DE102011055883A1 - Use an aggregate, in a polymer forming anchoring compound in fastening technology in building sectors, to increase the capacity of bonding between the substrate and to be fastened object, preferably in wet borehole - Google Patents

Abstract

Use at least one aggregate, in a polymer forming anchoring compound in fastening technology in the building sector, to increase the capacity of bonding between the substrate and to be fastened object, when compared with the capacity of the bonding using the less hard aggregate, is claimed, where the anchoring compound is introduced into a substrate and simultaneously or subsequently an article to be fixed is introduced into the anchoring compound, and at least a very hard aggregate with a Mohs-hardness of >= 8, preferably a filler is added.

Description

The invention relates to the use of certain (hard) additives described below in more detail in the case of polymer-forming chemical anchoring compositions in fastening technology in the construction sector and related inventions.

In construction, particulate fillers are known for use in polymer-forming chemical anchoring compositions (sometimes referred to as "chemical anchors") having one or more components, for example in the form of dual-chamber cartridges or dual-chamber cartridges, for securing anchoring elements in wellbores. However, the type of fillers, unless they are those which, like cement, even for example by hydraulic setting contribute to the solidification, usually considered not relevant. For example, mentions the EP 0 150 555 B1 expressly, the type of filler is not critical and a number of possible fillers are mentioned.

There is a need to further improve the properties of chemical anchoring compositions, in particular with regard to the level of resilience, ease of processing and usability and the possibility for use in moist, unpurified and / or (for example by cracking) pre-damaged boreholes in substrates such as Concrete or masonry.

So far, it is necessary for the building inspectorate approval of fastening systems with chemical anchoring masses, to specify precise regulations for the pre-cleaning of boreholes before using the chemical anchoring materials. As a rule, at least several blowouts, often brushing, are necessary, and these rules must also be meticulously met to ensure adequate strength and function. In humid boreholes (as they are often to be expected when used outdoors), they may fall short of the achievable or prescribed by the approval / defined or prescribed load capacities in the cured (polymer) state.

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 effecting special properties in anchoring compositions for the stated purpose, inter alia one or more of the following to realize improved properties:
an increased load capacity, which is expressed for example in an increased adhesion failure load; the possibility of achieving increased load capacities even in damp boreholes; the possibility of introducing the anchoring mass and anchoring elements without pre-cleaning the borehole and the possibility of achieving good connections between substrate, anchoring mass and anchoring element even when cracking in the substrate.

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

The invention relates in a first embodiment to the use of at least one aggregate in a polymer-forming (chemical) anchoring mass in fastening technology in the construction sector, wherein the anchoring mass is introduced into a substrate and at the same time, subsequently and / or (further) an object to be fastened, in particular an anchoring element, is introduced into the anchoring mass, characterized in that at least one very hard aggregate with a Mohs hardness of 8 or greater, in particular a filler, to increase the strength of the bond between the substrate and the object to be fastened compared to when added less hard aggregates achievable load capacity of the polymer-forming anchoring mass is or is added.

A specific embodiment of the invention relates to the said use, in which the anchoring mass is introduced into a borehole in a substrate before, simultaneously with or after the introduction (setting) of an anchoring element.

Preferred here, as in the other embodiments of the invention, the use in the context of setting operations for the anchoring element, which are associated with high friction (eg by a machine setting process, for example with a drill and by a increased friction-inducing setting resistance, by the Art , Shape and size of the fillers and the resin viscosity can be influenced), in particular the use of such anchoring materials in the form of multi-chamber cartridges, such as two-chamber cartridges, eg 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 well despite at least residual contamination of the same by drilling material, in particular without pre-cleaning the well, especially without brushing, blowing and / or rinsing , he follows.

In spite of lack of cleaning, composite 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 very particularly preferably more than 18 N / mm ² can be achieved.

The invention thus also relates to the use of an anchoring mass described above or below, which contains a very hard aggregate having a Mohs hardness of 8 or greater, and preferably additionally comprising a silane, for fixing an anchoring element in a borehole, characterized in that the anchoring mass is introduced before, simultaneously with or after an anchoring element without cleaning the borehole, in particular without blowing out, brushing out and rinsing out.

A particular variant of the invention is in this case that when using the above paragraph (without or with Silanzusatz) the substrate and / or well is wet, has cracks and / or is threatened by cracks (especially in the tension zone), in particular the performance of Systems are so high that ratios of load values measured in wet 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 failure loads measured in the 0.5 mm crack to which, measured in the 0.3 mm crack, is greater than or equal to 0.9. Due to the inventive design of the systems can also be achieved that the load values have a particularly low variance, in particular <15%.

A further embodiment of the invention relates to the use of an anchoring mass described above or below, which comprises a very hard aggregate having a Mohs hardness of 8 or greater, and preferably additionally a silane, for fastening an anchoring element in a borehole, characterized that the adhesive product is introduced before, simultaneously with and / or after an anchoring element in a drilled and / or cracked borehole.

The general terms used above and below preferably have the following meanings, wherein in all embodiments of the invention more general terms (one, several or all of them) can be replaced by more specific terms, which leads to further particular embodiments of the invention:
A polymer-forming (polyreaction-reactive, ie "polyreaction-reactive" prior to use) chemical anchoring composition (a synthetic mortar product for chemical anchoring) is to be understood above all as a two-component or multicomponent product. Here, in the German "polymerize" or "polymerization" for kinetic chain reactions as a subj ect of polyreactions, in contrast to the English "Polymerization", which stands for polyreaction in general. The latter is meant here with "polymerbildend", the German Unterfall only a special variant.

As the basis for the anchoring composition, it is conceivable to use all customary polymer-forming resins (with reactive, that is to say the polymer-forming constituents) in which monomers or prepolymers or macromonomers react in the course of use to give polymers

worin n für eine Zahl größer oder gleich 1 steht, wobei, wenn Gemische verschiedener Moleküle mit unterschiedlichen n-Werten vorliegen und durch die Formel repräsentiert werden, auch nicht-ganzzahlige Zahlen als Mittelwert möglich sind,
Urethan(meth)acrylate (erhältlich aus der Umsetzung von Di-, Tri- oder Polyisocyanaten, deren Präpolymeren und/oder Oligomeren mit Hydroxyalkyl(meth)acrylaten und ggf. weiteren Reaktanden mit Zerewitinoff-Wasserstoffatomen wie z.B. Alkylenglykolen oder Polyalkylenglykolen),
Harnstoff(meth)acrylate,
Urethan/Harnstoff(meth)acrylate,
ethoxylierte Bisphenol-A, Bisphenol-F- oder Novolak-di-(meth)acrylate, insbesondere ethoxylierte Bisphenol-A-di-(meth)acrylate (z.B. der Formel

worin a und b jeweils unabhängig voneinander für eine Zahl größer oder gleich 0 stehen mit der Maßgabe, dass vorzugsweise mindestens einer der Werte größer als 0 ist, vorzugsweise beide 1 oder größer sind (wenn Gemische verschiedener Moleküle mit unterschiedlichen a-und b-Werten vorliegen und durch die Formel repräsentiert werden, sind auch nicht-ganzzahlige Zahlen als Mittelwert möglich);
wobei auch Gemische von zwei oder mehr solchen Systemen in Frage kommen und wobei die in Klammern angegebenen Varianten jeweils Beispiele für mögliche Ausführungsformen sind. Examples of such multicomponent anchoring materials are, in particular, those based on di-, tri- and / or polyfunctional synthetic resins and one or more complementary hardeners, in particular based on epoxy resins (synthetic resin component di-, tri- and / or multifunctional epoxide, Hardener component di- and / or polyfunctional organic amino and / or mercapto), polyurethanes or polyureas or mixtures thereof (resin component di- and / or polyisocyanates, optionally also as prepolymers or oligomers, hardener component two or more hydroxy, amino or hydroxy and / or amino group-carrying organic compounds or mixtures thereof), alkoxysilane-terminated prepolymers (synthetic 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) polymerizing (before use so polymerizable) resin component (complementary hardener each radical curing agent) to mention, for example based on unsaturated polyesters, or
preferably based on (meth) acrylic esters or amides, where (meth) acryl 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 particular of reaction products of di- or polyepoxides, for example 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, where, when mixtures of different molecules with different n values are present and represented by the formula, non-integer numbers are also possible as an average value,
Urethane (meth) acrylates (obtainable from the reaction of di-, tri- or polyisocyanates, their prepolymers and / or oligomers with hydroxyalkyl (meth) acrylates and optionally further reactants with Zerewitinoff hydrogen atoms, for example alkylene glycols or polyalkylene glycols),
urea acrylates (meth)
Urethane / urea (meth) acrylates,
ethoxylated bisphenol A, bisphenol F or novolak di (meth) acrylates, in particular ethoxylated bisphenol A di (meth) acrylates (eg 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 1 or greater (when mixtures of different molecules having different a and b values are present and represented by the formula, even non-integer numbers are possible as an average);
mixtures of two or more such systems are also contemplated, and the parenthetical variants are each examples of possible embodiments.

The associated reactive constituents of the anchoring composition (monomers, prepolymers and / or macromonomers) may, for example, in a proportion of 5 to 100, e.g. from 7 to 90, from 8 to 75, from 9 to 70 or from 10 to 60% by weight.

One or more reactive diluents may be provided in the one or more synthetic mortar components, e.g. for free-radical 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 others or further reactive diluents, for example styrene, α-methylstyrene, divinylbenzene, alkylstyrenes, such as vinyltoluene or tert-butylstyrene. The reactive diluent (s) may be used, for example, in an amount of 0 to 80% by weight, e.g. from 1 to 50% by weight.

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

The proportion of the curing agent in an anchoring composition used according to the invention is preferably in a range from 0.1 to 60% by weight, e.g. 0.25 to 58% by weight, 0.4 to 55% by weight or 0.5 to 50% by weight.

An anchoring composition to be used according to the invention can be provided as a one-component system or preferably as a multi-component system (for example in a kit), with components which otherwise react with one another being kept spatially separate from one another until they are to react with one another at the desired site of use (in particular on or in the borehole).

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

As a kit, those come into consideration, the two or more separate, interconnected and / or nested (for example, coaxially arranged) containers, for example, in separate containers (such as bottles, tubes, foil bags, chambers of a cartridge (preferably with static mixer), or in particular cartridges (eg made of glass or plastic) or the like) present components, the example may be provided with a common outer packaging and / or instructions for common use. Examples of appropriate use in certain embodiments of the invention are two- or three-chamber cartridges, or preferably cartridge systems with an outer cartridge, which may include one or more of two cartridges, particularly hardeners, in addition to one of the reactive components.

To initiate the polyreaction in the chemical anchoring masses at the desired site, the components are mixed, for example, directly before or in a wellbore and introduced, if necessary, that there curing (polymerization) can take place. This may be separate, but for example as a set, for example in a common packaging or a common container, offered containers for the resin, the initiator or optionally further additives, as mentioned below.

Also, extrusion devices, such as squeeze guns, and / or static mixers or nozzles / cannulas for squeezing and / or further containers for mixing, such as bowls or cups, may be part of such a kit.

Particularly preferred is the embodiment as a cartridge system, as offered for example by fischerwerke GmbH & Co. KG, Waldachtal under the product name "Mortar cartridge RM". In these fastening systems, the hard fillers can ensure an 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 of the invention.

Such other additives (or additives) may include, for example, coupling agents, such as e.g. Silanes, rheology additives, such as thixotropic agents, e.g. precipitated or fumed silica, pigments, dyes, auxiliaries, such as dispersing agents, solvents, phthalic esters or paraffins, stabilizers (for example against acids or bases, oxidation, UV light and / or light), antistatic agents, thickeners, plasticizers, or the like, additives or additives be, or mixtures of two or more of them.

These further additives may be provided, for example, in a total amount of up to 80, for example from 0.01 to 50% by weight, or for example between 0.01 and 15% by weight, in the case of multicomponent systems, the components being different from one another Additives and / or may contain different amounts of additives or additives may be present only in one or a part of the components.

In the case of the polymer-forming (in particular polymerizing) systems, it is also possible to provide as additives inhibitors, accelerators and / or other catalytically active substances.

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

Examples of suitable inhibitors are phenolic or non-phenolic inhibitors. Hydroquinones, such as hydroquinone, trimethylhydroquinone or di- or tri (C ₁ -C ₇ -alkyl) -hydroquinones, such as 2.5, come as phenolic inhibitors (which are often provided as an already admixed constituent of commercially available polymer-forming adhesive products, but can also be omitted) Di-tert-butylhydroquinone, phenols such as 2,6-di-tert-butyl-4-methylphenol, butyl catechols such as 4-tert-butylcatechol or especially 4-methoxyphenol, or mixtures of two or more thereof , As non-phenolic or anaerobic (ie in contrast to the phenolic inhibitors also without oxygen effective) inhibitors are preferably phenothiazines, such as phenothiazine, or organic nitroxyl radicals into consideration. As organic nitroxyl radicals may be added, for example, as in the DE 199 56 509 which is hereby incorporated by reference in particular with respect to the compounds mentioned therein, in particular 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol ("4-OH-TEMPO"). The proportion by weight 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 by weight to 1% by weight.

Fixing means, in particular, an attachment by means of metal anchoring elements (for example undercut anchors, threaded rods or drilling anchors) in boreholes in solid substrates.

By "construction sector" is meant in particular the construction in the strict sense, for example the anchoring of components, such as panels for facades or the like, by means of anchoring elements on or in substrates (ie in the context of the present invention Aufnahmewerkstoffen, in particular, as far as components of man-made structures are, especially masonry (eg natural stone, bricks, bricks, bricks, Blähbetonsteinen or the like), concrete, plastic or wood).

The attachment of the anchoring elements takes place in all embodiments of the invention by their introduction before, simultaneously with or after the introduction of the anchoring material.

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

The proportion by weight of hard additive (s) is preferably 2 to 98, more preferably 5 or 20 to 80, e.g. at 10 to 65 or 40 to 65 or 50 to 65% by weight, based on the total weight of all components, if appropriate including "packaging", e.g. in the case of cartridges.

By increasing the strength of the bond between substrate and anchoring element in comparison with the addition of less hard fillers is in particular to be understood that the Adhesion failure load is higher than in an otherwise identical when using polymer-forming chemical adhesive product, in which only the filler material is replaced by a lower than the present invention used Mohs hardness, especially quartz (Mohs hardness 7), in the same weight fraction.

The components of an adhesive used according to the invention or used for comparison are used to determine the adhesive failure load with a commercially available cartridge (eg mortar cartridge RM as mentioned above) analogous to the above for using the Guideline from the European Organization 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) described conditions, as described in more detail in the following examples.

With regard to the use for increasing the load capacity even under conditions of wetness and / or residual contamination, especially in the borehole, the following should be noted:
That despite the least residual contamination of the same by boring material, in particular without pre-cleaning of the well, especially without its brushing, blowing and / or rinsing, the introduction of an inventively used (or for comparison purposes of a less hard filler material containing) is carried out, and still the inventive The purpose (to increase the strength of the bond between the substrate and the anchoring element in comparison to the load-bearing capacity of the polymerizing chemical anchoring compound which can be achieved when using less hard fillers) is also achieved by the following task:
In particular, new regulations increase the requirements even under conditions of relatively high humidity (also referred to here as moist) and residual pollution, such as in the analog Guideline from the European Organization 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) described conditions. Preferably, the improvement of the load capacity, in particular the adhesion failure load, is carried out as described in the examples.

For all previous chemical fastening systems on the market, a well cleaning is mandatory in order to achieve a uniform and sufficient load capacity with low scattering and without the risk of functional failure in the application. Surprisingly, it has now been found that with the described solution sufficiently safe and powerful chemical fastening systems can be provided which can be used without cleaning the borehole (for example by brushing or blowing out). A great advantage here is not only the saving of time-consuming cleaning, but also the full functionality and safety of the product in case of a forgotten cleaning process.

The crack resistance of a chemical anchor is given when the load in non-cracked concrete does not decrease significantly to the cracked concrete. These are the conditions, for example, after the Guidelines ETAG 001 Part 5 as well as the ICC AC308 to fulfill.

In addition, the fastening systems that can be produced by the described hard fillers are not only suitable for anchoring under predominantly static load, but also the specifications for the application under predominantly non-static load (also called dynamic load) can be fulfilled particularly well. Furthermore, by using the hard fillers described in fastening systems can be made that they are especially suitable for fasteners in earthquake areas, because the requirements for earthquake capability, for example ICC AC308 (seismic tension, seimic shear loads) can be met.

The improvement of the adhesion failure load in a substrate having a borehole cracking means, in particular, that an increased capacity in cracked concrete is found in comparison with corresponding anchoring materials without inventive filler (and optionally silane) additive according to the methods according to FIGS Guidelines from the European Organization 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, also show particularly good properties of the anchoring compositions of the invention in terms of performance in the tension zone, ie in cracked concrete.

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

Particularly good improvements in the load-bearing capacity are achieved if at least one (preferably polymer-free) silane is added as a further additive.

The silane or silanes are preferably one or more, none or at least one amino, sec. Silanes containing amino, mercapto, isocyanato, alkenyl, epoxy, anhydrido and / or in particular (meth) acryloyl group and containing at least one Si-bonded hydrolyzable group. These silanes in particular embodiments of the invention are those of the formula I, [R ₁ -X- (CH ₂ ) _n -] _p -Si (R ^B ) _q (L) _t (I) wherein
X is S or NR ₁ * or O or NCO or nothing; where X is nothing (= missing) when R _{1 is} anhydrido;
R ₁ and R ₁ *, all independently of one another, represent nothing, hydrogen, cycloalkyl, alkyl, aminoalkyl, (meth) acryloyl, aryl, aralkyl, acyl, heterocyclyl (in particular anhydride) or a radical of the formula - [(CH ₂ ) _{n *} ] _{p *} -Si (R ^{B *} ) _{3-t *} (L *) _{t *} or for epoxyalkyl, in which, in each case independently of the other radical, R ^B * are the meanings given below for R ^B , L * being the following meanings given for L and n *, p * and t * each have the meanings given below; where X is S, R ₁ of the radicals mentioned for R ₁ can only be hydrogen; wherein X is O when R _{1 is} epoxyalkyl or (meth) acryloyl;
wherein R _{1 is} nothing when X is NCO (= isocyanato);
R ^B independently of one another represents an alkyl, alkenyl, arylalkyl or aryl group, preferably alkyl and / or (further) alkenyl,
L is a hydrolyzable radical, in particular alkoxy,
n and, if present, n * independently of one another represent a positive integer, in particular 1 to 10;
p is 0 to 3 and, if present, p * is independently 1 to 3;
q is 0 to 2; and
t is 1 to 4 and, if present, t * is independently 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, (at least) those silanes which exhibit the alpha effect, e.g. wherein n and optionally n * in the above formula I is 1 (n = 1 and optionally n * = 1 in formula I), e.g. 3- (meth) acryloyl-oxymethyltrialkoxy (such as trimethoxy) silane.

Other silanes with hydrolyzable groups can be included, for example (based on the total weight of all silanes) to 80 wt .-%, to 70 wt .-%, to 60 wt .-%, to 50 wt .-%, to 40 wt. %, up to 30% by weight, up to 20% by weight or up to 10% by weight, this implies, for example, alkoxysilane compounds or silane crosslinkers, such as vinylalkoxysilanes, eg vinyltrimethoxysilane or vinyltriethoxysilane or (further or in particular) esters of (poly) -Kieselsäure (such as Dynasylan ^® an ethyl polysilicate) or Dynasylan ^® a, Evonik GmbH, Frankfurt am Main, Germany 40 () that allow for controlling the degree of crosslinking, or mixtures of two or more thereof.

Further particular embodiments of the presently disclosed subject matter include silanes of the formula III or their use, Si (R ^B ) _4-t (L) _t (III) in which R ^B, independently of one another, is an alkyl, alkenyl, arylalkyl or aryl group, preferably alkyl and / or (further) alkenyl,
L is a hydrolyzable radical, in particular alkoxy,
and
t stands for 1 to 4. These are silanes that do not have reactive groups capable of participating in polymerization with a resin.

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

Aryl, within this disclosure, is always preferably an unsubstituted or (e.g., alkyl, alkoxy (= alkyloxy), alkenyl, hydroxy, or further halogen, such as fluoro, chloro or bromo, or cyano), one or more independently, e.g. 1 to 3 times, substituted aromatic radical having 6 to 18 ring carbon atoms, for example phenyl, naphthyl or toluyl.

Aralkyl within this disclosure is always aryl as previously defined which is attached to alkyl as defined above, for example, benzyl, but may preferably be omitted from enumerations within this disclosure.

Cycloalkyl is 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 for cyclopentyl or cyclohexyl.

(die gestrichelte Linie markiert das Ende der Bindung zum Rest des Moleküls). Epoxyalkyl is preferably alkyl as defined above which is substituted by an epoxy group by ring formation. Epoxyalkyl is in particular epoxy-C ₁ -C ₇ -alkoxy, 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).

(die gestrichelte Linie markiert das Ende der Bindung zum Rest des Moleküls). Epoxyalkoxy is especially epoxy-C ₁ -C ₇ -alkoxy, in particular a radical of the formula

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

Acyl within this disclosure is always a radical of a carboxylic acid or a sulfonic acid, for example an aryl, alkyl or aralkyl-carboxylic acid or sulfonic acid radical, such as C ₁ -C ₇ alkanoyl, for example acetyl or propionyl, aroyl (aryl -C (= O) -), such as benzoyl, or the like.

Alkyl is always within this disclosure for particular unbranched or mono- or polysubstituted alkyl having, for example, 1 to 20, preferably 1 to 10 carbon atoms, for example having 1 to 4 carbon atoms, wherein one or more, for example 1 to 3, preferably not directly adjacent , especially by 2 carbon atoms separated and non-terminal, a carbon atom-containing chain segments (such as -CH ₂ - or -C (-) (H) - by one heteroatom, such as -N (-) -, -NH-, - O- or -S-, may be replaced, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.

Alkenyl throughout this disclosure is always an unbranched or mono- or poly-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 butene-1 or -2-yl.

Aminoalkyl is alkyl substituted with one or more amino groups, as just defined.

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

Aromatic means that the corresponding radicals, such as aryl, are defined above.

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

That "X is nothing" or X is nothing or the like means that the radical "-X-" in the respective formula stands for a simple bond. The fact that R _{1 is} "nothing" means that the radical R ₁ is missing.

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

Silanes that may or may not have reactive groups capable of participating in the polymerization, in other words, optionally contain these reactive groups, that is they may contain them.

Where "silanes" or other components in the plural is concerned, this always means "one or more".

(Meth) acryl is acrylic, methacrylic or acrylic and methacrylic (as a mixture).

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

Si-bonded hydrolyzable groups are in particular those groups L which are part of a group of the formula Z, Si (R ^B ) _3-t (L) _t (Z) in which R ^B independently of one another can be an alkyl, alkenyl, arylalkyl or aryl group, preferably alkyl and / or (further) alkenyl,
t stands for an integer from 1 to 3 and
L is an Si-bonded hydrolyzable group, in particular alkoxy.

The one or more or none or at least one amino, sec. Amino, mercapto, isocyanato, alkenyl, epoxy, anhydrido and / or in particular (meth) acryloyl group-containing, and at the same time containing at least one Si-bonded hydrolyzable group silane (s) preferably have middle or absolute molecular weights of 2,000 or less, 1,000 or less, 900 or less, 800 or less, 700 or less, 600 or less, or more preferably 500 or less, or more preferably 400 or less. Preferably, the silanes and low molecular weight, low viscosity substances, in particular other than relatively high molecular weight compounds (including, in particular, prepolymers fall).

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 at 10 Pa.s or lower, such as 1 Pa.s or lower. Very particularly preferred are extremely low-viscosity and low molecular weight silanes having viscosities of less than 100 mPa.s, in particular less than 10 mPa.s.

Viscosities are, unless otherwise stated, after DIN EN ISO 2555 measured with a Brookfield DV-III + viscometer with spindle 3 at 10 revolutions / minute (rpm) at 23 ° C and in Pa · s (hereinafter also referred to as Pa · s or Pas reproduced).

The no or at least one amino, sec. Amino, mercapto, isocyanato, alkenyl, epoxy, anhydride and / or (in particular) (meth) acryloyl group-bearing and containing at least one Si-bonded hydrolyzable group silanes are in an inventive or inventively used anchoring composition, for example in a proportion by weight of 0.1 to 50, in particular of 1 or more wt .-%, such as from 1 to 30 wt .-%, preferably from 2 or more wt .-%, such as from 2 to 30 or to 15 wt. %, from 3 or more wt%, such as from 3 to 20 or to 10 wt%, even more preferably from 4 or more wt%, eg from 4 to 20 or to 6 wt%, above.

Where weight percentages are given by weight, unless otherwise stated, they refer to the total weight of all reactive constituents and additions of the anchoring mass (ie, the constituents present in the post-mixing polymerizing mass which have been applied to a substrate or in particular get into a borehole and remain there, so also serving as fillers packaging materials, such as glass of cartridges / ampoules).

"To include" or "to embrace" means that there may be others in addition to the components or features mentioned above, so that for an incomplete enumeration, as opposed to "consist of", it is a final enumeration of the components or features enumerated in its use means.

"Partially or exclusively" or "at least partially" means that the components mentioned thereafter can be present in addition to other constituents of the corresponding component or exclusively, for example (in silanes or reactive resins or hardeners as components) based on the respectively defined component in fractions of up to a maximum of 10, 20, 30, 40, 50, 60, 70 or 80 to 90 or 100 wt .-%.

Where the attribute "further" is mentioned, it means that features without this attribute may be more preferable.

"And / or" means that said features / substances may each be present alone or in combination of two or more of the specified features / substances.

Preferred embodiments of the invention are also to be found in the claims, which are incorporated herein by reference.

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

Experimental procedure of determination of adhesion failure load:

A) Basic parameters:

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

B) Preparation of the drill holes

1a Experiments in dry borehole

Drill hole production: Drill holes were made in the horizontal concrete test specimen (low strength concrete of strength class C20 / 25) of dimensions 128 × 128 × 30 cm using a hammer drill and a hammer drill bit.

Part of the tests (labeled "cleaned") were followed by cleaning by drilling twice after drilling.

The other part of the tests (labeled "uncleaned") did not clean after drilling. Instead, in the course of the well production or after reaching the desired drilling depth of the drill was pulled out several times and introduced back into the hole. Meanwhile, the drill continuously rotated to effect the extraction of the drilling dust. This process was repeated at least four times.

1b Experiments in the moistened borehole

In the horizontal concrete test specimen (low-strength concrete C20 / 25), dimensions 128 × 128 × 30 cm), the pilot drill holes were made with a hammer drill and a hammer drill. These must have at least a drill diameter of 0.5 × d0, which was 7 mm in this experiment. On the pilot drill hole, a cylindrical cup with a hole in the area of the wellbore was glued and filled with water. The water remains in the borehole for at least 8 days until the water has penetrated into the concrete at a distance of 1.5 d to 2.5 d (d = anchor rod diameter) from the drilling axis. This ensures that the concrete in the area of the anchorage is saturated with water.

The beakers and the downhole water are removed by removing the beaker and shedding its contents, as well as drilling off the water in the borehole and drilling the final well with d0 (here 14 mm).

Your part of the experiments (labeled "cleaned") was cleaned following the well production by blowing out the well twice with a hand blower (e.g., fischer blower ABG, fischerwerke Gmbh & Co. KG, Waldachtal, Germany).

The other part of the tests (labeled "uncleaned") did not clean after drilling. It was simply pulled out several times in the course of the well production or after reaching the desired drilling depth of the drill and re-introduced into the hole. Meanwhile, the drill continuously rotated to effect the extraction of the drilling dust. This process was repeated at least four times.

B) Place anchor and pull

After making the wellbore, the reaction anchor cartridges were inserted into the wellbore (one per hole) and the anchor rods were rotationally driven with a hammer drill. The mortar excess was removed with a spatula. After the minimum curing time, here after 45 minutes, the extension direction was adapted and the armature was loaded with close support until failure

The experimental set-up complies with ETAG Nr1 Part 5.

Used compositions:

• E2BADMA

  technical ethoxylated bisphenol A dimethacrylate (vinyl ester)

  UMA

  Urethane methacrylate based on PMDI HPMA and BDDMA

  BDDMA

  butanediol

  HPMA

  2-hydroxypropyl methacrylate

  PMDI

  Polymeric diphenylmethane diisocyanate

  silane

  methacryloxypropyltrimethoxysilane

  quartz

  Quartz sand fraction 60-200 μm

  corundum

  Normal corundum 1100-1700 μm

It will be produced cartridges M12 consisting of a hardener inner tube and an outer tube. The inner tubes contain 0.32 g of a phlegmatized 50% dibenzoyl peroxide, consist of 1.05 g of glass and are thermally sealed. In the cartridge outer tubes with a glass weight of 3.60 g, the hardener inner tubes, the resin and the solid filler are introduced and also welded. 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 addition of 1.2 to 3% of an amine accelerator (toluidine derivative).

The following compositions are 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:

Vinylester anchoring compound V1 and urethane methacrylate anchoring compound V4, each containing quartz, were used to determine the following adhesion failure loads: II) Adhesion failure load when anchored to the anchoring masses cleaned uncleaned anchorage ground Filler / additive Adhesion Failure Load (kN) ± SD Filler / additive Adhesion failure (kN) ± SD Vinylester dry (1a) quartz 84.2 ± 4.8 quartz 54.54 ± 8.82 Vinylester damp (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 masses according to the invention with corundum

1.I) anchoring mass:

Vinylester anchoring compound V2 and urethane methacrylate anchoring compound V5, each with corundum, were used to determine the following adhesion failure rates: 1.II) Adhesion failure load when anchored to the anchoring masses with corundum cleaned uncleaned anchorage ground Filler / additive Adhesion failure load (kN) ± SD Filler / additive Adhesion failure load (kN) ± SD Vinylester dry (1a) corundum 93.99 ± 4.06 corundum 67.39 ± 7.07 Vinylester damp (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 increasing the adhesion failure load to quartz: anchorage ground Factor unpurified Adhesion failure load (corundum / quartz) Factor cleaned adhesion failure load corundum / quartz) Vinylester dry (1a) 1.24 1.12 Vinylester damp (1b) 1.13 1.33 Urethane methacrylate dry (1a) 1.07 1.06 Urethane methacrylate wet (1b) 1.15 0.98

Thus, except in the case of epoxy acrylate, there is an improvement in the adhesion failure load with corundum to quartz.

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

2.I) anchoring mass:

Vinylester 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) Adhesion failure load when anchored with corundum and silane anchoring compositions according to the invention cleaned uncleaned anchorage ground Filler / additive Adhesion failure load (kN) ± SD Filler / additive Adhesion failure load (kN) ± SD Vinylester dry (1a) Corundum and silane 99.37 ± 1.87 Corundum and silane 73.39 ± 5.97 Vinylester damp (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 of the Adhesion Failure Load to Quartz as Addition: anchorage ground Factor unpurified Adhesion failure load (corundum + silane / quartz) Factor cleaned adhesion failure load corundum + silane / quartz) Vinylester dry (1a) 1.35 1.18 Vinylester 1.46 1.45 damp (1b) Urethane methacrylate dry (1a) 1.23 1.13 Urethane methacrylate wet (1b) 2.28 1.43

Consequently, in all cases, corundum plus silane, in place of quartz, has a sometimes considerable increase in the adhesion failure load.

Example 3: Ratio of adhesion failure loads on unpurified vs. cleaned wellbore

From the tables of Example 1, Example 2 and the Comparative Example, the ratios of the adhesion failure load can be determined cleaned / uncleaned: Anchoring ground Ratio (factor) Adhesion failure load cleaned / uncleaned dry Ratio (factor) Adhesion failure load cleaned / uncleaned Wet Vinylester + quartz 1.54 1.27 Vinylester + corundum 1.39 1.49 Vinylester + corundum + silane 1.35 1.26 urethane 1.43 1.74 urethane 1.42 1.49 urethane 1.32 1.09

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

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

Example 4: crack and seismic

To Guideline ICC AC308, Table 4.2 Test no. 17 and 18 seismic tests are undertaken. The aim of the seismic tests is to pass the determined load level in the 0.3 mm crack and the resulting Neq, Nm, Ni without a failure during the periodic loading. If the armature fails early, a reduced load Neq, red is determined. This then results in a reduction factor α _seis eg 0.7. Without reduction α _seis = 1. Inventive anchoring materials can meet these requirements.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• EP 0150555 B1 [0002]
• DE 19956509 [0033]

Cited non-patent literature

• Guideline from the European Organization for Technical Approvals (EOTA) (2001): ETAG N ° 001 Edition November 2006 [0040]
• Guideline for European technical approval of metal anchors for use in concrete, Part 5: Bonded anchors, February 2008, under 5.1.2.1 (b) [0040]
• Guideline from the European Organization for Technical Approvals (EOTA) (2001): ETAG N ° 001 Edition November 2006 [0041]
• Guideline for European technical approval of metal anchors for use in concrete, Part 5: Bonded anchors, February 2008, under 5.1.2.1 (b) [0041]
• Guidelines ETAG 001 Part 5 [0043]
• ICC AC308 [0043]
• ICC AC308 [0044]
• Guidelines from the European Organization for Technical Approvals (EOTA) (2001): ETAG N ° 001 Edition November 2006 [0045]
• Guideline for European technical approval of metal anchors for use in concrete, Part 5: Bonded anchors, February 2008 [0045]
• DIN EN ISO 2555 [0076]
• Guideline ICC AC308, Table 4.2 Test no. 17 and 18 [0105]

Claims (18)

Use of at least one aggregate in an anchoring mass in the field of construction when using a polymer-forming anchoring mass, wherein the anchoring mass is introduced into a substrate and at the same time or subsequently an object to be fastened is introduced into the anchoring mass, characterized in that at least one very hard aggregate with a Mohs Hardness of 8 or greater, in particular a filler, to increase the load capacity of the bond between the substrate and the object to be fastened in comparison to the achievable with the addition of less hard additives load carrying capacity of the polymer-forming anchor mass is or is added. Use according to claim 1, characterized in that the very hard aggregate is corundum. Use according to one of claims 1 or 2, characterized in that the associated reactive constituents of the anchoring mass are present in a proportion of 5 to 100, e.g. from 10 to 60 wt .-%, are provided. Use according to any one of claims 1 to 3, wherein the adhesive product is introduced into a borehole in a substrate before, simultaneously with or after the introduction of an anchoring element. Use according to claim 4, characterized in that the introduction of the polymer-forming anchoring mass into the borehole despite at least residual contamination thereof by boring material, in particular without pre-cleaning of the borehole, especially without its brushing, blowing and rinsing, takes place. Use according to one of claims 1 to 5, characterized in that the polymer-forming anchoring mass is a multi-component, in particular a two-component product. Use according to one of claims 1 to 5, characterized in that the polymer-forming anchoring mass in use as a kit in a multi-chamber cartridge, in particular a two-chamber cartridge is configured. Use according to one of claims 1 to 7, characterized in that the polymer-forming anchoring mass as reactive constituents epoxy resins-resin component di- and / or multifunctional epoxy, hardener component di- and / or polyfunctional organic amino and / or Mercaptoverbindungen-, polyurethanes, Polyureas or their mixtures - synthetic resin component di- and / or polyisocyanates, optionally also as prepolymers, hardener component two or more hydroxyl, amino or hydroxyl and / or amino groups bearing organic compounds or mixtures thereof, alkoxysilane-terminated prepolymers - resin component alkoxysilane-terminated Prepolymer, hardener component water and / or organic or inorganic acid (s) -, or reactive olefins selected from unsaturated polyesters, (meth) acrylic esters or (meth) acrylic amides, and as complementary hardener component in each case free-radical hardener, mixtures of two or more such systems are also possible. Use according to any one of claims 1 to 8, wherein the associated reactive constituents of the anchoring composition are present in an amount of from 5 to 100, e.g. from 10 to 60 wt .-%, based on the total weight of all reactive constituents and additions of the anchoring mass, are provided. Use according to any one of Claims 1 to 9, characterized in that the proportion by weight of the very hard aggregate is 2 to 98, in particular 5 to 80, e.g. at 10 to 65 wt .-%, based on the total weight of all reactive constituents and additions of the anchoring mass is. Use according to any one of Claims 1 to 10, characterized in that 0.1 to 60% by weight, e.g. 0.5 to 50 wt .-% hardener, based on the total weight of all reactive constituents and additions of the anchoring composition, are provided, optionally one or more further additives in a total amount up to 80, for example from 0.01 to 50 wt .-%, are provided. Use according to one of claims 1 to 10, characterized in that, in order to further increase the load capacity of the bond between the substrate and the object to be fastened, a silane is additionally added. Use according to claim 12, characterized in that as silane one or more, no or at least one amino, sec. Amino, mercapto, isocyanato, alkenyl, (meth) acryloyl, anhydride and / or epoxy group-carrying and at least one Sigebundene hydrolyzable group-containing silane is provided. Use according to claim 12 or claim 13, characterized in that the silane or silanes in a weight fraction of 0.1 to 50, in particular of 1 or more% by weight, such as from 1 to 30 wt .-%, preferably of 2 or more wt%, such as from 2 to 20 or to 15 wt%, from 3 or more wt%, such as from 3 to 20 or to 10 wt%, even more preferably from 4 or more wt. -%, eg from 4 to 20 or to 6 wt .-%, are provided. Use of an anchoring mass as described in any one of claims 1 to 14, which includes a very hard aggregate having a Mohs hardness of 8 or greater, for fixing an anchoring element in a borehole, characterized in that the anchoring mass before, simultaneously with and / or after an anchoring element without cleaning the borehole, in particular without blowing, brushing and rinsing, is introduced. Use according to claim 15, characterized in that the borehole is moist. Use according to claim 15 or claim 16, characterized in that the borehole is in a cracked and / or by cracks, in particular in the tension zone, threatened substrate, in particular cracked concrete, is located. Use of an anchoring mass described in any one of claims 1 to 14, which includes a very hard aggregate having a Mohs hardness of 8 or greater, for fixing an anchoring element in a borehole, characterized in that the anchoring mass before, simultaneously with and / or after an anchoring element in a wet, cracked or is introduced by cracks, in particular in the tension zone, threatened or two or all three of these properties exhibiting borehole is introduced.