DE102024117056A1 - Radically curable synthetic resin fixing system with reactive thinner of balanced polarity - Google Patents

Abstract

A radically curable synthetic resin fastening system comprising a reactive resin component and a hardener component, wherein the reactive resin component contains one or more reactive diluents with balanced polarity, and other related inventive objects.

Description

The invention relates to a radically curable synthetic resin fastening system which comprises a reactive resin component and a hardener component, wherein the reactive resin component contains one or more reactive diluents with balanced polarity, the use of the reactive diluent(s) with balanced polarity as reactive diluents for such a synthetic resin fastening system, methods for producing the synthetic resin fastening system and the use of such a synthetic resin fastening system for fastening, for example, anchoring means in boreholes or gaps in building substrates, the use for increasing the robustness of a radically curable synthetic resin system, and a method for fastening, for example, anchoring means in boreholes or gaps using said synthetic resin fastening system which contains at least one of these radically curable reactive diluents.

The main factors influencing the performance of the synthetic resin fastening system are the quality of the borehole cleaning and the moisture of the mineral substrate. In damp and poorly cleaned boreholes, there is a significant reduction in performance, which is reflected in reduced load values or failure bond stresses. The resistance to these factors is referred to as the robustness of the synthetic resin fastening system. In the so-called "robustness test" - this means that the systems have as little difference as possible in the resulting values for performance (characterized in particular by the bond stress) when compared in use in damp and dry boreholes in building substrates - the aim is for the quotient of the bond stress determined in the damp and poorly cleaned borehole (hereinafter abbreviated to B7) to the bond stress in the dry, well-cleaned borehole (hereinafter abbreviated to R1) to be ≥ 0.9 (B7/R1 ≥ 0.9).

To overcome the loss of performance in wet and poorly cleaned boreholes, according to the DE 102010013196 A1 At least one methacryloxyalkyltrialkoxysilane and/or one poly(meth)acryloxyalkylsilsesquioxane is added to the resin component as a further constituent.

The EP 3 851 423 A1 proposes the use of a non-polar reactive resin mixture in the resin component of a mortar mass to improve adhesion to the surface of semi-cleaned and/or moist boreholes in mineral substrates. The reactive diluents for producing a non-polar reaction resin mixture are preferably selected from the group consisting of ethyl methacrylate (EMA), 3,3,5-trimethylcyclohexyl methacrylate (TMCHMA), isobornyl methacrylate (IBOMA), isobutyl methacrylate (i-BMA), tetrahydrofurfuryl methacrylate (THFMA), 2-ethylhexyl methacrylate (2-HEMA), cyclohexyl methacrylate (c-HMA), allyl methacrylate (AMA), benzyl methacrylate (BNMA), isodecyl methacrylate (IDMA), 1,12-dodecanediol dimethacrylate (1,12-DDDDMA), 1,6-hexanediol dimethacrylate (1,6-HDDMA), 1,4-butanediol dimethacrylate (1,4-BDDMA), 1,3-butanediol dimethacrylate (1,3-BDDMA), ethylene glycol dimethacrylate (EGDMA) and glycerol dimethacrylate.

It has been shown that neither the teaching of DE 102010013196 A1 nor the non-polar reaction resin mixture according to EP 3 851 423 A1 and also the combined teaching of both patent applications lead to robust synthetic resin fastening systems with a quotient B7/R1 ≥ 0.9.

Against this background, the object of the invention presented here was to find new reactive diluents - not previously known from the prior art or not intended for this purpose - which lead to extremely robust (quotient B7/R1 ≥ 0.9) synthetic resin fastening systems. The invention generally relates to a synthetic resin fastening system as mentioned at the beginning, whereby a reactive diluent with balanced polarity is to be understood as a reactive diluent which lies in a polarity range between hydrophilic and hydrophobic, in particular as defined below.

An example of a hydrophilic reactive diluent is polyethylene glycol 200 dimethacrylate (PEG200DMA), an example of a hydrophobic reactive diluent is 1,4-butanediol dimethacrylate (BDDMA) as in EP 3 851 423 A1 mentioned.

Surprisingly, it was found that the reactive diluents to be used according to the invention lead to extremely robust synthetic resin fastening systems which, in the robustness test (comparison of R1, B7), have a quotient B7/R1 of ≥ 0.80, preferably ≥ 0.89, in particular ≥ 0.9. This robustness is extremely important for synthetic resin fastening systems in order to achieve high performance, since lower quotients B7/R1 (larger sub- difference between dry and wet borehole) according to EAD330499-02-0601 Edition 04/2023 (hereinafter also referred to as "EAD" or "EAD 330499-02-0601") according to Table 2.2.5.6.1 can lead to higher reduction factors and thus reduce the overall performance of the synthetic resin fixing system on which the subsequent design is based. Increasing robustness means in particular a higher B7/R1 quotient compared to compositions with PEG200DMA (hydrophilic reference) and/or BDDMA (hydrophobic reference).

Examples of reactive diluents according to the invention are those compounds which are characterized by the presence of at least one or more propylene glycol or propylene oxide repeat units which have at least one reactive (meth)acrylate group directly or indirectly at the ends (i.e. are directly or indirectly “endcapped”).

These are in particular those reactive diluents which are selected from the group consisting of propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, furthermore tripropylene glycol di(meth)acrylate; furthermore tetrapropylene glycol di(meth)acrylate and block alkylene glycol di(meth)acrylates of the formula CYXYC in the form of ethoxylated propylene glycols terminally esterified with (meth)acrylate in a central propylene oxide block (X) with 5 or more (preferably up to 20) linearly arranged 1,2-propylene oxide units, which is extended at both ends with two or more ethylene oxide units (Y), independently of one another, each of which carries a (meth)acryloyl group (C) at both ends, or furthermore mixtures of two or more of the reactive diluents mentioned.

Examples of reactive diluents with balanced polarity which are preferably to be included/used according to the invention are dipropylene glycol di(meth)acrylate or tripropylene glycol di(meth)acrylate, or mixtures thereof.

Other examples of reactive diluents with balanced polarity that are preferably to be included/used according to the invention are block alkylene glycol di(meth)acrylates that are composed of propylene glycol and ethylene glycol, namely those of the formula CXYXC in the form of ethoxylated propylene glycol terminally esterified with (meth)acrylate with a central propylene oxide block (X) with 6 to 15 linearly arranged 1,2-propylene oxide units, which is extended at both ends with two to 4 ethylene oxide units (Y), each of which carries a (meth)acryloyl group (C) at both ends, such as ethoxylated propylene glycol di(meth)acrylates (e.g. Bisomer EP150DMA, Bisomer EP100DMA, or Miramer M2053).

Mixtures of one or more reactive diluents selected from two or more of those mentioned above are also to be included or used according to the invention.

Without wishing to be bound by this theory, the advantageous robustness of the synthetic resin fastening systems which contain the reactive diluents according to the invention can actually be related to the balanced polarity: Hydrophilic (water-loving) synthetic resin fastening systems readily absorb the water in a water-filled borehole or the moisture in a wet borehole, whereby this absorbed water/moisture has a softening effect in the hardening fastening system. In contrast, hydrophobic (water-avoiding) synthetic resin fastening systems, due to their water-repellent properties, can lead to a lack of wetting in wet boreholes and thus to adhesion problems. The reactive diluents according to the invention with balanced polarity, on the other hand, can ensure sufficient wetting coupled with good adhesion and reduced water/moisture absorption, whereby the softening effect is less pronounced and good performance can be achieved in both dry and wet boreholes.

• In einer ersten Ausführungsform betrifft die Erfindung daher (ein- oder insbesondere mehrkomponentige) radikalisch härtbare Kunstharz-Befestigungssysteme, welche ein oder
• mehrere Reaktivverdünner ausgewählt aus solchen, welche ein oder mehrere Reaktivverdünner, die durch Vorhandensein von einer oder mehreren Propylenglykol- bzw.
• Propylenoxid-Wiederholeinheiten gekennzeichnet sind, welche mindestens eine reaktive (Meth)Acrylatgruppe direkt oder indirekt an den Enden aufweisen, und welche ausgewählt sind aus der Gruppe bestehend aus Propylenglykoldi(meth)acrylat,
• Dipropylenglykoldi(meth)acrylat, ferner Tripropylenglykoldi(meth)acrylat; ferner Tetrapropylenglykoldi(meth)acrylat und Block-Alkylenglykoldi(meth)acrylaten der Formel CYXYC in Form von mit (Meth)acrylat terminal veresterten ethoxylierten Propylenglykolen in einem zentralen Propylenoxidblock (X) mit 5 oder mehr (vorzugsweise bis 20) linear angeordneten 1,2-Propylenoxideinheiten, der an beiden Enden mit unabhängig voneinander zwei oder mehr Ethylenoxideinheiten verlängert ist (Y), die an beiden Enden je eine (Meth)acryloylgruppe (C) tragen, oder ferner Mischungen von zwei oder mehr der genannten Reaktivverdünner, beinhalten; wobei insbesondere der oder die genannten Reaktivverdünner in einer radikalisch härtbaren Reaktivharzkomponente (A) in einem mehr-, in erster Linie zweikomponentigen radikalisch härtbaren Kunstharz-Befestigungssystem mit einer radikalisch härtbaren Reaktivharzkomponente (A) und einer Härterkompontente (B) beinhaltet ist oder sind.

In detail, the invention therefore relates primarily to the following inventive subjects (embodiments of the invention or embodiments of the invention):

• In a first embodiment, the invention therefore relates to (single- or in particular multi-component) radically curable synthetic resin fastening systems which contain one or
• several reactive diluents selected from those which comprise one or more reactive diluents characterized by the presence of one or more propylene glycol or
• Propylene oxide repeat units which have at least one reactive (meth)acrylate group directly or indirectly at the ends and which are selected from the group consisting of propylene glycol di(meth)acrylate,
• Dipropylene glycol di(meth)acrylate, furthermore tripropylene glycol di(meth)acrylate; furthermore tetrapropylene glycol di(meth)acrylate and block alkylene glycol di(meth)acrylates of the formula CYXYC in the form of ethoxylated propylene glycols terminally esterified with (meth)acrylate in a central propylene oxide block (X) with 5 or more (preferably up to 20) linearly arranged 1,2-propylene oxide units, which is extended at both ends with two or more ethylene oxide units (Y), independently of one another, each of which carries a (meth)acryloyl group (C) at both ends, or furthermore mixtures of two or more of the reactive diluents mentioned; wherein in particular the reactive diluent(s) mentioned is/are contained in a radically curable reactive resin component (A) in a multi-component, primarily two-component, radically curable synthetic resin fastening system with a radically curable reactive resin component (A) and a hardener component (B).

A preferred embodiment is such radically curable synthetic resin fastening systems according to the previous paragraph, in which the reactive diluent(s) consists of propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, further tripropylene glycol di(meth)acrylate or tetrapropylene glycol di(meth)acrylate, and further higher homologues and block alkylene glycol di(meth)acrylates which are composed of propylene and ethylene glycol, namely those of the formula CXYXC in the form of ethoxylated propylene glycol terminally esterified with (meth)acrylate with a central propylene oxide block (X) with 6 to 15 linearly arranged 1,2-propylene oxide units, which is extended at both ends with two to 4 ethylene oxide units (Y), each of which carries a (meth)acryloyl group (C) at both ends (e.g. Bisomer EP150DMA, Bisomer EP100DMA, or Miramer M2053), or mixtures of two or more thereof. The respective methacrylates are preferred.

Preferred embodiments of the invention are those which contain only one (1) of the reactive diluents according to the invention mentioned therein and preferably no further reactive diluent.

Preferred are such radically curable synthetic resin fastening systems for improving performance in poorly cleaned and/or moist boreholes in mineral substrates, characterized in that they have the highest possible quotient B7/R1 of the determined bond stress in the moist and poorly cleaned borehole B7 to the bond stress in the dry, well-cleaned borehole R1, in particular a quotient B7/R1 of ≥ 0.80, preferably ≥ 0.89, preferably ≥ 0.90, where B7/R1 can be determined or is preferably determined in accordance with EAD330499-02-0601 Edition 04/2023 (EAD). By definition, the upper limit is preferably 1.

In a second embodiment, the invention relates to the use of a synthetic resin fastening system as defined above and below as an adhesive in fastening technology, in particular for fastening anchoring means in drill holes or gaps, especially in a building substrate.

A third embodiment of the invention relates to a method for producing the synthetic resin fastening systems defined above and below, characterized in that reactive diluents as defined above and below are mixed into the remaining components, in particular a reactive resin component in a multi-component system, and in particular, in the case of multi-component systems in separate compartments, are filled into packaging.

A fourth embodiment of the invention relates to a method for fastening, for example, anchoring means in boreholes or cracks using one of the synthetic resin fastening systems defined above and below, which contains or contains at least one of the radically curable reactive diluents to be used according to the invention.

The reactive diluents for use in synthetic resin fastening systems according to the invention or their use in such a system also form a subject matter of the invention.

A further subject matter of the invention relates to a reactive resin component for a synthetic resin fastening system according to the invention as such, which contains a radically curable reactive resin and one or more of the reactive diluents mentioned that can be used according to the invention.

Further subject matter of the invention emerges from the claims, which are incorporated herein by reference, wherein subclaims represent preferred embodiments of the invention compared to the respective claims referred to.

The following definitions serve to clarify certain terms or symbols and to describe particular embodiments of the invention, whereby in the embodiments of the invention mentioned above and below, individual, several or all terms or symbols can be replaced by more specific definitions, each of which represents particular embodiments of the invention.

“Radically curable synthetic resin fastening systems (containing unsaturated bonds, in particular olefinic double bonds, in the reactive (synthetic) resin component)” means in particular that the synthetic resin fastening systems according to the invention are based on reactive synthetic resins (also referred to herein as reactive resins), but in addition to the components mentioned above and below, they can also contain other common ingredients (components; e.g. fillers, additives or other components mentioned above or below). These other ingredients can, for example, be present in a total mass fraction of up to 80%, preferably between 0.01 and 65%. “Based on” also means in particular that the component in question contains more than 50%, preferably more than 60%, such as more than 70% up to 100% (mass fraction based on the respective component, e.g. “synthetic resin component” or “hardener component”) of the substances mentioned after “based on”.

Above and below, percentage or content information means mass percentages in percent, indicated as %, preferably indicated as weight %, unless otherwise stated. Where no other information is provided, the percentage information refers to the total mass of the components of a multi-component synthetic resin system excluding the packaging (such as without the material of the casings of films, without (e.g. glass) walls of glass cartridges, without the material of the casing of plastic containers or cartridges (there also without static mixers) and the like).

The mass fraction of the reactive diluents according to the invention or to be used according to the invention in a synthetic resin fastening system according to the invention or to be used according to the invention is preferably in the range from 0.1 to 50%, in particular from 0.5 to 40%, particularly preferably from 1 to 25%. Based on a reactive resin component and only the reactive resin content and the amount of reactive diluent, the mass fraction is alternatively preferably in the range from 0.5 to 60%, in particular from 1 to 50%, in particular from 2 to 30%.

"Includes" or "comprising" or "containing" means that in addition to the components or features mentioned, others may be present, and therefore represents a non-exhaustive list, in contrast to "consisting of", which represents an exhaustive list of the components or features listed when it is used.

“Building substrates” are in particular concrete or masonry (including brick), especially concrete, but also wood.

A hole or gap is understood to mean a drill hole in particular. This can be cleaned (e.g. by blowing out and/or brushing once or several times) or used uncleaned for the use or method according to the invention, or as otherwise stated.

Anchoring elements are understood to mean in particular those made of metal, e.g. undercut anchors, threaded rods, screws, drilling anchors, bolts, or also another material, such as composite material, plastic or wood.

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

“A” means primarily the indefinite article (e.g., “one or more” or “at least one”), except where the context requires use as a numeral. Where the plural is indicated, this also includes the singular.

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

“Approximately” means in particular that a numerical value identified therewith may deviate from the stated value by ± 10%, preferably by ± 5%, for example by ± 2%. “Approximately” may be deleted for preferred embodiments of the invention. (Meth)acrylic or “(meth)acrylic) stands for acrylic, methac ryl or acrylic and methacrylic (as a mixture). “Methacrylic” or “methacrylic” indicates preferred compounds.

In the present disclosure, radically curable means the same as radically polymerizable.

Radically curing (= unsaturated) reactive (synthetic) resins are primarily those which, as radically curing (which includes “curable (e.g. before addition of hardener)”) components, contain or in particular consist of organic compounds with unsaturated (e.g. olefinic) radicals, in particular those which comprise curable esters with unsaturated carboxylic acid radicals; e.g. in particular (meth)acrylate or (meth)acrylamide monomers, such as acrylic acid and/or methacrylic acid or preferably their esters (referred to as (meth)acrylates) or amides, in particular (meth)acrylates such as mono-, di-, tri- or poly(meth)acrylates or (preferably in each case propoxylated or in particular ethoxylated) aromatic diol, such as bisphenol A, bisphenol F or novolak (in particular di-)(meth)acrylate), epoxy(meth)acrylates (in particular in the form of reaction products of di- or polyepoxides, e.g. bisphenol A, bisphenol F or novolak di- and/or poly-glycidyl ethers, with unsaturated carboxylic acids, e.g. C ₂ -C ₇ -alkenecarboxylic acids, such as in particular (meth)acrylic acid), urethane and/or urea(meth)acrylates (which, as is known to the person skilled in the art, are also advanced and/or oligomeric urethane and/or urea (meth)acrylates), and/or unsaturated polyester resins, or the like; or a mixture of two or more of these curable unsaturated organic components.

worin n für eine Zahl größer oder gleich 1 steht (wenn Gemische verschiedener Moleküle mit unterschiedlichen n-Werten vorliegen und durch die Formel repräsentiert werden, sind auch nicht-ganzzahlige Zahlen als Mittelwert möglich).Examples of epoxy(meth)acrylates present or used in particular embodiments of the invention are those of the formula (I)

where n is a number greater than or equal to 1 (if mixtures of different molecules with different n values are present and represented by the formula, non-integer numbers are also possible as the mean value).

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 im Falle der propoxylierten Verbindungen jeweils anstelle der Gruppe [-O-CH₂-CH₂]_a und/oder [-O-CH₂-CH₂]_b eine Anzahl „a“ und/oder „b“ an unverzweigten oder vorzugsweise verzweigten Oxypropylengruppen vorliegt.Examples of propoxylated or especially ethoxylated aromatic diols, such as bisphenol A, bisphenol F or novolak (especially di-)(meth)acrylates, useful in particular embodiments of the invention are those of the formula (II)

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 an average value), wherein in the case of the propoxylated compounds, instead of the group [-O-CH ₂ -CH ₂ ] _a and/or [-O-CH ₂ -CH ₂ ] _b, a number "a" and/or "b" of unbranched or preferably branched oxypropylene groups is present.

Examples of urethane (meth)acrylates present or used in particular embodiments of the invention are those which result, on the one hand, from the reaction of a pre-extended di- or polyisocyanate and/or, on the other hand, from the direct reaction of a di- or polyisocyanate (e.g. PMDI and/or MDI) with hydroxyethyl or hydroxypropyl (meth)acrylate. The di- or polyisocyanate can each have a monomeric, oligomeric and/or polymeric structure. The manner in which pre-extension reactions are carried out and the multitude of pre-extension reaction options are known to the person skilled in the art and are not explicitly described here. Reference is made here, for example, to the applications EP 0508183 A1 , EP 0432087 A1 and especially WO 2019/197190 A1 referred to.

Preferably, the only radically curable synthetic resin (reactive resin) present is an epoxy (meth)acrylate; more preferably a urethane (meth)acrylate or in particular an alkoxylated, aromatic (meth)acrylate of the formula (II), as described above in each case. The respective methacrylates are preferred.

The reactive resin(s) are preferably contained in a mass fraction of 2 to 80%, in particular 5 to 50%, primarily 10 to 40%.

The synthetic resin fastening systems according to the invention (which alternatively stands for “to be used according to the invention”) can contain, in addition to the components already mentioned, other conventional components (e.g. additives or other components mentioned above or below) in one or the synthetic resin component and/or one or the hardener component. These other components can be present, for example, in a mass fraction of up to 80% in total, preferably between 0.01 and 65%. Even where “based” is not expressly mentioned, such conventional components are possible.

Examples of further (“usual”) ingredients (additives, components) of reactive resins in synthetic resin fastening systems according to the invention or used according to the invention are metal salt-based or preferably amine accelerators, inhibitors, non-reactive diluents, reactive diluents, thixotropic agents, fillers and/or other additives, or mixtures of two or more of these ingredients.

Suitable amine accelerators are those with sufficiently high activity, such as in particular tertiary aromatic amines, in particular hydroxyalkylamino group-substituted aromatic compounds selected from the group consisting of epoxyalkylated anilines, toluidines or xylidines, such as ethoxylated or propoxylated toluidine, aniline or xylidine, for example N,N-bis(hydroxypropyl- or hydroxyethyl)-toluidines or dipropoxy-p-toluidine or -xylidines, such as N,N-bis(hydroxypropyl- or hydroxyethyl)-p-toluidine, N,N-bis(hydroxyethyl)-xylidine and very particularly corresponding higher alkoxylated technical products. One or more such accelerators are possible. The accelerators preferably have a mass fraction (concentration) of 0.005 to 10, in particular of 0.1 to 10%.

Non-phenolic (anaerobic) and/or phenolic inhibitors can be added as inhibitors.

Phenolic inhibitors or stabilizers (which are often included as an already added component of commercially available radical-curing reaction resins, but may also be missing) include (non-alkylated or alkylated) hydroquinones, such as hydroquinone, 2-methylhydroquinone, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butylhydroquinone, 2,6-dimethylhydroquinone, 2,3,5-trimethylhydroquinone, benzoquinone, 2,3,5,6-tetrachloro-1,4-benzoquinone, methylbenzoquinone, 2,6-dimethylbenzoquinone, naphthoquinone; (nonalkylated or alkylated) phenols, such as 2-methoxyphenol, 4-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol, 2,4,6-trimethylphenol, 2,4,6-tris (dimethylaminomethyl)phenol, 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 4,4'-isopropylidene diphenol, 6,6'-di-tert-butyl-4,4'-bis(2,6-di-tert-butylphenol), 2,2'-methylene-di-p-cresol, 4,4'-methylene-bis(2,6-di-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 6-tert-butyl-2,4-xylenol, 2,6-di-tert-butyl-p-cresol; (non-alkylated or alkylated) catechols (pyrocatechols) such as pyrocatechol, 4-tert-butylpyrocatechol and 4,6-di-tert-butylpyrocatechol, 3,5-di-tert-butyl-1,2-benzenediol, or mixtures of two or more thereof. These preferably have a mass fraction of up to 1%, in particular if present between 0.0001 and 0.5%, e.g. between 0.01 and 0.1%.

Phenothiazine or organic nitroxyl radicals are preferred as non-phenolic or anaerobic (i.e., in contrast to phenolic inhibitors, also effective without oxygen) inhibitors or stabilizers. Organic nitroxyl radicals can be HALS stabilizers as described in " Polyurethane, Plastics Handbook”, Chapter 3.4.8 Anti-aging agents, p. 121, 3rd edition, 1993, edited by Gerhard W. Becker and Dietrich Braun, Carl Hanser Verlag Munich Vienna such as in particular 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol (“4-OH-TEMPO”), 1-oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one, 1-oxyl-2,2,6,6-tetramethyl-4-carboxyl-piperidine, 1-oxyl-2,2,5,5-tetramethylpyrrolidine, 1-oxyl-2,2,5,5-tetramethyl-3-carboxylpyrrolidine, or sterically hindered amines such as (4,4'-di-octyl-diphenylamine), or for example those as described in the DE 199 56 509 , which is incorporated herein by reference, in particular with regard to the compounds mentioned therein, in particular 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol ("4-OH-TEMPO" or "TEMPOL"). The weight fraction of the non-phenolic inhibitors (if present) is preferably in the range from 1 ppm (by mass) to 2%, in particular, for example, in the range from 5 ppm to 1%, based on the reaction resin formulation.

As non-reactive diluents, for example, vegetable oils, such as castor oil, or furthermore bioalcohols and fatty acids and their esters, or mixtures of two or more thereof, for example in a proportion of 3 to 60%, e.g. from 4 to 55%, can be added.

Common rheological aids that cause thixotropy can be used as thixotropic agents, such as pyrogenic silica or surface-treated silica (e.g. with silanes). They can be added in a weight proportion of 0.01 to 50%, for example 0.5 to 20%.

The fillers may include conventional fillers, for example with coarser and/or finer particle sizes, in particular chalk, gypsum, quicklime, sand, such as quartz sand, quartz powder, corundum, glass (also as hollow spheres), porcelain, ceramics, silicates, clays or barite, which may be added as powder in granular form or in the form of molded bodies, or others, such as kernel or shell flour from plants or starch and their derivatives, which increases the biogenic carbon content, such as olive kernel flour, coconut shell flour or walnut shell flour, or mixtures of two or more thereof, wherein the fillers may also or in particular also be silanized. The fillers may be present in one or more components of a multi-component synthetic resin fastening system according to the invention, for example one or both components of a corresponding two-component kit; the mass fraction of fillers is preferably 0 to 90%, in particular 5 to 80%, for example 10 to 50% or 40 to 70% (whereby casing material destroyed during the introduction of anchoring elements (e.g. shattered glass or shattered plastic), for example shards from cartridges, can also be counted as fillers). In addition to or as an alternative to one or more of the fillers mentioned, hydraulically hardenable fillers such as gypsum, quicklime or cement (e.g. alumina or Portland cement), water glasses or active aluminum hydroxides, or two or more thereof, can also be added.

In order to improve the carbon footprint or carbon balance of the synthetic resin fastening system, powdered recycled materials from waste products can also be used as fillers. Preferably, a corresponding recycled filler is selected from the group consisting of concrete, bricks, sand-lime bricks, natural stones, fly ash, rubber, waste plastic, waste glass and possibly hardened chemical synthetic resin fastening system present during the processing of the recycled filler.

Other additives may also be added, such as non-reactive diluents, flexibilizers, stabilizers, rheology aids such as bentonites, alkyl celluloses such as methyl celluloses, castor oil derivatives or the like, plasticizers such as phthalic acid and sebacic acid esters, antistatic agents, flexibilizers, wetting and dispersing agents, coloring additives such as dyes or in particular pigments, for example for differently coloring the components for better control of their mixing, or furthermore plasticizers, or mixtures of two or more thereof. In addition, agents for improving the compatibility between resin and hardener components, such as ionic, non-ionic or amphoteric surfactants, soaps, wetting agents, detergents, polyalkylene glycol ethers, salts of fatty acids, mono- or diglycerides of fatty acids, sugar glycerides, lecithin, alkanesulfonates, alkylbenzenesulfonates, fatty alcohol sulfates, fatty alcohol polyglycol ethers, fatty alcohol ether sulfates, sulfonated fatty acid methyl esters, fatty alcohol carboxylates, alkyl polyglycosides, sorbitan esters, N-methylglucamides, sucrose esters, alkylphenols, alkylphenol polyglycol ethers, alkylphenol carboxylates, quaternary ammonium compounds, esterquats, carboxylates of quaternary ammonium compounds, can also be used. Such further additives can preferably be added in total mass proportions of 0 to 90%, for example 0 to 40%.

In addition to the reactive diluents included according to the invention, one or more further “reactive diluents” may be included.

As “reactive thinners” (so named to distinguish them from the “reactive thinners” mentioned in the definition of the invention), one or more radically curing unsaturated reactive thinners in biogenic or non-biogenic form can also be added in addition to the reactive thinners included in the invention, which primarily means those which, as radically curing (which includes “curable (e.g. before addition of hardener)”) components, contain organic compounds with unsaturated (e.g. olefinic) radicals or in particular consist of such compounds, e.g. in particular (meth)acrylate or (meth)acrylamide monomers, such as acrylic acid and/or methacrylic acid or preferably their esters (referred to as (meth)acrylates) or amides, in particular (meth)acrylates such as mono-, di-, tri- or poly(meth)acrylates (including hydroxy-lower alkyl(meth)acrylates, which also result from the U(M)A resin production according to the invention already at Excess may be included as reactive diluents, such as hydroxypropyl (meth)acrylate or hydroxyethyl (meth)acrylate; alkylene glycol di(meth)acrylates, such as diethylene glycol di(meth)acrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate; Methoxypolyethylene glycol mono(meth)acrylate, such as methoxypolyethylene glycol 350 or 500 methacrylate (MPEG350 or 500MA, mean n ≈ 8 or 11, or higher homologues; polypropylene glycol mono(meth)acrylate with a mean n ≈ 4 - 5; oligoethylene glycol di(meth)acrylates, such as polyethylene glycol 200 dimethacrylate (PEG200DMA, mean n ≈ 4), polyethylene glycol 400 dimethacrylate (PEG400DMA, mean n ≈ 9) or as in WO 2016/000807 A1 or EP 4 056 607 which are incorporated herein by reference; aliphatic or aromatic alkyl (meth)acrylates with 1 to 10 (meth)acrylate groups, such as mono-, di-, tri-, tetra-, penta-, hexa- or poly(meth)acrylates, e.g. alkyl di- or tri(meth)acrylates, such as 1,2-ethanediol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, butanediol di(meth)acrylate, such as 1,3- or in particular 1,4-butanediol di(meth)acrylate, hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2-ethylhexyl (meth)acrylate, acetoacetoxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, tert-butyl (meth)acrylate, 2-methacryloyloxyethyl phosphate, trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate, Polyglycerol poly(meth)acrylate, the reaction product of the acylation of glycerol formal (an equilibrium mixture of 5-hydroxy-1,3-dioxane and 4-hydroxymethyl-1,3-dioxolane, which is liquid at room temperature) with methacrylic acid or its reactive derivatives (known as GLYFOMA from Evonik), benzyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate; heteroalkyl (meth)acrylates, such as 2-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminomethyl (meth)acrylate, 3-dimethylaminopropyl (meth)acrylamide; Cycloalkyl, bicycloalkyl or heterocyclyl (meth)acrylates, in which cycloalkyl or bicycloalkyl can further be substituted and has 5 to 7 ring carbon atoms and heterocyclyl has 5 or 6 ring atoms, can further carry substituents and has 1 or 2 ring heteroatoms selected from N, O and S, such as tetrahydrofurfuryl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tricyclopentadienyl di(meth)acrylate, solketal (meth)acrylate, cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, isosorbide mono- and/or di(meth)acrylate or isobornyl (meth)acrylate; or furthermore styrenes, such as styrene, α-methylstyrene, vinyltoluene, tert-butylstyrene and/or divinylbenzene; or mixtures of two or more thereof, for example (if present) in a mass fraction of 0.1 to 90%, e.g. between 10 and 80%, 30 to 70% or 40 to 60%, here in each case based on the total weight of the mixture of reactive synthetic resin and reactive thinner without fillers, but, if present, with other additives. Preferably, however, no other "reactive thinners" are present apart from the reactive thinner(s) present or used according to the invention.

Preferably, the synthetic resin or reactive resin component can also contain an adhesion promoter. The adhesion promoter improves the cross-linking between the borehole wall and the synthetic resin fastening system and thus ensures increased adhesion in the cured state. This results in an increased bond failure stress, which is of great importance for the use of the synthetic resin fastening system. Suitable adhesion promoters are preferably selected from the group of silanes and/or siloxanes, which are functionalized with other reactive organic groups and can be incorporated into the polymer network. This group includes, for example, 3-(meth)-acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 3-(meth)acryloyloxymethyltrimethoxysilane, 3-(meth)acryloyloxymethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, functionalized ethyl or propyl polysilicate and mixtures of two or more thereof. In this respect, reference is made to the application DE 10 2009 059210 , the relevant content of which is hereby incorporated into this application. Such adhesion promoters can preferably be added in total mass proportions of 0 to 15%, for example 1 to 10%.

In the hardener component, the initiator for the hardening of the synthetic resin fixing systems according to the invention in the case of radical polymerization is, for example, radical-forming peroxides, e.g. organic peroxides such as peracids, for example diacyl peroxides, e.g. dibenzoyl peroxide, alkyl hydroxy peroxides, dialky peroxides, aldehyde peroxides, peracetals, perketals, ketone peroxides such as methyl ethyl ketone peroxide or cyclohexanone peroxide, peroxycarbonates, or alkyl peresters such as tert-butyl perbenzoate, inorganic Peroxides, persulfates or perborates, azides, azo compounds (such as AIBN), tetraazenes, and also halogen-containing initiators typical for ATRP, or mixtures thereof are used.

Alternatively, hardener components with other radical hardener systems can be used for curing, which can also do without the "per" compounds mentioned in the previous paragraph or can be used in parallel with such "classic" radical formers.

1. a) mindestens einen Aktivator in Form eines Metallsalzes
2. b) als Radikalkettenstarter mindestens eine Thiol- und/oder Thiolester-Gruppen beinhaltende Verbindung,

beinhaltet. Durch die Kombination bzw. das Mischen der beiden Bestandteile können Radikale gebildet werden, welche anstelle von bisher üblichen Radikalbildnern eine Polymerisation von nichtaromatischen Doppelbindungen, z.B. olefinischen Doppelbindungen, beispielsweise Acrylaten oder Methacrylaten, auslösen können. Es sei hier auf die Patentanmeldung WO 2015/090523 A1 verwiesen, die hier diesbezüglich durch Bezugnahme aufgenommen wird.For example, a hardener system can be used to harden the synthetic resin fastening systems according to the invention, which contains the following components:

1. a) at least one activator in the form of a metal salt
2. b) as radical chain initiator, a compound containing at least one thiol and/or thiolester group,

By combining or mixing the two components, radicals can be formed which, instead of the previously usual radical formers, can trigger a polymerization of non-aromatic double bonds, e.g. olefinic double bonds, for example acrylates or methacrylates. Reference is made here to the patent application WO 2015/090523 A1 which is incorporated herein by reference.

Examples of thiols are thioglycerin, methyl, ethyl mercaptan and higher homologues e.g. dodecyl mercaptan; dimercaptans, such as dimercaptopropanesulfonic acid, dimercaptosuccinic acid, dithiothreitol; poly(ethylene glycol)dithiols, of the general formula HS-[CH ₂ -CH ₂ -O] _n -CH ₂ -CH ₂ -SH, where n is a number between 0 and 10; liquid polysulfide polymers with thiol end groups e.g. Thioplast G types from Akzo Nobel; polymercaptan hardeners and crosslinkers e.g. SIQ-Amin 999 from SIQ-Kunstharze GmbH; ethoxylated and/or propoxylated alcohols from mono-, di-, tri-, tetra-, pentaols and/or other polyols with thiol end groups e.g. Capcure 3-800 from Cognis, or the compounds mentioned below as particularly suitable thiols. A particularly suitable thiol ester is octanethiolic acid S-[3(triethoxysilyl)propyl] ester. Examples of particularly suitable thiols are glycol di(3-mercaptopropionate), trimethylolpropane tri(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), dipentaerythritol hexa-3-mercaptopropionate, ethoxylated trimethylolpropane tris(3-mercaptopropionate) with different degrees of ethoxylation (e.g. ETTMP 700 and ETTMP 1300 from Bruno Bock), tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, 3-mercaptopropyltrimethoxysilane.

• a) mindestens einen Aktivator in Form eines Metallsalzes und
• b) als Radikalkettenstarter mindestens eine CH-acide Verbindung insbesondere der Formel A,
  
  worin
  • (i)
    • -A- für -C(R¹)(R²)- steht
    • -X- für eine Bindung, für -NR³- oder für -(CR⁴R⁵)_p- steht, oder für -O- steht,
    • Y für NR⁶ oder für (CR⁷R⁸)_q steht, oder für O steht,
    • wobei wenn X für O steht auch Y für O steht;
    • wobei vorzugsweise X für (CR⁴R⁵)_p steht und Y für CR⁷R⁸ steht,
    • oder X für NR³ und Y für NR⁶ steht;
    • Z¹ für O, S, S=O oder S(=O)₂ steht,
    • Z² für O, S, S=O oder S(=O)₂ steht,
    • Z³ für O, S, S=O oder S(=O)₂ oder für R9 und R10 steht,
    • p für 1, 2 oder 3 steht, vorzugsweise für 1 oder 2
    • q für 1, 2 oder 3 steht, vorzugsweise für 1;
    und die Reste R¹, R², R³, R⁴, R⁵, R⁶, R⁷ R⁸, R⁹ und R¹⁰ unabhängig voneinander für Wasserstoff, Alkyl, Aryl, Aralkyl, Cycloalkyl oder Cycloalkylalkyl stehen und jeweils unsubstituiert oder substituiert sind und/oder Heteroatome (anstelle von C-Atomen; vorzugsweise ausgewählt aus O, N, wie NH oder N-Alkyl, und S) aufweisen, mit der Maßgabe, dass mindestens einer der Reste R¹ und R² Wasserstoff bedeutet, oder
  • (ii) offenkettige Verbindungen, worin das die Brücke bildende Glied -C(=Z³)- fehlt,
    • -A- für -C(R¹)(R²)- steht, X und Y unabhängig voneinander für eine jeweils unverzweigte oder verzweigte, unsubstituierte oder substituierte, gegebenenfalls Heteroatome (anstelle von C-Atomen; insbesondere ausgewählt aus O, N, wie NH oder N-Alkyl, und S) aufweisende C₁-C₄-Alkylgruppe oder C₁-C₄-Alkoxygruppe oder vorzugsweise für eine jeweils unsubstituierte oder substituierte, gegebenenfalls Heteroatome (anstelle von C-Atomen; insbesondere ausgewählt aus O, N, wie NH oder N-Alkyl, und S) aufweisende C_1-C₄-Alkoxycarbonylmethylgruppe oder C_1-C₄-Alkylcarbonylmethylgruppe stehen,
    • R¹ und R² beide Wasserstoff bedeuten und
    • Z¹ und Z² die genannten Bedeutungen haben;
    • oder X für eine jeweils unverzweigte oder verzweigte, unsubstituierte oder substituierte, gegebenenfalls Heteroatome (anstelle von C-Atomen; insbesondere ausgewählt aus O, N, wie NH oder N-Alkyl, und S) aufweisende C₁-C₄-Alkylgruppe oder C₁-C₄-Alkoxygruppe oder C_1-C₄-Alkoxycarbonylmethylgruppe oder C₁-C₄-Alkylcarbonylmethylgruppe steht,
    • Y und Z² gemeinsam mit dem bindenden Kohlenstoffatom -CN bedeuten,
    • Z¹ die oben genannten Bedeutungen hat, und
• R¹ und R² jeweils wie oben definiert sind mit der Maßgabe, dass mindestens einer der Reste Wasserstoff bedeutet; und/oder Salze davon.

Alternatively, a hardener system containing the following components can be used to harden the synthetic resin fastening systems according to the invention:

• a) at least one activator in the form of a metal salt and
• b) as radical chain initiator at least one CH-acidic compound, in particular of formula A,
  
  wherein
  • (i)
    • -A- stands for -C(R ¹ )(R ² )-
    • -X- stands for a bond, for -NR ³ - or for -(CR ⁴ R ⁵ ) _p -, or for -O-,
    • Y stands for NR ⁶ or for (CR ⁷ R ⁸ ) _q , or for O,
    • where if X stands for O then Y also stands for O;
    • where preferably X is (CR ⁴ R ⁵ ) _p and Y is CR ⁷ R ⁸ ,
    • or X is NR ³ and Y is NR ⁶ ;
    • Z ¹ stands for O, S, S=O or S(=O) ₂ ,
    • Z ² stands for O, S, S=O or S(=O) ₂ ,
    • Z ³ stands for O, S, S=O or S(=O) ₂ or for R9 and R10,
    • p stands for 1, 2 or 3, preferably 1 or 2
    • q is 1, 2 or 3, preferably 1;
    and the radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ R ⁸ , R ⁹ and R ¹⁰ independently of one another represent hydrogen, alkyl, aryl, aralkyl, cycloalkyl or cycloalkylalkyl and are each unsubstituted or substituted and/or have heteroatoms (instead of C atoms; preferably selected from O, N, such as NH or N-alkyl, and S), with the proviso that at least one of the radicals R ¹ and R ² is hydrogen, or
  • (ii) open-chain compounds in which the bridging link -C(=Z ³ )- is missing,
    • -A- stands for -C(R ¹ )(R ² )-, X and Y independently of one another stand for a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group, which is in each case unbranched or branched, unsubstituted or substituted, optionally containing heteroatoms (instead of C atoms; in particular selected from O, N, such as NH or N-alkyl, and S), or preferably for a C _1- C ₄ alkoxycarbonylmethyl group or a C _1- C 4 alkylcarbonylmethyl group, which is in each case unsubstituted or substituted, optionally containing heteroatoms (instead of C atoms; in particular selected from O, N, such as NH or _N -alkyl, and S),
    • R ¹ and R ² both represent hydrogen and
    • Z ¹ and Z ² have the meanings given above;
    • or X represents a C ₁ -C ₄ alkyl group or C 1 -C 4 alkoxy group or C ₁ -C ₄ alkoxycarbonylmethyl group or C ₁ -C ₄ alkylcarbonylmethyl group, each of _which is unbranched or branched, unsubstituted or substituted and optionally contains heteroatoms (instead of C atoms _; in particular selected from O, N, such as NH or N-alkyl, and S),
    • Y and Z ² together with the bonding carbon atom represent -CN,
    • Z ¹ has the meanings given above, and
• R ¹ and R ² are each as defined above with the proviso that at least one of the radicals is hydrogen; and/or salts thereof.

Preferred examples of such compounds are 2,4,6-pyrimidinetrione derivatives are barbituric acid (2,4,6-pyrimidinetrione) itself, 1-benzyl-5-phenylbarbituric acid (1-(phenylmethyl)-5-phenyl-2,4,6-pyrimidinetrione), 5-butylbarbituric acid (5-butyl-2,4,6-pyrimidinetrione), 1-cyclohexyl-5-ethylbarbituric acid (1-cyclohexyl-5-ethyl-2,4,6-pyrimidinetron) or 2-thiobarbituric acid (4,6-dihydroxy-2-mercaptopyrimidine), 1,3-cyclohexanedione, 2-methyl-1,3-cyclohexanedione, 1,3-cyclopentanedione, 2-methyl-1,3-cyclopentanedione, 4,4-dimethyl-1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione (dimedone), 2,2-dimethyl-1,3-dioxane-4,6-dione or 2,2,5-trimethyl-1,3-dioxane-4,6-dione, 3-oxoglutaric acid dimethyl ester, and/or diethyl 1,3-acetonedicarboxylate, ethyl cyanoacetate, methyl cyanoacetate or 2-ethylhexyl cyanoacetate, or in the DE 10 2011 078 785 1,3-dioxo compounds. Here we refer to the WO 2015/154861 A1 which is incorporated by reference in this regard.

The DE 10 2011078785 discloses hardener components with CH-azide compounds of other structural formulas, which can also be used as hardener systems.

WO 2016/206777 A1 shows the use of imines, especially aldimines or ketimines, and their precursors (aldehydes or ketones and amines) as initiators in hardener systems for radical polymerization and corresponding synthetic resin fastening systems. Here too, at least one activator in the form of a metal salt is used. These are also suitable as hardener systems for synthetic resin fastening systems according to the invention - aldimine and/or ketimine-based systems are particularly preferred as hardeners.

The primary amines added as such or suitable for the synthesis of the imines include, for example, mono-, di- or polyamines, or mixtures of two or more thereof. The molecular framework of the mono- and/or di- and/or polyamines can contain aliphatic, heteroaliphatic, alicyclic, heterocyclic, aromatic, aliphatic-aromatic and silane/siloxane molecular structures or two or more independently selected ones thereof. Primary and/or secondary and tertiary amino groups can be present in the molecule, but at least one primary amino group (-NH ₂ ) must be present to form an aldimine or ketimine.

The mono-, di- or polyamines are preferably from the group of alkyl or alkylene(mono or di)amines (such as 2-methylpentanediamine, or 2,2,4- or 2,4,4-trimethylhexamethylenediamine), heteroalkyl or heteroalkylene(mono or di)amines (such as 1,13-diamino-4,7,10-trioxatridecane, commercially available amine-functionalized polyoxyalkylenes [Jeffamines] from Huntsman Corp, such as in particular Jeffamine ED600, or e.g. triethylenetetramine and/or higher homologues), cycloalkyl or cycloalkylene(mono or di)amines (such as isophoronediamine, 1,3-bisaminomethylcyclohexane, TCD-diamine), heterocycloalkyl or heterocycloalkylene(mono or di)amines (such as Aminoethylpiperazine), aminols or amino alcohols (such as 1,3-diaminopropan-2-ol), and aliphatic-aromatic (mono or di)amines (such as 1,3- or 1,4-benzenedimethanamine), and/or from the group of aminosilanized fillers.

Also preferred are the mono-, di- or polyamines from the group of aminoamides, polyaminoamides, Mannich bases and amine adducts (epoxide-amine adducts such as in EP 0 387 418 A2 described, isocyanate-amine adducts [for example from unreacted amino groups from imine synthesis or from the above-mentioned aminols - when using the aminols, the conversion to the imine preferably takes place first and then the addition to the isocyanate], Bucherer adducts and Michael addition adducts) and aminoalkylsilanes which contain at least one hydrolysable group, such as alkoxy, e.g. methoxy or ethoxy - bonded to the silicon.

worin:

• R₂, R₃ unabhängig voneinander Wasserstoff und/oder einen unsubstituierten oder
• substituierten und/oder einen gegebenenfalls Doppelbindungen und/oder Heteroatome aufweisenden ein- oder mehrfach verzweigten oder geradkettigen organischen Rest,
• welcher aliphatische, heteroaliphatische, alicyclische, heterocyclische Molekülstrukturen und/oder Kombinationen aus den vorgenannten Molekülstrukturen umfassen kann, bedeutet.

The aldehydes and ketones added as such or used or suitable for the synthesis of the aldimines and/or ketimines are in particular those of the formula (III):

wherein:

• R ₂ , R ₃ independently of one another are hydrogen and/or an unsubstituted or
• substituted and/or optionally containing double bonds and/or heteroatoms, singly or multiply branched or straight-chain organic radical,
• which may comprise aliphatic, heteroaliphatic, alicyclic, heterocyclic molecular structures and/or combinations of the aforementioned molecular structures.

The aldehydes and/or ketones are preferably compounds which have at least one or more (primary and/or secondary) hydrogen atoms on the α-carbon atom adjacent to the carbonyl group. Examples of such aldehydes are propanal, valeraldehyde, isovaleraldehyde, or methoxyacetaldehyde, or 3,7-dimethyl-6-octenal (citronellal) or 3,7-dimethyl-7-hydroxyoctanal (hydroxycitronellal). Examples of such ketones include methyl isobutyl ketone, acetone, or methyl ethyl ketone or 6-methyl-5-hepten-2-one.

The aldehydes and/or ketones are particularly preferably compounds which have a double bond and/or branching on the α-carbon atom adjacent to the carbonyl group. As a result, the particularly preferred aldehydes and/or ketones only have one (tertiary) hydrogen atom on the α-carbon atom adjacent to the carbonyl group. Examples of particularly preferred aldehydes are isobutyraldehyde, 2-ethylhexanal, 2-methylbutanal, 2-ethylbutanal, 2-methylvaleraldehyde, 2,3-dimethylvaleraldehyde, cyclohexylcarboxaldehyde, or 3,7-dimethyl-2,6-octadienal (citral), 3-(4-tert-butylphenyl)-2-methylpropanal (Lilial, Lysmeral), tetrahydrofuran-3-carboxaldehyde, tetrahydro-2-furancarboxaldehyde, 4-formyltetrahydropyran, tetrahydro-2H-pyran-2-carbaldehyde or tetrahydro-pyran-3-carbaldehyde. As Particularly preferred ketones are, for example, diisopropyl ketone, 3-methyl-2-pentanone, 2-methylcyclohexanone or ß-ionone, or preferably isobutyraldehyde.

DE 10 2015 118 136 A1 shows hardener systems that contain one or more catalytically active bases and carbonyl compounds. These are also suitable as hardener systems for synthetic resin fastening systems according to the invention.

Regardless of the type of hardener, the following applies: The proportion of hardener in a synthetic resin fastening system according to the invention is preferably in a range of 1 to 80%, e.g. 2 to 70%. In particular embodiments, the peroxide content is < 1% based on the hardener; in a further possibility, the peroxide content is < 1% based on all components, preferably 0% when using a different hardener with alternative initiators and activators in the form of metal salts as mentioned above and optionally below.

The activators used in the form of a metal salt, which also includes metal complexes and metal oxides, are preferably one or more metal salts, in particular of organic and/or inorganic acids with metals, e.g. selected from copper, iron, vanadium, manganese, cerium, cobalt, zirconium, or bismuth, or mixtures of two or more thereof. Preference is given to metal salts selected from the group consisting of vanadium, iron, manganese and copper, in particular in the form of salts or complexes with inorganic acid residues, such as sulfate and/or carbonate residues and/or organic acid residues, for example carboxylate residues - the organic acids preferably being saturated - such as carboxylates with CH ₃ , C ₂ -C ₂₀ alkyl, a C ₆ -C ₂₄ aryl residue or C ₇ -C ₃₀ aralkyl residue, for example octoate, eg 2-ethylhexanoate (isooctanoate), neodecanoate, or acetylacetonate. Particularly preferred are manganese carboxylates, such as Mn acetate or Mn octoate, copper carboxylates, such as copper octoate, copper neodecanoate or copper naphthenate, copper quinolates, iron carboxylates, such as iron octoate and/or vanadium carboxylates and/or the group of metal salts with inorganic acids, which includes, for example, iron chloride, iron sulfate, copper sulfate and copper chloride. Where copper is mentioned, it is preferably copper(II) salts.

Additives for a hardener component to be used or contained according to the invention are, in addition to the initiator(s) and/or hardener system(s) (in particular with radical formers and activators) as described above, selected from fillers as mentioned above, drying agents (e.g. zeolite), plasticizers or phlegmatizers, such as phthalic acid, sebacic acid esters, ethylene glycol dibenzoate or ethylene glycol dibenzoate, stabilizers (in particular as mentioned above), rheology aids, such as pyrogenic silica gel as such or in hydrophobized form, pigments or dyes, and also non-reactive diluents and wetting agents; or mixtures of two or more of the substances mentioned. Such additives can preferably be added in total weight proportions of 0 to 90%, for example from 0.1 to 40%.

In a particular and advantageous embodiment of the invention, the curable components (synthetic resin component comprising reactive resin and the associated hardener component) of a synthetic resin fastening system according to the invention are stored separately from one another in a two- or multi-component system or kit before they are mixed together at the desired location (e.g. at or in a hole or gap, such as a drill hole) when they are used.

A multi-component two- or further multi-component system is to be understood in particular as a two- or (further) multi-component kit (preferably a two-component kit) comprising one (or in the case of the two-component system consisting of one) component (A), which contains one or more reactive resins, as described above and below, and the respective associated hardener as component (B) as defined above and below, wherein further additives can be provided in one or both of the components, preferably a two- or further multi-chamber device, in which the mutually reactive components (A) and (B) and optionally further separate components are contained in such a way that their components do not come into contact with one another during storage before use, but which makes it possible to mix the components (A) and (B) and optionally further components for fastening at the desired location, for example directly in front of or in a hole, and if necessary to introduce them so that the curing reaction can take place there. Cartridges are also suitable, for example cartridges nested inside one another, such as ampoules; and in particular multi- or in particular two-component cartridges (which are also particularly preferred), in the chambers of which the several or preferably two components (in particular (A) and (B)) of the synthetic resin fastening system according to the invention with the compositions mentioned above and below for storage before use, whereby a static mixer is preferably also included in the corresponding kit. The chambers of the multi-component or, in particular, two-component cartridges can be made purely from plastic or as foil bags (in particular, multi-layer foil bags).

Plastics can be used as the material for a film bag that can be used according to the invention, such as compostable plastics, e.g. based on starch, polyester, polyester amides, polyurethanes, polyvinyl alcohols, cellulose, lignocellulose, polylactic acid, polyhydroxyalkanoates, or mixtures of two or more such materials. Preference is given to water-, moisture- and water vapor-tight materials, in particular those that are metallized (e.g. by vapor deposition) and/or are composite films made of a plastic and a metal, in particular aluminum, film.

When using a synthetic resin fastening system according to the invention for fastening anchoring means to holes (in particular drill holes) or recesses in (building) substrates, such as masonry or concrete or wood, the use is particularly in the form of a multi-component, in particular two-component kit, whereby the reactive components can only come into contact with one another and react at the place of use and can thus serve, for example, to fix the anchoring elements in the said holes or recesses.

Also corresponding processes or methods, in particular for fastening anchoring elements (anchoring means) in holes or gaps, in which a one- or multi-component synthetic resin fastening system according to the invention is used for mortaring (gluing in) anchoring means, wherein the components of the synthetic resin fastening system and an anchoring means (= anchoring element) are introduced one after the other, in particular first the components of the synthetic resin fastening system, then the anchoring means, or (at least substantially) simultaneously, into a hole or gap in a substrate (also in a cracked substrate, such as in cracked concrete), or mixed forms of these two variants with partial introduction in each case, form an embodiment of the invention.

The following examples illustrate the invention without limiting its scope.

The determination methods for determining parameters are also valid for the general part of the description:

Pull-out tests from concrete / Determination of load values

• Zur Bestimmung der Lastwerte der ausgehärteten Massen verwendet man eine Gewindestange M12, die in ein Bohrloch in Beton mit einem Durchmesser von 14 mm und einer Bohrlochtiefe von 84 mm mit dem erfindungsgemäßen Kunstharz-Befestigungssystem eingedübelt wird. Man ermittelt die mittlere Versagenslast durch zentrisches Ausziehen der Gewindestange mit enger Abstützung unter Verwendung hochfester Gewindestangen. Es werden jeweils 5 Gewindestangen eingedübelt und nach 24 Stunden Aushärtung bei Raumtemperatur ihre Lastwerte bestimmt. Die Lastwerte wurden zum einen unter Referenzbedingungen (trockenes, gereinigtes Bohrloch (R1) (Ausblasen mit Handausbläser (2x), Bürsten mit Drahtbürste (2x), Ausblasen mit Handausbläser (2x)) und zum anderen in einem feuchten und halbgereinigten Bohrloch (B7) (Ausblasen mit Handausbläser (1x), Bürsten mit Drahtbürste (1x), Ausblasen mit Handausbläser (1x)) bestimmt. Bei den hierbei ermittelten Lastwerten handelt es sich um den Mittelwert der 5 Einzelmessungen.

For pull-out tests with M12 threaded rods and to determine the load values of the synthetic resin fastening systems according to the invention and the references, the following procedure is followed, according to EAD330499-02-0601:

• To determine the load values of the hardened masses, an M12 threaded rod is used, which is anchored into a drill hole in concrete with a diameter of 14 mm and a drill hole depth of 84 mm using the synthetic resin fastening system according to the invention. The average failure load is determined by centrally pulling out the threaded rod with close support using high-strength threaded rods. 5 threaded rods are anchored in each case and their load values are determined after 24 hours of hardening at room temperature. The load values were determined under reference conditions (dry, cleaned borehole (R1) (blowing out with hand blower (2x), brushing with wire brush (2x), blowing out with hand blower (2x)) and in a wet and semi-cleaned borehole (B7) (blowing out with hand blower (1x), brushing with wire brush (1x), blowing out with hand blower (1x)). The load values determined here are the mean of the 5 individual measurements.

The following Table 1 explains the abbreviations and terms used in the examples: Table 1: Explanations of the abbreviations used abbreviation / term Explanation E2BADMA Ethoxylated bisphenol A dimethacrylate (technical product: various degrees of ethoxylation possible) PEG200DMA Polyethylene glycol 200 dimethacrylate (average n ≈ 4, technical product: various ethylene glycol repeat units possible) BDDMA 1,4-butanediodimethacrylate DPGDMA dipropylene glycol dimethacrylate EP150DMA Bisomer EP150DMA (GEO Specialty Chemicals) MEMO 3-Methacryloxypropyltrimethoxysilane BDC8 Borchers Deca Copper 8 (copper2+neodecanoate; active content: 7.8 - 8.2%, Borchers GmbH 6HS Calcilit 6HS (hydrophobic calcium carbonate; Alpha Calcite) KS hydrophob pyrogenic surface-treated silica Aldimine Aldimine from Jeffamine ED600 and isobutyraldehyde TDMAP 2,4,6-Tris-(dimethylaminomethyl)-phenol (technical product: various degrees of alkylation in the form of “dimethylaminomethyl” possible) KS hydrophil fumed silica characteristic bond stress corresponds to the 5% fractile: statistically determined value design composite stress Design value of resistance for failure in case of pull-out under tensile load EAD European Assessment Document

Example 1: Formulation compositions of the reference and the inventive synthetic resin fastening systems with inventive propylene glycol dimethacrylates and block alkylene glycol di(meth)acrylates and their extraction values

A fischer 10:1 cartridge is filled with the following components from Table 2: Table 2: Components of the mortar and hardener compositions component / part Reference hydrophilic [%] Reference hydrophobic [%] According to the invention Dipropylene glycol dimethacrylate [%] According to the invention block alkylene glycol di(meth)acrylate [%] Comp. A (10 parts by volume) E2BADMA 25.0 25.0 25.0 25.0 PEG200DMA 5.0 - - - BDDMA - 5.0 - - DPGDMA - - 5.0 - EP150DMA - - - 5.0 MEMO 5.0 5.0 5.0 5.0 BDC8 0.6 0.6 0.6 0.6 Inhibitor* ¹ 0.2 0.2 0.2 0.2 quartz powder 22.4 22.4 22.4 22.4 quartz sand 30.0 30.0 30.0 30.0 6HS 10.0 10.0 10.0 10.0 KS hydrophob 1.8 1.8 1.8 1.8 Density [g/mL] 1.77 1.76 1.75 1.78 Viscosity [Pas] 180 160 160 166 Comp. B (1 volume part) hardener composition [%] Aldimine 51.3 Color 0.8 quartz powder 45.2 rheology additive* ² 0.1 KS hydrophil 2.6 Density [g/mL] 1.45 Viscosity [Pas] 180
* ¹ Inhibitor: Combination (50/50) of TEMPOL (1% in PEG200DMA) and TDMAP (50% in PEG200DMA)
* ² “Thixboosters” can be used as rheology additives, which enhance the rheological properties in combination with hydrophilic silica; for example from Byk, such as Byk P2720 or Byk R605.

Both the reference examples and the examples according to the invention were subjected to a robustness test as described under "Concrete pull-out tests / Determination of load values". Table 3 below shows the bond stresses determined and the corresponding quotient of B7 and R1.

Table 3: Determined characteristic values for robustness testing of the reactive diluents according to the invention and the references EAD parameters reference hydrophil reference hydrophobic According to the invention propylene glycol dimethacrylate According to the invention block alkylene glycol di(meth)acrylate R1 23.5 19.4 20.3 20.5 B7 16.5 15.8 18.4 19.8 quotient B7/R1 0.70 0.81 0.91 0.97 robustness factor α* 1.4 1.2 1.0 1.0 *results from the EAD

Table 3 shows that synthetic resin fastening systems with the reactive diluents according to the invention consisting of propylene glycol di(meth)acrylates and/or block alkylene glycol di(meth)acrylates produce significantly more robust systems with a significantly higher B7/R1 ratio in the robustness test. According to EAD330499-02-0601 Table 2.2.5.6.1, this results in significantly lower reduction factors, which increases the overall performance or the bond stress that can be used for the actual design. The following example 2 is intended to illustrate this again.

Example 2: Example results to illustrate the influence of mitigation factors resulting from the robustness test

Table 4 shows typical parameters as given in European technical assessments. For simplicity, the reduction factor is derived from the robustness factor here. Table 4: typical parameters of European technical assessments reference According to the invention characteristic bond stress [N/mm2] 12.0 10.0 reduction factor (from the robustness test) 1.4 1.0 design bond stress (characteristic bond stress / robustness factor) 8.6 10.0

Example 2 is intended to illustrate that "robust" synthetic resin fastening systems, which have a consistently balanced performance, are advantageous for the actual design bond stress. The reason for this is that the consistently balanced performance, which is determined in the robustness test, for example, leads to lower reduction factors. Example 2 shows that the synthetic resin fastening system according to the invention with balanced performance (and thus lower reduction factors) offers a higher design bond stress despite a lower characteristic bond stress than the reference. This resistance to external influences, such as those that can occur under construction site conditions, must be strengthened in order to be able to give the end user a robust and reliable product.

QUOTES INCLUDED IN THE DESCRIPTION

This list of documents listed by the applicant was 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 accepts no liability for any errors or omissions.

Cited patent literature

• DE 102010013196 A1 [0003, 0005]
• EP 3 851 423 A1 [0004, 0005, 0007]
• EP 0508183 A1 [0041]
• EP 0432087 A1 [0041]
• WO 2019/197190 A1 [0041]
• DE 199 56 509 [0049]
• WO 2016/000807 A1 [0056]
• EP 4 056 607 [0056]
• DE 10 2009 059210 [0057]
• WO 2015/090523 A1 [0060]
• DE 10 2011 078 785 [0063, 0064]
• WO 2015/154861 A1 [0063]
• WO 2016/206777 A1 [0065]
• EP 0 387 418 A2 [0068]
• DE 10 2015 118 136 A1 [0072]

Cited non-patent literature

• Polyurethane, Plastics Handbook”, Chapter 3.4.8 Anti-aging agents, p. 121, 3rd edition, 1993, edited by Gerhard W. Becker and Dietrich Braun, Carl Hanser Verlag Munich Vienna [0049]

Claims (20)

A radically curable synthetic resin fastening system which comprises one or more reactive diluents which are characterized by the presence of one or more propylene glycol or propylene oxide repeat units which have at least one reactive (meth)acrylate group directly or indirectly at the ends and which are selected from the group consisting of propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, and also tripropylene glycol di(meth)acrylate; furthermore tetrapropylene glycol di(meth)acrylate and block alkylene glycol di(meth)acrylates of the formula CYXYC in the form of ethoxylated propylene glycols terminally esterified with (meth)acrylate in a central propylene oxide block (X) with 5 or more (preferably up to 20) linearly arranged 1,2-propylene oxide units, which is extended at both ends with two or more ethylene oxide units (Y), independently of one another, each of which carries a (meth)acryloyl group (C) at both ends, or furthermore mixtures of two or more of the reactive diluents mentioned. A radically curable synthetic resin fixing system according to claim 1 , characterized in that the reactive diluent is selected from dipropylene glycol di(meth)acrylate and further tripropylene glycol di(meth)acrylate, and further a mixture thereof. A radically curable synthetic resin fixing system according to claim 1 , wherein the reactive diluent is a block alkylene glycol di(meth)acrylate of the formula CXYXC in the form of ethoxylated propylene glycol terminally esterified with (meth)acrylate with a central propylene oxide block (X) having 6 to 15 linearly arranged 1,2-propylene oxide units, which is extended at both ends by two to 4 ethylene oxide units (Y), each of which carries a (meth)acryloyl group (C) at both ends. A radically curable synthetic resin fixing system according to one of the Claims 1 until 3 , where the groups (C) are methacrylate groups. A radically curable synthetic resin fixing system according to one of the Claims 1 until 4 , characterized in that it contains only one (1) of the reactive diluents according to the invention mentioned therein and preferably no further reactive diluent, A radically curable synthetic resin fixing system according to one of the Claims 1 until 5 , in multi-component, in particular two-component form, which contains the reactive diluent(s) in a radically curable reactive resin component (A) and contains a hardener component (B), in particular in the form of a two-component kit. A radically curable synthetic resin fixing system according to one of the Claims 1 until 6 , for improving the performance in poorly cleaned and/or damp boreholes in mineral substrates, characterized in that it has the highest possible quotient B7/R1 from the determined bond stress in the damp and poorly cleaned borehole B7 to the bond stress in the dry, well-cleaned borehole R1, in particular a quotient B7/R1 of ≥ 0.80, preferably ≥ 0.89, where B7/R1 is determinable or preferably determined according to EAD330499-02-0601 Edition 04/2023 (EAD). A radically curable synthetic resin fixing system according to one of the Claims 1 until 7 , characterized in that in addition to the reactive diluent(s) mentioned in the respective claim, at least one adhesion promoter in the form of a silane and/or siloxane is contained. A radically curable synthetic resin fixing system according to one of the Claims 1 until 8 , wherein the reactive diluent(s) mentioned in the respective claim is/are contained in a mass fraction in the range from 0.1 to 50%, in particular from 0.5 to 40%, particularly preferably from 1 to 25%. A radically curable synthetic resin fixing system according to one of the Claims 1 until 8 wherein, based on the reactive resin component (A) and thereof only the reactive resin content and the mass of the reactive diluent, the mass fraction is in the range from 0.5 to 60%, preferably 1 to 50%, in particular from 2 to 30%. A radically curable synthetic resin fixing system according to one of the Claims 1 until 10 , which contains as reactive resin in the reactive resin component one or more epoxy(meth)acrylates, in particular of the formula (I) as shown below; more preferably one or more urethane(meth)acrylates, or in particular which contains one or more alkoxylated, aromatic (meth)acrylates, in particular one or more propoxylated or in particular ethoxylated aromatic diols, such as bisphenol A, bisphenol F or novolak (in particular di-)(meth)acrylates, preferably those of the formula (II); the formulas being defined as follows:

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 for n are also possible as the average value;

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, wherein, when 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 average value, and wherein in the case of the propoxylated compounds, instead of the group [-O-CH ₂ -CH ₂ ] _a, a number "a" of unbranched or preferably branched oxypropylene groups is present. A radically curable synthetic resin fixing system according to one of the Claims 1 until 10 , comprising a hardener component (B) which contains one or more radical-forming peroxides, azides, azo compounds, tetraazenes, halogen-containing initiators typical for ATRP, or a radically curing hardener system which contains at least one activator in the form of a metal salt and a radical chain initiator selected from compounds containing thiol and/or thiolester groups, a CH-acidic compound, one or more aldimines, ketimines, precursors of aldimines and/or ketimines in the form of amines and aldehydes and/or ketones; and/or aldehydes and ketones, catalytically active bases and carbonyl compounds or radically polymerizable compounds; with one or more aldimines and/or ketimines being particularly preferred. A radically curable synthetic resin fixing system according to one of the Claims 1 until 12 which contains one or more other conventional additives, in particular a filler, and preferably an adhesion promoter. A radically curable synthetic resin fixing system according to one of the Claims 1 until 13 which contains one or more further reactive thinners in addition to the reactive resin thinner(s). A radically curable synthetic resin fixing system according to one of the Claims 1 until 14 with a reactive resin component (A) and a hardener component (B), in which the volume ratio of components A:B is (3-20):1, in particular (5-12):1, preferably 10:1. Reactive resin component for a radically curable synthetic resin fixing system according to claim 5 which contains only one (1) of the reactive diluents defined therein, or according to one of the Claims 1 until 4 or 6 until 15 which contains one or more reactive diluents as defined in any one of the preceding claims and a radically curable reactive resin. Use of a radically curable synthetic resin fixing system as in one of the Claims 1 until 15 as an adhesive in fastening technology, in particular for fastening anchoring elements in drill holes or gaps, in particular in a building substrate; in particular for fastening anchoring elements in semi-cleaned and/or moist drill holes in a building substrate, in particular masonry or concrete. Use of a reactive thinner such as for a radically curable synthetic resin fixing system in one of the Claims 1 until 4 defined to increase the robustness of a radically curable synthetic resin fastening system, defined as a small difference in the value for the bond stress in the wet and poorly cleaned borehole B7 compared to the bond stress in the dry, well-cleaned borehole R1, preferably with the highest possible ratio of B7/R1 of ≥ 0.80, in particular a quotient B7/R1 of 0.90 to 1.00, where B7/R1 is determinable or preferably determined according to EAD330499-02-0601 Edition 04/2023 (EAD) Process for producing a radically curable synthetic resin fastening system according to one of the Claims 1 until 15 , characterized in that the remaining components, in particular a reactive resin component in a multi-component system, are admixed with reactive diluents as in one of the Claims 1 until 15 be mixed in a defined manner and, in particular, in the case of multi-component systems in separate compartments, be filled into packaging. Method for fixing anchoring means in boreholes or cracks using a method specified in one of the Claims 1 until 15 defined radically curable synthetic resin fixing system which contains at least one of the radically curable reactive diluents mentioned therein.