DE102011055883B4 - Use of anchoring compounds with very hard aggregates to fix an anchoring element in a borehole - Google Patents

Abstract

Use of an anchoring compound which contains a very hard aggregate with a Mohs hardness of 8 or greater for fastening an anchoring element in a borehole, characterized in that the polymer-forming anchoring compound, when used, is introduced into the borehole before, simultaneously with and/or after an anchoring element and without cleaning the borehole, in particular by blowing out, brushing out and/or rinsing, and remains there, wherein the anchoring compound is designed as a kit in a multi-chamber glass cartridge which, after the anchoring element has been introduced by rotating impact, also serves as a filler, wherein the weight proportion of the hard aggregate, based on the total weight of all components including the cartridge as packaging, is 40 to 65 wt.% and wherein the polymer-forming anchoring compound, when used, contains ethoxylated bisphenol A di-(meth)acrylates or urethane (meth)acrylates in combination with silanes as reactive components.

Description

The invention relates to the use of certain (hard) aggregates, described in more detail below, in polymer-forming chemical anchoring compounds used in fastening technology in the construction sector.

In the construction industry, aggregates in the form of particulate fillers are known for use in polymer-forming chemical anchoring compounds (sometimes referred to as "chemical anchors") with one or more components, for example in the form of two-chamber cartridges, for securing anchoring elements in drilled holes. However, the type of filler is generally considered irrelevant, unless it is a filler that, like cement, contributes to consolidation, for example through hydraulic setting. For example, the EP 0 150 555 B1 explicitly states that the type of filler is not critical and a number of possible fillers are mentioned. Further relevant prior art is represented by the publications DE 43 15 788 A1 , DE 195 31 649 A1 , DE 198 52 720 A1 , DE 10 2008 001 904 A1 , DE 10 2009 019 898 A1 and DE 10 2010 008 971 A1 .

There is a need to further improve the properties of chemical anchoring compounds, particularly with regard to their load-bearing capacity, ease of processing and use, and the possibility of use in damp, uncleaned and/or pre-damaged (e.g., due to cracking) drill holes in substrates such as concrete or masonry.

For example, the building authority approval of fastening systems with chemical anchoring compounds currently requires precise specifications for pre-cleaning drill holes before using the chemical anchoring compounds. This generally requires at least multiple blow-outs, often also brushing, and these specifications must be meticulously adhered to to ensure sufficient strength and functionality. In damp drill holes (as is often expected in outdoor applications), the achievable load-bearing capacities in the cured (polymer) state, as advertised/defined or prescribed in the approval, may be exceeded.

It has now surprisingly been found that very hard aggregates with a Mohs hardness of 8 or greater, in particular fillers, such as preferably corundum, are capable of imparting special properties to anchoring compounds for the said purpose, including one or more of the following improved properties: increased load-bearing capacity, which is expressed, for example, in an increased adhesive failure load; the ability to achieve increased load-bearing capacities even in moist boreholes; the ability to introduce the anchoring compound and anchoring elements without pre-cleaning the borehole, and the ability to achieve good connections between the substrate, anchoring compound and anchoring element even in the event of cracks in the substrate.

These properties can be improved even further by adding silanes in addition to the very hard fillers mentioned (primarily non-polymeric).

The subject matter of the invention is defined by the use claims 1 to 11.

In a first embodiment, the invention relates to the use of an anchoring compound which contains a very hard aggregate with a Mohs hardness of 8 or greater for fastening an anchoring element in a borehole, characterized in that the polymer-forming anchoring compound, when used, is introduced into the borehole before, simultaneously with and/or after an anchoring element and without cleaning the borehole, in particular by blowing, brushing and/or rinsing, and remains there, wherein the anchoring compound is designed as a kit in a multi-chamber glass cartridge which, after the anchoring element has been introduced by rotating impact, also serves as a filler, wherein the weight proportion of the hard aggregate, based on the total weight of all components including the cartridge as packaging, is 40 to 65 wt.% and wherein the polymer-forming anchoring compound, when used, contains ethoxylated bisphenol A di-(meth)acrylates or urethane (meth)acrylates in combination with silanes as reactive components.

Preferably, the anchoring compound is designed as a two-chamber cartridge made of glass.

The very hard aggregate is advantageously corundum.

Associated reactive components of the anchoring mass are preferably provided in a proportion of 5 to 60 wt.% based on the total weight of all reactive components and additives, including the glass serving as filler of the cartridge.

The weight proportion of the very hard aggregate is in particular 50 to 65 wt.%, based on the total weight of all reactive components and additives, including the glass serving as filler of the cartridge.

Preferably, 0.1 to 60 wt.%, e.g. 0.5 to 50 wt.% of hardener, based on the total weight of all reactive components and additives of the anchoring mass, including the glass of the cartridge serving as a filler, are provided, with optionally one or more further additives being provided in a total amount of 0.01 to 50 wt.%, based on the total weight of all reactive components and additives, including the glass of the cartridge serving as a filler.

A preferred embodiment of the invention is characterized in that, to further increase the strength of the bond between the substrate and the object to be fastened, one or more silanes are additionally added, even in the case of ethoxylated bisphenol A di(meth)acrylates as the reactive component. The silane is preferably one or more silanes containing no or at least one amino, secondary amino, mercapto, isocyanato, alkenyl, (meth)acryloyl, anhydrido, and/or epoxy group and containing at least one Si-bonded hydrolyzable group. The silane(s) are advantageously present in a weight fraction of 0.1 to 20 wt. %, based on the total weight of all reactive components and additives, including the glass of the cartridge serving as filler.

In particular, a use according to the invention according to claim 1 is characterized in that the borehole is moist. The borehole is preferably located in a cracked and/or crack-prone concrete substrate.

The use is preferred in the context of setting processes for the anchoring element which are accompanied by strong friction (e.g. by a mechanical setting process, for example with a drill, as well as by a setting resistance which triggers increased friction and which can be influenced by the type, shape and size of the fillers and the resin viscosity), using such anchoring masses in the form of multi-chamber cartridges, such as two-chamber cartridges, made of glass.

In a further embodiment, the invention relates to the last-mentioned use, characterized in that the introduction of the polymer-forming anchoring mass into the borehole takes place despite at least residual contamination of the borehole by drilling material, in particular without pre-cleaning the borehole, especially without brushing, blowing out and/or flushing it.

Despite the lack of cleaning, bond stresses of more than 13 N/mm ² , for example more than 15 N/mm ² , more than 16 N/mm ² , preferably more than 17 N/mm ² and most preferably more than 18 N/mm ² can be achieved.

A particular variant of the invention is that when used according to claim 1 (with or without silane additive), the substrate and/or borehole is moist, has cracks and/or is at risk of cracking (particularly in the tensile zone), wherein in particular the performance of the systems is so high that ratios of the load values measured in moist concrete to those measured in dry concrete are greater than or equal to 0.75, in particular greater than or equal to 0.9, or in cracked concrete the ratio of the failure loads measured in a 0.5 mm crack to those measured in a 0.3 mm crack is greater than or equal to 0.9. The inventive design of the systems can also achieve that the load values have a particularly low variance, in particular < 15%.

• Unter einer bei Verwendung polymerbildenden (unter Polyreaktion reagierenden, also vor der Verwendung „unter Polyreaktion reaktiven“ chemischen Verankerungsmasse (einem Kunstmörtelprodukt für die chemische Verankerung)) ist vor allem ein zwei- oder mehrkomponentiges Produkt zu verstehen. Hierbei steht im Deutschen „polymerisieren“ oder „Polymerisation“ für kinetische Kettenreaktionen als Unterfall von Polyreaktionen, im Gegensatz zum englischen „Polymerization“, das für Polyreaktion allgemein steht. Letzteres ist hier mit „polymerbildend“ gemeint, der deutsche Unterfall nur eine besondere Variante.

The general terms used above and below preferably have the following meanings, whereby in all embodiments of the invention, more general terms (one, several or all) can be replaced by more specific terms, resulting in further particular embodiments of the invention:

• A polymer-forming chemical anchoring compound (a synthetic mortar product for chemical anchoring) is primarily understood as a two- or multi-component product when used (a polymer-forming chemical anchoring compound that reacts under a polyreaction, i.e., is "reactive under a polyreaction" before use). In German, "polymerisieren" or "Polymerisation" stands for kinetic chain reactions as a subcategory of polyreactions, in contrast to the English term "polymerization", which generally refers to polyreactions. The latter is what is meant here by “polymer-forming,” the German sub-case merely being a special variant.

All common polymer-forming resins (with reactive, i.e. polymer-forming components) in which monomers or prepolymers or macromonomers react to form polymers during use are conceivable as the basis for the anchoring mass, whereby according to the invention the polymer-forming anchoring mass contains ethoxylated bisphenol A di-(meth)acrylates or urethane (meth)acrylates in combination with silanes as reactive components.

Examples of such multi-component anchoring compounds are, in particular, those based on mainly di-, tri- and/or polyfunctional synthetic resins and one or more complementary hardeners, such as, in particular, those based on epoxy resins (synthetic resin component: di-, tri- and/or multifunctional epoxy, hardener component: di- and/or polyfunctional organic amino and/or mercapto compounds), polyurethanes or polyureas or mixtures thereof (synthetic resin component: di- and/or polyisocyanates, optionally also as prepolymers or oligomers, hardener component: two or more organic compounds bearing hydroxyl, amino or hydroxyl and/or amino groups or mixtures thereof), alkoxysilane-terminated prepolymers (synthetic resin component: alkoxysilane-terminated prepolymer, hardener component: water and/or organic or inorganic acid(s)),
or in particular those based on reactive olefins as (when used) polymerising (i.e. polymerisable before use) synthetic resin component (complementary hardener component in each case radical hardener), e.g. based on unsaturated polyesters, or
preferably based on (meth)acrylic esters or amides, where (meth)acrylic or "(meth)acrylic" above and below always stands for acrylic and/or methacrylic), such as mono-, di-, tri-, tetra-, penta- or poly(meth)acrylates, in particular mono-, di- or tri(meth)acrylates (including hydroxypropyl(meth)acrylate, hydroxyethyl(meth)acrylate, ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, in particular vinyl esters, such as epoxy acrylates in the form, in particular, of reaction products of di- or polyepoxides, e.g. bisphenol A, bisphenol F or novolak di- and/or polyglycidyl ethers, with (meth)acrylic acid, in particular epoxy(meth)acrylate of the formula where n is a number greater than or equal to 1, whereby, if mixtures of different molecules with different n-values are present and are represented by the formula, non-integer numbers are also possible as the mean value,
Urethane (meth)acrylates (obtainable from the reaction of di-, tri- or polyisocyanates, their prepolymers and/or oligomers with hydroxyalkyl (meth)acrylates and possibly other reactants with Zerewitinoff hydrogen atoms such as alkylene glycols or polyalkylene glycols),
Urea (meth)acrylates,
Urethane/urea (meth)acrylates,
ethoxylated bisphenol-A, bisphenol-F or novolak di-(meth)acrylates, in particular ethoxylated bisphenol-A di-(meth)acrylates (e.g. of the formula wherein a and b each independently represent a number greater than or equal to 0, with the proviso that preferably at least one of the values is greater than 0, preferably both are 1 or greater (if mixtures of different molecules with different a and b values are present and are represented by the formula, non-integer numbers are also possible as the mean value);
wherein mixtures of two or more such systems are also possible and wherein the variants indicated in brackets are each examples of possible embodiments, with the proviso that according to the invention the polymer-forming anchoring mass used contains ethoxylated bisphenol A di(meth)acrylates or urethane(meth)acrylates in combination with silanes as reactive components.

The corresponding reactive components of the anchoring mass (monomers, prepolymers and/or macromonomers) can be present in a proportion of 5 to 60, e.g. from 7 to 60, 8 to 60, 9 to 60 or 10 to 60 wt.%.

One or more reactive diluents may be included in the synthetic mortar component(s), e.g., for radically curing systems, hydroxyalkyl (meth)acrylate and/or alkyl (meth)acrylate, such as hydroxypropyl (meth)acrylate, hydroxyethyl (meth)acrylate, ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, or trimethylolpropane trimethacrylate, or one or more other or additional reactive diluents, such as styrene, α-methylstyrene, divinylbenzene, alkyl styrenes, such as vinyltoluene or tert-butylstyrene. The reactive diluent(s) may be included, for example, in an amount of 0 to 80 wt.%, e.g., 1 to 50 wt.%.

Suitable radical hardeners in the context of the present invention are, for example, compounds (= initiators) that are capable of initiating a chain reaction for polymerization in molecules with olefinic (double) bonds. Suitable for this purpose are cationic, anonic, or, in particular, radical-forming initiators (which cause radical polymerization in monomers or prepolymers bearing olefinic groups, such as unsubstituted or substituted vinyl groups), such as, for example, organic peroxides, such as diacyl peroxides, e.g., benzoyl or bis(4-chlorobenzoyl) peroxide, ketone peroxides, or alkyl peresters, such as tert-butyl perbenzoate, or furthermore, azo initiators, persulfates, or perborates, as well as mixtures thereof. The initiators can be provided in pure form or, preferably, desensitized, e.g., with inorganic fillers such as gypsum or chalk, or with water, phthalates, or chloroparaffins. The initiator may be included in an amount of 0.01 to 80, preferably 0.5 to 60 wt.%, and the desensitizer in an amount of 1 to 99.5, preferably 30 to 70 wt.%, each based on the total amount of hardener component. In other reactive systems, as is known to those skilled in the art, certain components may also be referred to as "hardeners," for example, those mentioned above.

The proportion of the hardener in an anchoring compound used according to the invention is preferably in a range from 0.1 to 60 wt.%, e.g. 0.25 to 58 wt.%, 0.4 to 55 wt.% or 0.5 to 50 wt.%.

An anchoring compound to be used according to the invention is provided as a multi-component system in a kit, whereby components which would otherwise react with one another are stored spatially separated from one another until they are to react with one another at the desired location (in particular at or in the borehole).

If an anchoring compound to be used according to the invention consists of two components (e.g. (a), e.g. containing reactive olefin, and (b), e.g. containing hardener), these can be provided, for example, in a ratio of (a) : (b) equal to 100 : 1 to 1 : 20, for example 20 : 1 to 1 : 10 parts by weight.

Kits that may be considered are those comprising two or more separate, interconnected and/or nested (e.g., coaxially arranged) containers in the form of glass cartridges containing the present components, which may, for example, be provided with a common outer packaging and/or with instructions for joint use. Examples of corresponding use in certain embodiments of the invention are cartridge systems with an outer cartridge that, in addition to one of the reactive components, may contain one or two further cartridges, in particular with hardeners.

According to the invention, the use as a cartridge system, such as that offered by fischerwerken GmbH & Co. KG, Waldachtal under the product name “Mortar Cartridge RM”. In fastening systems, the hard fillers can ensure intensive mechanical post-processing of the borehole surface particularly well during the setting process and thus lead particularly effectively to the surprisingly found advantages as described above.

One or more further additives may be included in all components of the compositions according to the invention.

Such further additives (or additives) can be, for example, adhesion promoters, such as silanes, rheology additives such as thixotropic agents, e.g. precipitated or fumed silica, pigments, dyes, auxiliaries such as dispersing agents, solvents, phthalic acid esters or paraffins, stabilizers (e.g. against acids or bases, oxidation, UV light and/or light), antistatic agents, thickeners, plasticizers, or similar additives or additives, or mixtures of two or more thereof.

These further additives can be provided, for example, in an amount of 0.01 to 50% by weight, or for example between 0.01 and 15% by weight, wherein in the case of multi-component systems the components can contain different additives and/or different amounts of additives, or additives can be present only in one or some of the components.

In the case of polymer-forming (especially polymerizing) systems, inhibitors, accelerators and/or other catalytically active substances may also be included as additives.

Suitable accelerators include, for example, aminic accelerators with sufficiently high activity. Examples of preferred aminic accelerators are dimethylaniline or diethylaniline, N,N-bis(hydroxyC1-C7-alkyl)anilines, -toluidines, or -xylidines, such as in particular N,N-bis(hydroxyethyl)toluidines or -xylidines, or very particularly corresponding ethoxylated or propoxylated technical products that essentially contain N-unsubstituted, N-mono-, or N,N-bis-substituted anilines, p-toluidines, or xylidines with varying degrees of ethoxylation or propoxylation and in random distribution, such as technical "ethoxylated p-toluidine." One or more such accelerators are possible. The accelerators preferably have a proportion of 0.001 to 10, in particular 0.01 to 5 wt. %.

Suitable inhibitors include, for example, phenolic or non-phenolic inhibitors. Phenolic inhibitors (which are often included as a pre-mixed component in commercially available polymer-forming adhesive products, but may also be omitted) include hydroquinones such as hydroquinone, trimethylhydroquinone, or di- or tri( _C1 - _C7- alkyl)hydroquinones such as 2,5-di-tert-butylhydroquinone, phenols such as 2,6-di-tert-butyl-4-methylphenol, butylcatechols such as 4-tert-butylcatechol or, in particular, 4-methoxyphenol, or mixtures of two or more thereof. Non-phenolic or anaerobic inhibitors (i.e., in contrast to phenolic inhibitors, also effective without oxygen) are preferably phenothiazines such as phenothiazine, or organic nitroxyl radicals. Organic nitroxyl radicals can be added, for example, as described in DE 199 56 509 , which is incorporated herein by reference, particularly with regard to the compounds mentioned therein, in particular 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol ("4-OH-TEMPO"). The weight fraction of the phenolic and/or non-phenolic inhibitors is preferably in the range from 1 ppm to 2%, preferably in the range from 5 ppm to 1 wt.%.

Fastening is understood to mean, in particular, fastening using metal anchoring elements (e.g. undercut anchors, threaded rods or drill anchors) in drilled holes in solid substrates.

The term “construction sector” is to be understood in particular as meaning construction in the narrower sense, for example the anchoring of building elements, such as panels for facades or the like, with the aid of anchoring elements on or in substrates (i.e., in the context of the present invention, receiving materials, in particular insofar as they are components of structures erected by human hands, in particular masonry (e.g. made of natural stone, solid bricks, perforated bricks, bricks, expanded concrete blocks or the like), concrete, furthermore plastic or wood).

In all embodiments of the invention, the anchoring elements are fixed by inserting them before, simultaneously with or after the anchoring compound is inserted.

A very hard aggregate (filler) is one that has a hardness on the Mohs ordinal scale of 8 or higher, preferably 9 or higher, such as, in a possible preferred embodiment of the invention, corundum, granulated metal slag, ceramic or hard metal granules of suitable hardness, carbides and nitrides (particularly of Si and B), and zirconium oxide. The grain size can be from 1 to 6000 µm, depending on the product. For the particularly preferred cartridge systems, grain sizes of 200-6000 µm, in particular 500-3500 µm, are suitable, depending on the cartridge size. For example, grain sizes of 200 to 2500 µm, in particular 700-2000 µm, are particularly suitable for cartridge systems up to M12.

The weight proportion of the hard aggregate(s) is 40 to 65 or 50 to 65 wt% based on the total weight of all components including “packaging” in the case of cartridges.

Increasing the load-bearing capacity of the bond between substrate and anchoring element compared to the addition of less hard fillers means in particular that the adhesion failure load is higher than with an otherwise identical polymer-forming chemical adhesive product, in which only the filler material is replaced by one with a lower Mohs hardness than that used according to the invention, in particular quartz (Mohs hardness 7), in the same proportion by weight.

The components of an adhesive product used according to the invention or of an adhesive product used for comparison are tested to determine the adhesion failure load using a commercially available cartridge (e.g. mortar cartridge RM as mentioned above) in accordance with the methods 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 the conditions described in 5.1.2.1 (b), as further described in the examples below.

• Dass im Bohrloch trotz mindestens Restverschmutzung desselben durch Ausbohrmaterial, insbesondere ohne Vorreinigung des Bohrloches, vor allem ohne dessen Ausbürsten, Ausblasen und/oder Ausspülen, die Einbringung eines erfindungsgemäß verwendeten (oder zu Vergleichszwecken eines ein weniger hartes Füllmaterial beinhaltenden) erfolgt, und dennoch der erfindungsgemäße Zweck (Erhöhung der Belastbarkeit der Bindung zwischen Substrat und Verankerungselement im Vergleich zur bei Zugabe weniger harter Füllstoffen erzielbaren Belastbarkeit der bei Verwendung polymerisierenden chemischen Verankerungsmasse) erzielt wird, dient auch der Lösung folgender Aufgabe:
  • Insbesondere neue Vorschriften erhöhen die Anforderungen auch unter Bedingungen relativ großer Nässe (hier auch als feucht bezeichnet) und Restverschmutzung, wie beispielsweise analog in der Leitlinie von der European Organisation for Technical Approvals (EOTA) (2001): ETAG N° 001 Ausgabe November 2006 , Leitlinie für die europäische technische Zulassung für Metalldübel zur Verankerung im Beton, Teil 5: Verbunddübel, Februar 2008 , unter 5.1.2.1 (b) beschriebenen Bedingungen. Vorzugsweise wird die Verbesserung der Belastbarkeit, insbesondere der Adhäsionsversagenslast, wie in den Beispielen beschrieben durchgeführt.

For disclosure purposes only, the following should be noted regarding the use to increase load-bearing capacity even under conditions of wetness and/or residual contamination in the borehole:

• The fact that a filler material used according to the invention (or, for comparison purposes, one containing a less hard filler material) is introduced into the borehole despite at least residual contamination of the borehole by drilling material, in particular without pre-cleaning the borehole, especially without brushing, blowing out and/or flushing it, and yet the purpose of the invention (increasing the load-bearing capacity of the bond between substrate and anchoring element compared to the load-bearing capacity of the polymerising chemical anchoring mass that can be achieved when less hard fillers are added) is achieved, also serves to solve the following problem:
  • In particular, new regulations increase the requirements even under conditions of relatively high wetness (here also referred to as humid) and residual contamination, as for example in 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 the conditions described in 5.1.2.1 (b). Preferably, the improvement in load-bearing capacity, particularly the adhesion failure load, is carried out as described in the examples.

For all chemical fastening systems currently on the market, borehole cleaning is mandatory in order to achieve uniform and sufficient load-bearing capacity with minimal variation and without the risk of functional failure in the application. Surprisingly, it has now been discovered that the described solution can provide sufficiently safe and high-performance chemical fastening systems that can be used without cleaning the borehole (e.g., by brushing or blowing). A major advantage here is not only the elimination of time-consuming cleaning, but also the full functionality and safety of the product in the event of a forgotten cleaning process.

The crack resistance of a chemical anchor is given if the load in the uncracked concrete does not decrease significantly compared to the cracked concrete. This requires compliance with the requirements, for example, according to the guidelines of ETAG 001 Part 5 and ICC AC308.

The fastening systems that can be produced using the described hard fillers are not only suitable for anchoring under predominantly static loads, but they also meet the requirements for applications under predominantly non-static loads (also dynamic loads). Furthermore, the use of the hard fillers described in fastening systems can make them particularly suitable for fastenings in earthquake zones because the requirements for earthquake resistance, e.g. according to ICC AC308 (seismic tension, seismic shear loads), can be met.

The improvement of the adhesion failure load in a substrate exhibiting cracking around a borehole means in particular that an increased performance in cracked concrete is found compared to corresponding anchoring compounds without the filler according to the invention (and optionally silane) additive according to the methods according to the Guidelines 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 .

Surprisingly, the anchoring compounds used according to the invention also show particularly good properties with regard to performance in the tensile zone, i.e. in cracked concrete.

The determination of the adhesion failure load when used in a wet borehole is preferably carried out as described in the examples.

Particularly good improvements in load-bearing capacity are achieved when at least one (preferably polymer-free) silane is added as an additional additive.

The silane(s) are preferably one or more silanes bearing no or at least one amino, secondary amino, mercapto, isocyanato, alkenyl, epoxy, anhydrido, and/or, in particular, (meth)acryloyl group and containing at least one Si-bonded hydrolyzable group. In particular embodiments of the invention, these silanes are those of the formula I, $${\left[{\text{R}}_1-\text{X}-{\left({\text{CH}}_2\right)}_{\text{n}}-\right]}_{\text{p}}-\text{Si}{\left({\text{R}}^{\text{B}}\right)}_{\text{q}}{\left(\text{L}\right)}_{\text{t}}$$
wherein
X stands for S or NR ₁ * or O or NCO or nothing; where X is nothing (= missing) when R ₁ stands for anhydrido;
R ₁ and R 1*, all independently of one another, represent nothing, hydrogen, cycloalkyl, alkyl, aminoalkyl, (meth)acryloyl, aryl, aralkyl, acyl, heterocyclyl (especially anhydrido) or a radical of the formula -[(CH ₂ ) _n* ] _p* -Si(R ^B* ) _3-t *(L*)t* or epoxyalkyl, in which, in each case independently of the other radical, R ^B * has the meanings given below for R ^B , L* has the meanings given below for L and n*, p* and t* each have the meanings given below; where if X is S, R ₁ of the radicals mentioned for R ₁ can only be hydrogen; where X is O if R ₁ is epoxyalkyl or (meth)acryloyl; where R ₁ is nothing if X is NCO (= isocyanato);
R ^B independently represents an alkyl, alkenyl, arylalkyl or aryl group, preferably alkyl and/or (further) alkenyl,
L represents a hydrolyzable radical, in particular alkoxy,
n and, if present, n* independently represent a positive integer, in particular 1 to 10;
p stands for 0 to 3 and, if present, p* independently stands for 1 to 3;
q stands for 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.

In one embodiment of the invention, it is possible to use (at least also) those silanes which exhibit the alpha effect, e.g. where n and optionally n* in the above formula I is equal to 1 (n = 1 and optionally n* = 1 in formula I), e.g. 3-(meth)acryloyloxymethyltrialkoxy (such as -trimethoxy-) silane.

Further silanes with hydrolyzable groups may 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 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.

Further particular embodiments of the presently disclosed subject matter of the invention include silanes of the formula III or their use, $$\text{Si}{\left({\text{R}}^{\text{B}}\right)}_{4-\text{t}}{\left(\text{L}\right)}_{\text{t}}$$
wherein R ^B independently represents an alkyl, alkenyl, arylalkyl or aryl group, preferably alkyl and/or (further) alkenyl,
L represents a hydrolyzable radical, in particular alkoxy,
and
t stands for 1 to 4. These fall under silanes, which do not contain reactive groups capable of participating in polymerization with a synthetic resin.

Mixtures with two or more of the silanes of formulas I, II and/or III mentioned in the above or following paragraphs, or their respective uses, also form particular variants of the embodiments according to the invention.

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.

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

Cycloalkyl represents in particular 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 cyclopentyl or cyclohexyl.

Epoxyalkyl preferably represents alkyl as defined above which is substituted by an epoxy group to form a ring. Epoxyalkyl is in particular epoxy-C ₁ -C ₇ -alkoxy, such as in particular (2,3-epoxy-propan-1-yl) of the formula (the dashed line marks the end of the bond to the rest of the molecule).

Epoxyalkoxy is in particular epoxy-C ₁ -C ₇ -alkoxy, such as in particular a radical of the formula (the dashed line marks the end of the bond to the rest of the molecule).

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 C ₁ -C ₇ alkanoyl, e.g. acetyl or propionyl, aroyl (aryl-C(=O)-), such as benzoyl, or the like.

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, e.g. 1 to 3, preferably not directly adjacent, in particular separated by 2 carbon atoms and not terminal, a C atom chain sections (such as -CH ₂ - or -C(-)(H)-) can each be replaced by a heteroatom, such as -N(-)-, -NH-, -O- or -S-, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.

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.

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

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 present as 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 (resulting in 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. One possible preferred example is 2,5-dioxo-oxolan-3-yl, another is 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, and another is a 2,5-dioxolan-3-yl radical benzofused in the 3,4-position. Aromatic means that the corresponding radicals are defined as aryl above.

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

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 R ₁ is "nothing" means that the residue R ₁ is missing.

"If present" refers to the fact that a radical or a symbol may be present or absent depending on other definitions, for example, that in the case that only when p in formula I is 1 to 3 and R ₁ is a radical of the formula -[(CH ₂ ) _n* ] _p* -Si(R ^B* ) _3t* (L*) _t* , n*, p*, R ^B* , L* and t* can be present at all.

Silanes that may or may not contain reactive groups capable of participating in polymerization contain these reactive groups optionally, i.e. they may contain them.

Wherever “silanes” or other components are mentioned in the plural, this always means “one or more”.

(Meth)acrylic stands for acrylic, methacrylic or acrylic and methacrylic (as a mixture).

Si-bonded hydrolyzable groups (also symbolized by L in this disclosure) are, for example, halogen atoms (halogen, such as chloro), ketoximates, amino, aminoxy, mercapto, acyloxy, aryloxy, aralkyloxy (= arylalkoxy) or in particular alkyloxy (alkoxy).

Si-bonded hydrolyzable groups are understood to mean in particular those groups L which are part of a group of the formula Z, $$\text{Si}{\left({\text{R}}^{\text{B}}\right)}_{3-\text{t}}{\left(\text{L}\right)}_{\text{t}}$$
wherein R ^B can independently represent an alkyl, alkenyl, arylalkyl or aryl group, preferably alkyl and/or (further) alkenyl,
t stands for an integer from 1 to 3 and
L represents a Si-bonded hydrolyzable group, in particular alkoxy.

The silane(s) added according to the invention which contain(s) no or at least one amino, sec. amino, mercapto, isocyanato, alkenyl, epoxy, anhydrido and/or in particular (meth)acryloyl group and at the same time contain(s) at least one Si-bonded hydrolyzable group preferably have average or absolute molecular weights of 2000 or less, 1000 or less ner, 900 or less, 800 or less, 700 or less, 600 or less, or in particular 500 or less, or in particular 400 or less. Preferably, the silanes are low-molecular-weight, low-viscosity substances, in particular other than higher-molecular-weight compounds (which include, for example, prepolymers).

Particularly preferred are one or more silanes selected from (meth)acryloyloxypropyltrimethoxysilane, (meth)acryloyloxypropyltriethoxysilane, (meth)acryloyloxymethyltrimethoxysilane and (meth)acryloyloxymethyltriethoxysilane

Preferably, in all embodiments of the invention, the viscosity of the silanes is 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.

Unless otherwise stated, viscosities are measured according to DIN EN ISO 2555 using a Brookfield DV-III+ viscometer with spindle 3 at 10 revolutions per minute (rpm) at 23 °C and are given in Pa s (hereinafter also referred to as Pa ∗ s or Pas).

The silanes which carry no or at least one amino, secondary amino, mercapto, isocyanato, alkenyl, epoxy, anhydrido and/or (in particular) (meth)acryloyl group and which contain at least one Si-bonded hydrolyzable group are present in an anchoring composition according to the invention or to be used according to the invention, for example, in a weight proportion of 0.1 to 50, in particular of 1 or more wt.%, such as of 1 to 30 wt.%, preferably of 2 or more wt.%, such as of 2 to 30 or up to 15 wt.%, of 3 or more wt.%, such as of 3 to 20 or up to 10 wt.%, even more preferably of 4 or more wt.%, e.g. of 4 to 20 or up to 6 wt.%.

Where weights are given in percent (wt%), unless otherwise stated, these refer to the total weight of all reactive components and additives of the anchoring compound (i.e. the components present in the compound polymerising after mixing which enter a drill hole and remain there, including packaging materials serving as fillers, i.e. glass from cartridges/ampoules).

“Include” or “comprise” means that there may be other components or features in addition to those mentioned, and therefore represents a non-exhaustive list, in contrast to “consist of”, which means an exhaustive list of the components or features listed when it is used.

“Partially or exclusively” or “at least partially” means that the constituents named thereafter may be present alongside other constituents 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.

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

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

Preferred embodiments of the invention are also set forth in the claims, which are incorporated herein by reference.

Examples: The following examples serve to illustrate the invention without limiting its scope.

Test procedure for determining adhesion failure load:

A) Basic parameters:

• Anchoring depth (hef) = 95 mm
• Drill diameter (d0) = 14 mm
• Anchor: metric threaded rod M12 (grade 12.9)
• Drilling method = hammer drilling 4 kg class (Bosch GBH 4-32)

B) Preparation of the boreholes

1a Tests in dry borehole

Drill hole preparation: The drill holes were created in the horizontally lying concrete test specimen (low-strength concrete of strength class C20/25) with dimensions 128x128x30cm using a hammer drilling machine and a hammer drill.

In some of the tests (marked “cleaned”), cleaning was carried out after the borehole had been drilled by blowing out twice.

In the other part of the tests (marked "uncleaned"), no cleaning was performed after the borehole was drilled. Instead, the drill bit was withdrawn and reinserted into the borehole several times during the borehole drilling process or after reaching the desired drilling depth. The drill bit rotated continuously during this time to expel the drilling debris. This process was repeated at least four times.

1b Tests in a moist borehole

Pilot boreholes were drilled into the horizontally positioned concrete test specimen (low-strength concrete C20/25), measuring 128 x 128 x 30 cm, using a hammer drill and a hammer bit. These boreholes must have a minimum diameter of 0.5 x d0, which in this test was 7 mm. A cylindrical cup with a hole was glued to each pilot borehole in the borehole area and filled with water. The water remained in the borehole for at least 8 days until the water had penetrated the concrete to a distance of 1.5 d to 2.5 d (d = anchor rod diameter) from the borehole axis. This ensures that the concrete is water-saturated in the anchorage area.

The cups and the water in the borehole are removed by pulling off the cup and throwing away its contents, as well as sucking out the water in the borehole and drilling the final borehole with d0 (here 14 mm).

In some of the tests (marked with “cleaned”), the borehole was cleaned after drilling by blowing out the borehole twice using a hand blower (e.g. the fischer blower ABG, fischerwerke Gmbh & Co. KG, Waldachtal, Germany).

In the other part of the tests (marked "uncleaned"), no cleaning was performed after the borehole was drilled. The drill bit was simply withdrawn and reinserted into the borehole several times during the borehole drilling process or after reaching the desired drilling depth. The drill bit rotated continuously during this time to expel the drilling debris. This process was repeated at least four times.

B) Set and pull anchor

After drilling the borehole, the reaction anchor cartridges were inserted into the borehole (one per hole), and the anchor rods were driven in using a rotary hammer drill. Excess mortar was removed with a spatula. After the minimum curing time, in this case after 45 minutes, the pull-out direction was adjusted, and the anchor was loaded with tight support until failure.

The test setup complies with ETAG No. 1 Part 5.

Compositions used:

E2BADMA

technical ethoxylated bisphenol A dimethacrylate (vinyl ester)

UMA

Urethane methacrylate based on PMDI HPMA and BDDMA

BDDMA

Butanediol dimethacrylate

HPMA

2-Hydroxypropyl methacrylate

PMDI

Polymeric diphenylmethane diisocyanate

Silane

Methacryloxypropyltrimethoxysilane

quartz

Quartz sand fraction 60-200 µm

corundum

Normal corundum 1100-1700 µm

M12 cartridges are manufactured, consisting of an inner hardener tube and an outer tube. The inner tubes contain 0.32 g of a desensitized 50% dibenzoyl peroxide, are made of 1.05 g of glass, and are thermally sealed. The inner hardener tubes, the resin, and the solid filler are inserted into the outer cartridge tubes, which weigh 3.60 g of glass, and are also sealed. The resins are given a base stabilization with 500-700 ppm of a phenolic inhibitor and are adjusted to a gel time of 3-4 minutes at 23 °C by adding 1.2 to 3% of an amine accelerator (toluidine derivative).

The examples marked with ** are comparative examples. The following compositions were used: E2BADM A UMA BDDMA HPMA Silane quartz corundum V1 3.55 0.29 0.15 8.6 V2 3.55 0.29 0.15 11.9 V3 3.13 0.82 11.9 V4** 3.44 0.30 0.30 8.6 V5** 3.44 0.30 0.30 11.9 V6 3.23 0.82 11.9

Comparative example: Compositions with quartz sand as filler

Where “quartz” is mentioned, this refers to quartz sand as an additive.

Anchoring compound: Vinyl ester anchoring compound V1 and urethane methacrylate anchoring compound V4, each with quartz, were used and the following adhesion failure loads were determined: II) Adhesive failure load when anchored with the anchoring compounds cleaned uncleaned Anchoring Filler/ Adhe- Filler/ Adhesion mass Addition sion failure load (kN) ± SD Addition failure load (kN) ± SD Vinyl ester dry (1a) quartz 84.2 ±4.8 quartz 54.54 ±8.82 Vinyl ester wet (1b) quartz 52.08 ±1.87 quartz 41.15 ± 5.57 Urethane methacrylate dry (1a) quartz 77.24 ±4.31 quartz 53.89 ±4.25 Urethane methacrylate wet (1b) quartz 65.2 ±3.27 quartz 37.45 ±3.21

Example 1: Anchoring compounds according to the invention with corundum

• 1.I) Anchoring compound: Vinyl ester anchoring compound V2 and urethane methacrylate anchoring compound V5, each with corundum, were used and the following adhesion failure rates were determined:
• 1.II) Adhesive failure load when anchoring with the anchoring masses with corundum

cleaned uncleaned Anchoring compound Filler/ additive Adhesive failure load (kN) ± SD Filler/ additive Adhesive failure load (kN) ± SD Vinyl ester dry (1a) corundum 93.99 ±4.06 corundum 67.39 ±7.07 Vinyl ester wet (1b) corundum 69.49 ±3.15 corundum 46.56 ±5 Urethane methacrylate dry (1a)** corundum 82.25 ±4.15 corundum 57.77 ±2.43 Urethane methacrylate wet (1b)** corundum 64.14 ±5.78 corundum 43.16 ±3.41

• 1.III) Factor of increase in adhesion failure load compared to quartz:

Anchoring compound Factor uncleaned (adhesion failure load corundum/quartz) Factor purified (adhesion failure load corundum/quartz) Vinyl ester dry (1a) 1.24 1.12 Vinyl ester wet (1b) 1.13 1.33 Urethane methacrylate dry (1a)** 1.07 1.06 Urethane methacrylate wet (1b)** 1.15 0.98

Accordingly, except in the case of wet urethane methacrylate, there is an improvement in the adhesion failure load with corundum compared to quartz.

Example 2: Anchoring compounds according to the invention with corundum and silane

• 2.I) Anchoring compound: Vinyl ester anchoring compound V3 and urethane methacrylate anchoring compound V6, each with corundum and silane, were used and the following adhesion failure loads were determined:
• 2.II) Adhesive failure load when anchoring with anchoring compounds according to the invention with corundum and silane

cleaned uncleaned Anchoring compound Filler/ additive Adhesive failure load (kN) ± SD Filler/ additive Adhesive failure load (kN) ± SD Vinyl ester dry (1a) Corundum and silane 99.37 ±1.87 Corundum and silane 73.39 ±5.97 Vinyl ester wet (1b) Corundum and silane 75.49 ±4.38 Corundum and silane 59.97 ±5 Urethane methacrylate dry (1a) Corundum and silane 87.36 ±6.84 Corundum and silane 66.32 ±6.09 Urethane methacrylate wet (1b) Corundum and silane 93.5 ±4.34 Corundum and silane 85.39 ±2.4

C) Factor of increase in adhesion failure load compared to quartz as additive: Anchoring compound Unpurified factor (adhesion failure load corundum+silane/quartz) Factor purified (adhesion failure load corundum+silane/quartz) Vinyl ester dry (1a) 1.35 1.18 Vinyl ester wet (1b) 1.46 1.45 Urethane methacrylate dry (1a) 1.23 1.13 Urethane methacrylate wet (1b) 2.28 1.43

Consequently, in all cases, corundum plus silane instead of quartz results in a considerable increase in the adhesion failure load.

Example 3: Ratio of adhesion failure loads for uncleaned versus cleaned borehole

From the tables of Example 1, Example 2 and the comparative example, the ratios of the adhesion failure load cleaned/uncleaned can be determined: Anchoring mass Ratio (factor) adhesion failure load cleaned/uncleaned dry Ratio (factor) adhesion failure load cleaned/uncleaned wet Vinyl ester + quartz** 1.54 1.27 Vinyl ester + corundum 1.39 1.49 Vinyl ester + corundum + silane 1.35 1.26 Urethane methacrylate + quartz** 1.43 1.74 Urethane methacrylate + corundum** 1.42 1.49 Urethane methacrylate + corundum + silane 1.32 1.09

This shows that in wet boreholes, an improvement in the adhesion failure load is always found compared to quartz with corundum or with a combination of corundum and silane as additives. In dry boreholes, an improvement in the adhesion failure load is also always found for the measured compositions.

It is noteworthy that in the dry borehole, the adhesion failure load for epoxy acrylate with the combination of corundum and silane is higher even in the uncleaned borehole than for the cleaned borehole. It is also noteworthy that in the wet borehole, the adhesion failure load is higher in all cases, even in the uncleaned borehole, than for quartz in the cleaned borehole.

Example 4: Crack and seismic

Seismic tests are conducted according to ICC Guideline AC308, Table 4.2, Test Nos. 17 and 18. The objective of the seismic tests is to withstand the determined load level in the 0.3 mm crack and the resulting Neq, Nm, Ni without failure during periodic loading. If the anchor fails prematurely, a reduced load Neq,red is determined. This then results in a reduction factor α _seis , for example, 0.7. Without reduction, α _seis = 1. Anchoring compounds according to the invention can meet these requirements.

Claims (11)

Use of an anchoring compound containing a very hard aggregate with a Mohs hardness of 8 or greater for fixing an anchoring element in a borehole, characterized characterized in that the polymer-forming anchoring mass, when in use, is introduced into the borehole before, simultaneously with and/or after an anchoring element and without cleaning the borehole, in particular by blowing out, brushing out and/or rinsing, and remains there, wherein the anchoring mass is designed as a kit in a multi-chamber cartridge made of glass, which also serves as a filler after the anchoring element has been introduced by rotating and impact, wherein the weight proportion of the hard aggregate, based on the total weight of all components including the cartridge as packaging, is 40 to 65 wt.% and wherein the polymer-forming anchoring mass, when in use, contains ethoxylated bisphenol A di-(meth)acrylates; or urethane (meth)acrylates in combination with silanes; as reactive components. Use according to Claim 1 , characterized in that the anchoring mass is designed as a two-chamber cartridge made of glass. Use according to Claim 1 or 2 , characterized in that the very hard aggregate is corundum. Use according to one of the Claims 1 until 3 , characterized in that the associated reactive components of the anchoring mass are provided in a proportion of 5 to 60 wt.%, based on the total weight of all reactive components and additives, including the glass serving as filler of the cartridge. Use according to one of the Claims 1 until 4 , characterized in that the weight proportion of the very hard aggregate is 50 to 65 wt.%, based on the total weight of all reactive components and additives of the anchoring mass, including the glass of the cartridge serving as filler. Use according to one of the Claims 1 until 5 , characterized in that 0.1 to 60 wt.% of hardener, based on the total weight of all reactive components and additives of the anchoring mass, including the glass of the cartridge serving as filler, are provided, wherein optionally one or more further additives are provided in a total amount of 0.01 to 50 wt.%, based on the total weight of all reactive components and additives, including the glass of the cartridge serving as filler. Use according to one of the Claims 1 until 6 , characterized in that in order to further increase the strength of the bond between the substrate and the object to be fastened, one or more silanes are additionally added as a reactive component, even in the case of ethoxylated bisphenol A di(meth)acrylates. Use according to one of the Claims 1 until 7 , characterized in that the silane provided is one or more silanes carrying no or at least one amino, secondary amino, mercapto, isocyanato, alkenyl, (meth)acryloyl, anhydrido and/or epoxy group and containing at least one Si-bonded hydrolyzable group. Use according to one of the Claims 1 until 8 , characterized in that the silane(s) are provided in a weight proportion of 0.1 to 20 wt.%, based on the total weight of all reactive components and additives, including the glass serving as filler of the cartridge. Use according to one of the Claims 1 until 9 , characterized in that the borehole is moist. Use according to Claim 1 or 10 , characterized in that the borehole is located in a cracked and/or crack-prone concrete substrate.