol- -3-yl with a double bond between the C atoms in positions 3 and 4 of the ring, another a 2,5-dioxolan-3-yl radical benzo-annelated in the 3,4-position.

[0050] Aromatic means that the corresponding radicals are defined as aryl above.

[0051] Aromatic-aliphatic (e.g. arylalkyl) means that the corresponding radicals contain combinations of aliphatic radicals and aromatic radicals, as mentioned above.

[0052] The fact that "X stands for nothing" or X is nothing, or something similar, means that the residue "-X-" in the respective formula represents a single bond. The fact that Ri is "nothing" means that the residue Ri is missing.

[0053] “If present” refers to the fact that a radical or a symbol may be present or absent depending on other definitions, for example, in the case that only when p in formula I is 1 to 3, and Ri is a radical of the formula -[(CH2)n*]p*-Si(R B *)3- t*(L*) t * means n*, p*, R B *, L* and t* can even exist.

[0054] Silanes which may or may not contain reactive groups capable of participating in polymerisation with a resin based on the curing reactive epoxy-based resin(s) contain these reactive groups optionally, i.e. they may contain them.

[0055] Where reference is made to “silanes” or other components or features mentioned above and below (such as building substrates, anchoring materials, fibres, fabrics, wovens or composites) in the plural, this always means “one or more”.

[0056] “Contain” or “comprise” means that in addition to the named components or features, others may be present, and therefore represents a non-exhaustive list, in contrast to “consist(ing) of,” which means an exhaustive list of the components or features listed when it is used. “Consist(ing) of” can preferably be chosen instead of a non-exhaustive list. “Partially or exclusively” or “at least partially” means that the components named thereafter may be present alongside other components of the corresponding component or exclusively, for example (e.g. in the case of silanes or reactive resins or hardeners as components) in proportions of up to a maximum of 10, 20, 30, 40, 50, 60, 70 or 80 to 90 or 100 wt.%, based on the respectively defined component.

[0057] Where the attribute “further” is mentioned, this means that features without this attribute may be more preferred.

[0058] “And / or” means that the mentioned characteristics / substances can be present alone or in combination of two or more of the mentioned characteristics / substances.

[0059] "At least substantially free of trimethylolpropane TGE" means completely free of or a proportion of < 1 wt.%, in particular < 0.3 wt.%, of trimethylolpropane TGE in the fixing mortar system. "At least partially replacing" or "at least partially avoiding the use of trimethylolpropane triglycidyl ether" also means complete replacement or complete avoidance (whichever is preferred), or that < 1 wt.%, in particular < 0.3 wt.%, of trimethylolpropane TGE may still be present.

[0060] “Mortar” or “mortar” refers to “artificial mortar” or “artificial mortar”.

[0061] (Meth)acryl stands for acrylic, methacrylic or acrylic and methacrylic (as a mixture).

[0062] Si-bonded hydrolyzable groups (also symbolized by L in this disclosure) are to be understood as meaning, for example, halogen atoms (halogen, such as chloro), ketoximates, amino, aminoxy, mercapto, acyloxy, aryloxy, aralkyloxy (= arylalkoxy) or in particular alkyloxy (alkoxy), preferably methoxy or ethoxy.

[0063] The hardening (here also used synonymously with “hardenable”) reactive synthetic resins based on epoxy that are included when using or in fixing mortar systems according to the invention comprise an epoxy reactive resin constituent or an epoxy reactive resin component, preferably based on glycidyl compounds, for example those with an average glycidyl group functionality of 1.5 or greater, in particular of 2 or greater, e.g. from 2 to 10, which can optionally comprise further glycidyl ether(s) apart from trimethylolpropane TGE as a reactive diluent. In the case of the epoxides of the epoxy component (of which trimethylolpropane TGE is also preferably completely or partially excluded, in particular completely or in an amount of <1 wt.%, preferably <0.3 wt.%, is present) are preferably poly(including di)glycidyl ethers of at least one polyhydric alcohol or phenol, such as novolak, bisphenol F or bisphenol A, or mixtures of such epoxides, obtainable, for example, by reacting the corresponding polyhydric alcohols with epichlorohydrin. Examples are novolak epoxy resins, bisphenol A-epichlorohydrin resins and / or bisphenol F-epichlorohydrin resins, for example with an average molecular weight of <2000. The epoxy resins can, for example, have an epoxy equivalent of 120 to 2000, preferably 150 to 400, such as in particular 155 to 195, for example 165 to 185. The proportion of the reactants and additives in the fixing mortar system is preferably 5 to less than 100 wt.%, in particular 10 to 80 wt.%, 10 to 70 wt.%, or 10 to 60 wt.%. Mixtures of two or more such epoxy components are also possible.Suitable epoxy resins, reactive diluents and hardeners can also be found in the standard work by Lee H and Neville K, “Handbook of Epoxy Resins” (New York: McGraw-Hill), 1982 (these compounds are incorporated herein by reference).

[0064] The epoxy-based reactive resin must contain glycerol triglycidyl ether as a reactive diluent, preferably in a mass fraction, based on the entire fixing mortar system without packaging, of 0.2 to 30 wt.%, in particular of 2 to 20 wt.%, more preferably of 5 to 15 wt.%, for example of 10 ± 2 wt.%. The overall mass fraction of reactive resin and reactive diluent preferably remains within one of the ranges specified in the last paragraph.

[0065] Alternatively or in addition to glycerol triglycidyl ether, neopentyl glycol diglycidyl ether, which also does not require an H360F classification, can also be used in all embodiments of the invention. The corresponding mass fractions of glycerol triglycidyl ether and / or neopentyl glycol diglycidyl ether are then preferably the values ​​in wt.% specified in the previous paragraph. Where only glycerol triglycidyl ether is mentioned, "glycerol triglycidyl ether, furthermore neopentyl glycol diglycidyl ether, or a mixture of the two" can be read or used.

[0066] In addition to the reactive diluent glycerol triglycidyl ether and / or neopentyl glycol diglycidyl ether included according to the invention, one or more further reactive diluents may be included, preferably those without H360F classification.

[0067] As further reactive diluents (which should not be present in a hardener component, i.e. preferably included in the epoxy reactive resin component (e.g. component (A)), glycidyl ethers of aliphatic, cycloaliphatic, araliphatic or aromatic mono- or especially polyalcohols can be used, such as monoglycidyl ethers, e.g. o-cresyl glycidyl ether, and / or in particular glycidyl ethers with an epoxy functionality of at least 2, such as 1,4-butanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, hexanediol diglycidyl ether and / or in particular tri- or higher glycidyl ethers, e.g. pentaerythritol tetraglycidyl ether, or in particular neopentyl glycol diglycidyl ether, or further mixtures of two or more of these reactive diluents. Glycidylsilanes, e.g. according to WO2011 / 113533, are also possible. Reactive diluents are preferably present in amounts of 0 to 60 wt., based on the total weight of the epoxy component (a).-%, in particular from 1 to 30 wt.%.

[0068] Epoxy equivalents refer to the values ​​specified by the manufacturer (also referred to as EP equivalent in the examples). Epoxy equivalent values ​​are usually specified on the raw materials by the manufacturer or are determined or calculated using known methods. They indicate the amount in g of resin that corresponds to one mole of epoxy groups.

[0069] "Based" means in particular that the fixing mortar systems according to the invention or to be used according to the invention (synonymously also referred to as (injection) synthetic mortar systems) may contain, in addition to the components mentioned (such as synthetic resin component (A) and hardener (B)), other customary ingredients (e.g., additives or other components mentioned above or below). These additional ingredients may, for example, be present in a total amount of up to 80% by weight, preferably between 0.01 and 65% by weight. Even where "based" is not expressly mentioned, such customary ingredients are included.

[0070] Important examples of additional ingredients (additives) are one or more selected from accelerators, inhibitors, reactive diluents, thixotropic agents, fillers and / or other additives.

[0071] Accelerators which may be included as accelerators are, for example, tert-amines such as imidazoles or tert-aminophenols such as 2,4,6-trimethylaminomethylphenol, organophosphines or Lewis bases or acids such as phosphoric acid esters, or mixtures of two or more thereof, in one or (particularly in multi-component systems) in several of the components, preferably in each case in a hardener component, for example in a weight proportion of 0.001 to 15 wt.%, based on the total mass of the reactants and additives of the fixing mortar system.

[0072] In particular, the hardener component may contain novolaks (= novolak resins), which also have an accelerating effect, preferably those of the formula (I), wherein R 1 and R 2 each independently represent H or -CH 3, R 4, R 5 and R 6 each independently represent H, -CH 3 or an aliphatic radical, preferably a linear, saturated or partially unsaturated, branched or preferably unbranched hydrocarbon chain having up to 15, preferably up to 4 carbon atoms, or an alkylaryl radical, in particular -C 5 H 6 , and n is 0 to 20, preferably 0 to 15.

[0073] According to formula (I), the novolak resin may also be, in particular, bisphenol F.

[0074] Particularly preferably, the novolak resin corresponds to formula (II), wherein

[0075] Ri is H, R2 is a Ci-Cis-alkyl radical, preferably methyl or tert-butyl, m is 0, 1 or 2, preferably 1 or 2, in particular 1, and n is 0 to 15, preferably 0 to 6.

[0076] Here, 2,4'- and / or 4,4'-dihydroxydiphenylmethane (bisphenol F and / or the isomer 2,4-bisphenol-F, and / or alternative novolaks are preferred novolak-type accelerators.

[0077] The novolak content in the hardener is, based on the mass of the organic components of the hardener, preferably 5 to 30 wt.%, in particular 8 to 25 wt.%.

[0078] Preferred embodiments of the invention with novolaks in the hardener comprise, in the epoxy resin component, in addition to the above-mentioned epoxides, glycerol triglycidyl ether (preferred) or neopentyl glycol diglycidyl ether, each in a total proportion of 0.2 to 30 wt.%, in particular of 2 to 20 wt.%, more preferably of 5 to 15 wt.%, for example of 10 ± 2 wt.%, in each case based on the total mass of the reactants and additives of the fastening system, are largely (i.e. in particular < 1 wt.%, in particular < 0.3 wt.%) or in particular completely free of trimethylolpropane TGE, and in the hardener component novolaks, such as bisphenol F, preferably in a proportion of 5 to 30, in particular of 8 to 25 wt.%, based on the mass of the organic compounds in the hardener; and preferably contain one or more silanes, in particular as defined above, preferably in a proportion of 0.1 to 30 wt.%, in particular 0.2 to 20 wt.-%, may be present.

[0079] Common rheological aids, such as fumed silica, can be used as thixotropic agents. They can be added in a weight proportion of 0.001 to 50 wt.%, for example, 1 to 20 wt.%.

[0080] Conventional fillers are used, in particular cements (e.g. Portland cements or high-alumina cements), chalks, sand, quartz sand, quartz flour or the like, which can be added as powder, in granular form or in the form of shaped bodies, or others, as mentioned for example in WO 02 / 079341 and WO 02 / 079293 (which are incorporated herein by reference), or mixtures thereof, wherein the fillers can furthermore or in particular also be silanized, for example as amino- or epoxysilane-treated quartz flour, such as Silbond AST or EST® from Quarzwerke GmbH, as amino- or glycidylsilane-treated silica, such as Aktisil AM or EM® from Hoffmann Mineral, or amino- or glycidylsilane-treated pyrogenic silicas. Additionally or alternatively, hydraulically curable fillers, such as gypsum, quicklime or cement (e.g.Alumina or Portland cement), water glasses, or active aluminum hydroxides, or two or more of these, can be added. To improve the environmental performance and CO2 footprint of the cement mortar system, pulverized recycled materials from waste products can also be used as fillers.

[0081] The recycled filler is preferably selected from the group consisting of powders or flours of concrete, bricks, sand-lime bricks, natural stones, fly ash, rubber, recycled plastics, recycled glass, thermosets, elastomers, gypsum (e.g., obtained from Regips boards), carbon black, and, for example, cured chemical fixing mortar systems present during the processing of the recycled filler, or generally powder of a cured chemical anchor. The filler(s) may be present in one or more components, for example, of a multi-component kit according to the invention, for example, one or both components of a corresponding two-component kit; the proportion of fillers is preferably 0 to 90 wt.%, for example, 10 to 90 wt.%.

[0082] Other additives may also be added, such as plasticizers, non-reactive diluents, flexibilizers, stabilizers, rheological aids, wetting agents, coloring additives such as dyes or, in particular, pigments, for example, for differentially coloring the components to better control their mixing, or the like, or mixtures of two or more thereof. Such further additives can preferably be added in total weight proportions of 0 to 90%, for example, from 0 to 40% by weight, in particular from 0 to 20% by weight.

[0083] Certain of the compounds mentioned in the definition of epoxides, which have a lower viscosity than epoxides containing aromatic groups, can also be used as reactive diluents, for example in a weight proportion of 0.1 to 90 wt.%, e.g. between 0.5 and 75 wt.% or between 1 and 40 wt.%.

[0084] The hardener contains at least one compound commonly used for epoxy curing (reactant in the polyaddition). The term “hardener” preferably means at least one compound commonly used for epoxy curing, with or without filler additives and / or other additives, such as water, thickeners, and / or other additives, such as dyes and the like; in other words, the complete hardener component. This hardener can be incorporated as a separate component and / or (particularly in a protected form, e.g., in microencapsulated form) also in the reaction resin formulation (as a curable component, e.g., one that hardens by polymerization after mixing with the hardener after breaking open the shell of the microcapsule). Common additives can be added, such as:Fillers (in particular as defined above) and / or (in particular for producing a paste or emulsion) solvents such as benzyl alcohol and / or water may be added, whereby water or acids or mixtures thereof, such as water, salicylic acid and / or acetic acid, may serve as a “hardener” (initiator) for the condensation of the silanes containing hydrolyzable groups and is only included if the hardener component itself is otherwise free of hydrolyzable silanes.

[0085] The compounds commonly used for epoxy curing in hardeners (which act as reactants in the polyaddition, the hardeners in the narrower sense) are in particular those with two or more groups selected from amino, imino, and mercapto, for example corresponding amines (preferred), thiols, or aminothiols, or mixtures thereof, for example as mentioned in Lee H and Neville K, “Handbook of Epoxy Resins” (New York: McGraw-Hill), 1982, which is incorporated herein by reference, for example di- or polyamines, and / or di- or polythiols mentioned therein. The compounds commonly used for epoxy curing include, for example, in all embodiments of the invention, preferably

[0086] - Amine hardeners, i.e. di- or polyamines such as in particular aliphatic (such as ethylenediamine), cycloaliphatic and aromatic di- or polyamines, amidoamines, amine adducts, polyetherdiamines or polyphenyl / polymethylene polyamines, Mannich bases, polyamides and the like (wherein in the case of Mannich bases in particular those as disclosed in the publication WO 2005 / 090433, especially on pages 3, last, to page 6, 2nd paragraph, as in Example 1 or in particular 2 thereof, which is incorporated herein by reference, alone or in admixture with one or more further di- or polyamines are particularly preferred), or mixtures of two or more thereof; preferred are diamines, in particular xylylenediamines, such as m-xylylenediamine (= MXDA; preferred, synonymously m-phenylenebis(methylamine)), C1-C10 alkanedi- or polyamines, e.g.1,2-Diaminoethane, trimethylhexane-1,6-diamine, diethylenetriamine or triethylenetetraamine; oligomeric diamines of the formula H2N-(CH2)i-NH-[(CH2)j-NH]k-(CH2)l-NH2, where i, j and I independently of one another are 2 to 4 and k is 0, 1 or 2, in particular “triethylenetetramine” (TETA = N,N'-bis(2-aminoethyl)ethylenediamine) or tetraethylenepentamine (TEPA); cycloaliphatic amines, such as 1,2-diaminocyclohexane or bis(aminomethyl)tricyclodecane (TCD) or bis(4-aminocyclohexyl)methane (PACM), amine adducts; N,N'-bis(3-amino-n-propyl)piperazine (BAPP), 1,3-bis(aminomethyl)cyclohexane (BAG), N-(2-aminoethyl)piperazine (AEP) or 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine = IPDA), or Mannich bases; or mixtures of two or more thereof;.

[0087] - furthermore di- or polythiols such as in particular di- or higher-functional thiols, for example dimercapto-a,w-C1-C12-alkanes, 4,4'-dimercapto-dicyclo- ,hexyhmethane, dimercaptodiphenylmethane or the like;

[0088] - furthermore aliphatic aminos, such as in particular hydroxy-lower alkylamines, such as ethanolamine, diethanolamine or 3-aminopropanol, or aromatic aminos, such as 2-, 3- or 4-aminophenol.

[0089] Particularly preferred are mixtures of Mannich bases and diamines (such as MXDA in particular).

[0090] Mixtures of two or more of the compounds commonly used for epoxy curing may also be used or included.

[0091] The compounds commonly used for epoxy curing are, if present, preferably present in amounts of up to 95 wt.%, preferably from 2 to 70 wt.%, based on the total mass of the reactants and additives of the mass of the fixing mortar system to be cured (e.g. fixing resin system, in particular injection resin system).

[0092] Based on the hardener component of a multi-component fixing mortar system according to the invention, the proportion of the corresponding compounds in a possible preferred embodiment of the invention is 1 to 100 wt.%, e.g. 4 to 95 wt.%, 5 to 90 wt.% or 10 to 80 wt.%.

[0093] An alternative for a hardener (for homopolymerization) can also be a tertiary amine, such as 1,4-diazabicyclo[2.2.2]octane, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 8-diazabicyclo[5.4.0]undec-7-ene, N,N,N',N'-tetramethylethylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine or in particular 2,4,6-tris(dimethylaminomethyl)phenol.

[0094] In particular embodiments of the invention, the compounds commonly used for epoxy curing, the epoxy base, or both, do not have any rubber modification in order not to impair strength. The compounds commonly used for epoxy curing include, for example, in one embodiment of the invention

[0095] - di- or polyamines such as in particular aliphatic (such as ethylenediamine), cycloaliphatic and aromatic di- or polyamines, amidoamines, amine adducts, polyetherdiamines or polyphenyl / polymethylene polyamines, Mannich bases, polyamides and the like (Mannich bases, in particular as disclosed in the document WO 2005 / 090433, in particular on pages 3, last, to page 6, 2nd paragraph, as in Example 1 or in particular 2 thereof, which is incorporated herein by reference in this regard, alone or in admixture with one or more further di- or polyamines are particularly preferred);

[0096] - di- or polythiols such as in particular di- or higher-functional thiols, for example dimercapto-a,co-C1-C12-alkanes, 4,4'-dimercapto-dicyclohexylmethane, dimercaptodiphenylmethane or the like;

[0097] - furthermore aliphatic aminos, such as in particular hydroxy-lower alkylamines, such as ethanolamine, diethanolamine or 3-aminopropanol, or aromatic aminos, such as 2-, 3- or 4-aminophenol.

[0098] Mixtures of two or more of the compounds commonly used for epoxy curing may also be used or included.

[0099] The reactivity of the amine hardeners can also be increased by other ingredients in the hardener, such as phenols, bisphenols, novolaks, salts (as described, for example, in EP 4 121 474 B1 or WO 2020 / 058015).

[0100] The compounds commonly used for epoxy curing, if present, are preferably present in amounts of up to 95 wt.%, preferably from 2 to 70 wt.%, based on the total mass of the reactants and additives of the mass of the injection resin system to be cured.

[0101] Based on the hardener component, the proportion of the corresponding compounds in a possible preferred embodiment of the invention is 1 to 100 wt.% (since aminosilanes alone can also be used as hardeners), for example 3 to 95 wt.%, e.g. 4 to 95 wt.%, 5 to 90 wt.% or 10 to 80 wt.%.

[0102] Particularly in the case of a hardener component of a multi-component system according to the invention, further additives may also be part of the “hardener”, such as (in the presence of silanes with hydrolyzable groups) water, or organic solvents such as benzyl alcohol, fillers (e.g. as mentioned above) and other of the above-mentioned additives, for example in a total weight proportion of 0.01 to 70 wt.%, e.g. from 1 to 40 wt.%.

[0103] A hole or gap is understood to mean a hole or gap that is present in a solid (in particular already finished as such) substrate, in particular masonry or concrete, in particular a cracked substrate such as cracked concrete, and is accessible from the outside, for example a drill hole, or furthermore an area left out when mortaring with cement or plaster or the like.

[0104] Buildings can be, for example, houses, bridges, towers, fortification or retaining walls (including concrete walls), walls (including concrete walls) of other types, monuments or the like.

[0105] In a particular embodiment of the invention, the epoxide(s) (epoxy reactive resin component) and the (associated) hardener (compound(s) commonly used for epoxy curing) are stored separately from each other in a two- or multi-component system before they are mixed together at the desired location (e.g. at or in a hole or gap, such as a borehole) and thus caused to react.

[0106] In particular, these are two-component systems in which the weight ratio of a first component (A) (reactive resin component or synthetic resin component) to a second component (B) (hardener component) is 99:1 to 1:99, 99:1 to 50:50, 99:1 to 60:40 or 99:1 to 70:30.

[0107] Components that would otherwise react undesirably with each other, such as water and / or acids and the hydrolyzable groups of the silanes or water and cement optionally used according to the invention, should preferably be kept separate from each other before use in the hole or gap.

[0108] For example, component (A) of such a two- or multi-component system contains the epoxide(s), while component (B) contains the hardener. The optional silanes can be provided independently as a third component, or they are part of the epoxy reactive resin component and / or the hardener. The optional silanes which have an amino, secondary amino and / or mercapto group are preferably contained in the hardener component, while silanes carrying epoxy, and also isocyanato, (meth)acryloyl and / or anhydrido groups are preferably contained in the epoxy component. Silanes which have hydrolyzable groups can be present in both components. In all cases, the components in which silanes with hydrolyzable groups are present must be kept largely free of water (e.g. less than 0.1%, in particular less than 0.05 wt.-% water based on the total weight of the respective component) in order not to cause undesired hydrolysis and crosslinking by means of the Si-bonded hydrolyzable groups, or such silanes and the water must be kept separate from each other (for example by microencapsulation).

[0109] Fixing mortar systems according to the invention can therefore be provided (prepared) and also used as a single-component system (if otherwise reactive components, e.g. the hardener, are protected, for example encapsulated, with other components present) or preferably as a multi-component system (multi-component kit).

[0110] A multi-component kit is to be understood in particular as a two- or (further) multi-component kit (preferably a two-component kit) with a component (A) which contains an epoxy reactive resin component, as described above and below, e.g. one or more compounds carrying epoxy such as glycidyl groups, as described above and below, and hardener (component (B)), wherein further additives can be provided in one or both of the components, preferably a two- or further multi-chamber device, in which the mutually reactive components (A) and (B) and optionallyfurther separate components are contained in separate compartments in such a way that their components cannot react with each other during storage (in particular during curing), preferably in such a way that their components do not come into contact with each other before use, but which makes it possible to mix components (A) and (B) and, if necessary, further components for fastening at the desired location, for example directly in front of or in a hole, and to introduce them if necessary, so that the curing reaction can take place there.Also suitable are cartridges, for example made of plastic, ceramic or in particular glass, in which the components are arranged separated from one another by destructible boundary walls (for example when driving an anchoring element into a hole or a gap, such as a borehole) or integrated, separate destructible containers, for example as nested cartridges, such as ampoules; as film bags containing several, in particular two, compartments; and as, in particular, multi-component or, in particular, two-component cartridges (which are likewise particularly preferred), in the chambers of which the several or preferably two components (in particular (A) and (B)) of the fixing mortar according to the invention with the compositions mentioned above and below are contained for storage before use, wherein a static mixer is preferably also part of the corresponding kit.

[0111] The use of a fixing mortar according to the invention at the desired location is carried out by mixing the associated components, in particular close to and / or directly in front of a hole or (for example, in particular when using cartridges with static mixers) directly in front of and / or (in particular when destroying corresponding cartridges or ampoules) within a hole or gap, e.g. a borehole.

[0112] "Mortaring" refers in particular to the (material and / or form-fitting) fastening of anchoring elements made of metal (e.g. undercut anchors, threaded rods, screws, drill anchors, bolts) or of another material, such as plastic or wood, into solid (preferably already finished as such) substrates, such as concrete or masonry, in particular as far as they are components of artificially constructed structures, especially masonry, ceilings, walls, floors, slabs, pillars or the like (e.g. made of concrete, natural stone, masonry made of solid or perforated bricks, also plastic or wood), in particular in holes, such as drill holes. These anchoring elements can then be used to fasten, for example, railings, covering elements such as panels, facades or other building elements.

[0113] Where reference is made to “mixtures of two or more thereof”, this includes in particular mixtures of at least one of the components mentioned, which are highlighted as preferred, with one or more other components, in particular one or more components also marked as preferred.

[0114] "Completed as such" means, in particular, that the substrates are already finished (e.g., as building blocks or walls) except for possible surface modifications (such as coating, e.g., plastering or painting) or the like, and are not finished at the same time as the fixing mortar or consist of it. In other words, the fixing mortar is preferably not itself a finished substrate.

[0115] The anchoring agent(s) are preferably introduced shortly after mixing the components of the inventive fixing mortar, preferably 30 minutes or less. For explanation: With the mixing and introduction of the components onto or into the desired locations where the anchoring agents are to be secured, particularly holes such as drill holes, several reactions begin, essentially proceeding in parallel and / or with only a slight temporal offset, in particular polyaddition. The final curing occurs in situ.

[0116] Specific embodiments of the invention are defined above or in the examples or in the claims.

[0117] The proportion of epoxy components in the total mass of reactants and additives of the fixing mortar system is, for example, preferably 5 to less than 100 wt.%, in particular 10 to 80 wt.%, 10 to 70 wt.%, or 10 to 60 wt.%. Mixtures of two or more such epoxy components are also possible.

[0118] A preferred fixing mortar system according to the invention or used according to the invention is characterized in that it is a two-component system, in particular in the form of a two-chamber cartridge with or without a static mixer.

[0119] The invention also relates to the use of a fixing mortar system, as defined above or below, for mortaring anchoring elements into holes or gaps, in particular in boreholes, such as wet boreholes, in which the fixing mortar system and an anchoring means are introduced into a hole or gap in a building substrate, such as masonry or concrete, and the fixing mortar system is allowed to harden.

[0120] The invention also relates to the use of a fixing mortar system, as defined above and below, for fixing fibers, scrims, fabrics or composites for reinforcing structures, in particular walls, ceilings or floors, in which the components of the fixing mortar system are mixed and applied to fibers, scrims, fabrics or composites and / or to the surfaces of structures to be fixed, in particular walls, ceilings or floors, and the fibers, scrims, fabrics or composites for reinforcing structures and the surfaces of the structures are brought into contact with one another and the fixing mortar system is caused to harden so that the surfaces are bonded together.

[0121] The invention also relates to a process or method for mortaring anchoring elements and holes or gaps, in which a fixing mortar system as defined above or below is used for mortaring anchoring elements, wherein the fixing mortar system and an anchoring element are introduced into a hole or gap and the fixing mortar system is allowed to harden.

[0122] The invention also relates to a process or method for fastening fibers, scrims, fabrics or composites for reinforcing structures, in particular walls, ceilings or floors, in which the components of the fastening mortar system are mixed and applied to fibers, scrims, fabrics or composites and / or to the surfaces of structures to be fastened, in particular walls, ceilings or floors, and the fibers, scrims, fabrics or composites for reinforcing structures and the surfaces of the structures are brought into contact with one another and the fastening mortar system is caused to harden so that the surfaces are bonded together.

[0123] In a preferred embodiment, the invention also relates to the use of glycerol triglycidyl ether and / or neopentyl glycol diglycidyl ether as a reactive diluent in a fixing mortar system for anchoring agents based on one or more curing epoxy-based reactive resins for replacing a reactive diluent having a CMR and / or allergenic or skin-sensitizing effect and / or for avoiding CMR and / or allergenic or skin-sensitizing effects of a reactive diluent; in each case in particular instead of or avoiding the use of trimethylolpropane triglycidyl ether as a reactive diluent; preferably in each case while maintaining the percentage mass fractions of all other constituents of a fixing mortar system based on one or more curing epoxy-based reactive resins and a hardener.

[0124] In a very preferred embodiment, the invention relates to the use of glycerol triglycidyl ether and / or neopentyl glycol diglycidyl ether as reactive diluents in a fixing mortar system to increase chemical resistance compared to trimethylolpropane TGE (in particular added in the same mass fraction and at least partially replaced according to the invention). Neopentyl glycol diglycidyl ether may also be preferred over glycerol triglycidyl ether in all embodiments of the invention. Alternatively, glycerol triglycidyl ether may be preferred in all embodiments. As a further alternative, a mixture of glycerol triglycidyl ether and neopentyl glycol diglycidyl ether may be preferred in all embodiments (“and”). In all embodiments, glycerol triglycidyl ether is particularly preferred over neopentyl glycol diglycidyl ether.

[0125] The following examples serve to illustrate the invention without limiting its scope.

[0126] Example 1: Comparison of simple compositions with trimethylolpropane TGE (comparison) and glycerol triglycidyl ether (example) as reactive diluents:

[0127] The mixtures listed in Table 1 were prepared. For curing, 10 g of the respective mixture were mixed with 1.98 g of MXDA and cured for 7 days at 23 °C.

[0128] The calorimetric analysis of the samples to determine the glass transition temperature was carried out using the DSC Q200 from TA Instruments (with the Universal Analysis software) according to ISO 11357-2:2020-8 with a heating rate of 20 K / min.

[0129] Table 1: Example recipe

[0130] Results of the comparative study:

[0131] The resin mixture with the reactive diluent trimethylolpropane triglycidyl ether gaveT Compared to the reactive diluent glycerol triglycidyl ether according to the invention, a higher glass transition temperature was observed in both the first and second runs. For this reason, a lower tendency to creep (especially at elevated temperatures) is also to be expected with glycerol triglycidyl ether.

[0132] To test chemical resistance, cuboidal test specimens measuring 60 x 13 x 2 mm were prepared from the above-mentioned mixtures and immersed in acetone, ethanol, and petroleum ether for 24 hours. The swelling levels are given in weight percent.

[0133] This shows that, especially against polar solvents, significantly better chemical resistance can be achieved with glycerol triglycidyl ether than with trimethylolpropane TGE, where the test specimen is completely destroyed by severe swelling under the influence of acetone. Resistance to non-polar solvents such as petroleum ether is very good for both reactive diluents, with swelling < 0.1%.

[0134] Example 2: Reference example and inventive fixing resin mortar

[0135] In the existing product FIS EM Plus from fischer (Component A (synthetic resin component): bisphenol A / F epichlorohydrin resin with an average molecular weight of < 700, white Portland cement, trimethylolpropane triglycidyl ether; Component B (hardener component): Mannich base, m-phenylenebis(methylamine), 2,4,6-tris(dimethylaminomethyl)phenol, benzyl alcohol, Portland cement), the 10% trimethylolpropane triglycidyl ether contained in the mortar was replaced with the same amount of glycerol triglycidyl ether. The exchange was easily possible from a stoichiometry perspective, as the epoxy equivalents are the same at 140-150 g / g.

[0136] In the case of neopentyl glycol ether, the hardener component would have had to be reformulated due to the different epoxy equivalent to obtain comparable pull-out values. This was omitted; a 1:1 exchange was made. Due to the resulting different stoichiometry, only the extrusion force of the mortar with neopentyl glycol diglycidyl ether was determined.

[0137] The components are subjected to an adhesion failure test in the commercially available 2-chamber cartridge with static mixer under the conditions described above using the guideline from the “European Organisation for Technical Approvals” (EOTA) (2001): ETAG N° 001 Edition November 2006, Guideline for European technical approval of Metal Anchors for Use in Concrete, Part 5: Bonded Anchors, February 2008, under 5.1.2.1 (b) and the mean value of the adhesion failure load is determined from 5 tests for M12 bolts at an embedment depth of 72 mm.

[0138] The following pull-out values ​​and extrusion forces were measured:

[0139] With the glycerol triglycidyl ether and also with neopentyl glycol diglycidyl ether, consistently better or at least equally good extraction values ​​were achieved than / as with the trimethylolpropane triglycidyl ether.

[0140] Surprisingly, however, a significantly lower extrusion force was measured with glycerol triglycidyl ether at 5 °C, which is advantageous for the user, as the cartridge is then easier to extrude and can be emptied more quickly. The difference in extrusion force between higher and lower temperatures is also smaller for glycerol triglycidyl ether and neopentyl glycol diglycidyl ether than for trimethylolpropane TGE.

[0141] / Claims

Claims

Claims:

1. A fixing mortar system for mortaring anchoring agents based on one or more curing epoxy-based reactive resins into holes or gaps, characterized in that it contains glycerol triglycidyl ether and / or neopentyl glycol diglycidyl ether as reactive diluent and is at least substantially free from trimethylolpropane triglycidyl ether.

2. Fixing mortar system according to claim 1, characterized in that it is a multi-component system or a multi-component kit comprising an epoxy reactive resin component and a hardener (hardener component), which are contained in different compartments of a multi-chamber device in a reaction-inhibiting manner prior to use; wherein glycerol triglycidyl ether and / or further neopentyl diglycidyl ether are present in a mass fraction of preferably from 0.2 to 30 wt.%, in particular from 2 to 20 wt.%, more preferably from 5 to 15 wt.%, for example from 10 ± 2 wt.%.

3. Fixing mortar system according to claim 2 in the form of a two-component system which contains an epoxy reactive resin component (A) and a hardener (B), in particular in the form of a two-chamber cartridge or a foil bag with two compartments.

4. Fixing mortar system according to one of the preceding claims in the form of a multi-component, in particular two-component system, which contains an epoxy reactive resin component in the form of a glycidyl ether, but is at least largely free of trimethylolpropane triglycidyl ether, which contains glycerol glycidyl ether and / or further neopentyl glycol diglycidyl ether as a reactive diluent, and a hardener selected from di- or polyamines and further di- or polythiols or aliphatic aminos, or a mixture of two or more thereof, preferably selected from two or more di- or polyamines selected from Mannich bases and xylylenediamines.

5. Fixing mortar system according to one of the preceding claims in the form of a multi-component, in particular two-component system, which contains one or more further additives selected from accelerators, inhibitors, fillers, plasticizers, non-reactive diluents, flexibilizers, stabilizers, rheological aids such as thixotropic agents, wetting agents, coloring additives such as dyes or in particular pigments.

6. Fixing mortar system according to one of the preceding claims in the form of a multi-component, in particular two-component system, which contains as filler one or more pulverized recycling fillers in one or more of the components, preferably selected from the group consisting of powders or flours of concrete, bricks, sand-lime bricks, natural stones, fly ash, rubber, waste plastic, waste glass, thermosets, elastomers, gypsum, carbon black and, for example, hardened chemical fixing mortar systems present during the processing of the recycling filler or generally flour of a hardened chemical anchor.

7. Fixing mortar system according to one of the preceding claims, characterized in that it contains neopentyl glycol diglycidyl ether as a further reactive diluent in addition to glycerol triglycidyl ether.

8. Fixing mortar system according to one of the preceding claims in the form of a multi-component, in particular two-component system, characterized in that it contains one or more silanes, preferably those with reactive groups capable of participating in the polymerization with a reactive synthetic resin based on epoxy.

9. Fixing mortar system according to one of the preceding claims, in particular in the form of a multi-component, in particular two-component system, characterized in that it contains novolak epoxy resins, bisphenol A epichlorohydrin resins and / or bisphenol F epichlorohydrin resins as the epoxy reactive resin component.

10. Fixing mortar system according to one of the preceding claims, characterized in that it contains novolak as an accelerator in the hardener, in particular bisphenol F, preferably as a mixture of the 4,4'- and 2,4'-isomers.

11. Fixing mortar system according to one of claims 1 to 10, characterized in that it is a two-component system comprising a component A (synthetic resin component) with bisphenol A / F-epichlorohydrin resin with an average molecular weight of < 700, white Portland cement, glycerol triglycidyl ether and / or further neopentyl glycol diglycidyl ether, and a Component B (hardener component), consisting of Mannich base, m-phenylenebis(methylamine), 2,4,6-tris(dimethylaminomethyl)phenol, benzyl alcohol and Portland cement.

12. Fastening system according to one of claims 1 to 11, characterized in that it is a multi-component, in particular two-component system which contains a component A (synthetic resin component) with bisphenol A, bisphenol F or bisphenol A / F-epichlorohydrin, reactive diluent selected from neopentyl glycol diglycidyl ether, glycerol triglycidyl ether (preferred) and a mixture of glycerol triglycidyl ether and neopentyl glycol diglycidyl ether, and a component B (hardener component) which contains a Mannich base, and preferably one or more further polyamines selected from 1,3-cyclohexanedimethanamine, m-xylylenamine, 2,4,6-tris(dimethylaminomethyl)phenol and bis(dimethylamino)methylphenol; and one or more accelerators selected from 2,4'- and / or 4,4'-dihydroxydiphenylmethane (bisphenol F and / or 2,4-bisphenol F), novolak, wherein the accelerator(s) are present in a proportion of 5 to 30 wt.% in the hardener component, preferably 8 to 25 wt.-%, based on the organic components of the hardener component.

13. Fixing mortar system according to one of the preceding claims, in particular in the form of a multi-component, in particular two-component system, characterized in that the mass fraction of glycerol triglycidyl ether and / or neopentyl glycol diglycidyl ether, based on the entire fixing mortar system without packaging, is 0.2 to 30 wt.%, in particular 2 to 20 wt.%, more preferably 5 to 15 wt.%, for example 10 ± 2 wt.%.

14. Use of a fixing mortar system according to one of the preceding claims for mortaring anchoring means into holes or gaps, in particular in boreholes, such as damp boreholes, in which the fixing mortar system and an anchoring element are introduced into a hole or gap, in particular in a cracked substrate, such as cracked concrete, and the fixing mortar system is allowed to harden, or process or method for mortaring an anchoring element in a hole or gap, in which a fixing mortar system according to one of claims 1 to 13 is used for mortaring the anchoring element, wherein the fixing mortar system and an anchoring element are introduced into a hole or gap, in particular in a cracked substrate, such as cracked concrete, and the fixing mortar system is allowed to harden.

15. Use of glycerol triglycidyl ether and / or further neopentyl glycidyl ether as a reactive diluent instead of a potentially harmful reactive diluent in a fixing mortar system for mortaring anchoring agents based on of one or more curing reactive epoxy-based resins - in particular as defined in one of the preceding claims - into holes or gaps to reduce or prevent health impairments during and after use.

16. Use according to claim 15, wherein the potentially harmful reactive diluent is trimethylolpropane triglycidyl ether.

17. Use, in particular according to claim 15 or claim 16, of glycerol triglycidyl ether and / or further neopentyl glycol diglycidyl ether as a reactive diluent in a fixing mortar system for mortaring in anchoring agents based on one or more curing reactive resins based on epoxy, for at least partially replacing a reactive diluent having a CMR and / or allergenic or skin-sensitizing effect and / or for avoiding CMR and / or allergenic or skin-sensitizing effects of a reactive diluent; in each case in particular at least largely avoiding the use of trimethylolpropane triglycidyl ether as a reactive diluent; preferably in each case while maintaining the percentage mass fractions of all other constituents of a fixing mortar system based on one or more curing reactive resins based on epoxy.

18. Use of glycerol triglycidyl ether and / or neopentyl glycol diglycidyl ether as reactive diluents in a fixing mortar system to increase chemical resistance compared to trimethylolpropane TGE (in particular added in the same mass fraction).

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