DE102015118134A1 - Aldimines and ketimines as initiators in hardener systems and corresponding resin compositions, among others for fastening technology - Google Patents

Abstract

A hardener system for a synthetic resin composition comprising free-radically polymerizable compounds which comprises the following constituents: a) at least one activator in the form of a metal salt and as radical initiator b1) (i) at least one aldehyde and / or ketone and at least one primary amine, and / or b2) (ii) at least one aldimine or (iii) at least one ketimine, or a mixture of two or more of components (i) to (iii), and resin compositions having such a hardener system for use primarily in fastening technology, and related art subjects of the invention.

Description

The invention relates to a hardener system comprising (i) at least one aldehyde and / or ketone and at least one primary amine, (ii) at least one aldimine or (iii) at least one ketimine, or a mixture of two or more of components (i) to (iii) and at least one activator (accelerator) in the form of a metal salt as an initiator system for a radically polymerizable compound-containing resin composition, preferably suitable or adapted for use or for methods in chemical fastening technology; a synthetic resin composition containing such a hardener system, the use of the hardener system or the synthetic resin composition, in particular in the attachment area, and related further subject matter of the invention, such as methods, methods and uses.

Synthetic resin compositions based on free-radically polymerizable (curable) compounds, such as unsaturated polyester resins and vinyl ester resins, are known as adhesives and adhesives. Often, these are two-component systems in which the resin mixture and the curing agent are contained in separate components. In order to cure such (especially at ambient temperature curable) resin compositions, so-called radical initiators (initiators) are needed. Due to their properties, two initiator systems have become established in chemical fastening technology. The DE 3 226 602 A1 describes an initiator system comprising benzoyl peroxide as an initiator and an amine compound as an accelerator. The EP 1 586 569 A1 suggests, on the other hand, one based on a perester as a radical initiator and a metal compound as an activator.

However, a disadvantage of these known initiator systems is the use of peroxides as radical initiators. These are thermally sensitive and sensitive to contamination, resulting in significant limitations in the formulation of pasty curing agent compositions in terms of storage temperature, storage stabilities and the selection of suitable ingredients. To stabilize peroxides, phlegmatizers, such as phthalates or water, are added. Acting as a plasticizer, these significantly affect the mechanical strength of the resin compositions.

Also for ecological reasons and because peroxides must be labeled as sensitizing in many countries above a certain concentration (for example with dibenzoyl peroxide from 1%), it is desirable to avoid such initiators. The same applies to Aminic accelerators, some of which are also subject to labeling.

Aldimines or ketimines (hereinafter also referred to collectively as imines, which means "ketimine or preferably aldimine") are condensation products of primary amines and aldehydes or ketones. Upon contact with water, such imines can hydrolyze to the corresponding amines and aldehydes or ketones. Therefore, they can be used as a protected form of amines, or of aldehydes or ketones. Thus aldimines are often used in polyurethane chemistry or epoxy chemistry, where they serve as moisture activatable crosslinkers ("blocked amines" or "latent hardeners") for isocyanate groups or epoxy groups having compositions and thus effect a curing according to the principle of polyaddition. Examples of such applications can be found in EP 1 329 469 A1 . EP 1 975 190 A1 and EP 2 017 260 ,

Imines in radically curable synthetic resin compositions are used in US 4,348,506 mentioned. Here, vinyl ester resins are cured with peroxides, especially ketone peroxide, as initiator and a) with a cobalt-aldimine complex and / or b) with a cobalt naphthenate and an equivalent amount of aldimine as accelerator. An "active" use of imines as actual radical starter (without peroxides) - in combination with metal activators - for radical polymerizations is not mentioned here and not yet known.

The EP 2 824 117 A1 describes the use of copper (II) salts and nitrogen-containing ligands as a peroxide-free initiator system for radically polymerizable compounds. The nitrogen-containing ligands are preferably tertiary aliphatic amines having readily removable hydrogen atoms on the α-carbon atom to the nitrogen. As examples, the EP 2 824 117 A1 including N, N, N`, N``, N``-pentamethyldiethylenetriamine (PMDETA) and its higher and lower homologues. A disadvantage of reaction resin compositions according to EP 2 824 117 A1 is that they only allow low strength or bond stresses and sometimes have questionable markings (PMDETA is marked with a skull).

Thus, the object was to provide new hardener or resin compositions which overcome the disadvantages described in the prior art, but where available its advantages (eg, low-temperature curing, robustness of the mixing ratios between resin and hardener) maintain or exceed and optionally have other advantages; and allow suitable strengths and usability for the purposes mentioned above, without relying on peroxides as initiators.

It has now surprisingly been found that (i) aldehydes and / or ketones can be used together with primary amines, (ii) aldimines and (iii) ketimines in combination with metal salts as initiator systems for free-radically polymerizable (curable) compounds containing resin compositions.

Furthermore, it has been found that the imines which can be used according to the invention, which - in contrast to the nitrogen-containing ligands of the EP 2 824 117 A1 - Contain a sp ² -hybridized nitrogen, lead to particularly powerful hardener systems. This manifests itself not only in the improved strengths or bond stresses, but also in a wider range of possible metal salts for use as accelerators, which is not limited to copper only.

• a) mindestens einen Aktivator in Form eines Metallsalzes und als Radikalstarter
• b1) mindestens ein Aldehyd und/oder Keton und mindestens ein primäres Amin, und/oder
• b2) mindestens ein Imin, welches ein oder mehrere Imin-Strukturinkremente der Formel (I) beinhaltet:
  
  worin unabhängig voneinander: die gewellte Linie den organischen Rest des (jeweils) verwendeten Amins darstellt, oder für Wasserstoff steht; und R₂ und R₃ unabhängig voneinander Wasserstoff und/oder einen unsubstituierten oder substituierten, gegebenenfalls Doppelbindungen und/oder Heteroatome aufweisenden, ein- oder mehrfach verzweigten oder geradkettigen organischen Rest, welcher mindestens eine aliphatische, heteroaliphatische, alicyclische oder heterocyclische Molekülstruktur, oder eine Kombination von zwei oder mehr der vorgenannten Molekülstrukturen beinhaltet, bedeutet; und/oder Salze davon.

Against this background, in a first embodiment of the invention, the invention relates to a hardener system for a synthetic resin composition with radically polymerizable compounds, which comprises the following constituents:

• a) at least one activator in the form of a metal salt and as a radical initiator
• b1) at least one aldehyde and / or ketone and at least one primary amine, and / or
• b2) at least one imine which contains one or more imine structural units of the formula (I):
  
  wherein, independently of one another, the corrugated line represents the organic radical of the (respectively) used amine, or represents hydrogen; and R ₂ and R ₃ independently of one another are hydrogen and / or an unsubstituted or substituted, optionally double bonds and / or heteroatoms, mono- or polysubstituted or straight-chain organic radical which has at least one aliphatic, heteroaliphatic, alicyclic or heterocyclic molecular structure, or a combination of two or more of the aforementioned molecular structures, means; and / or salts thereof.

Preferably, the molecular weight of the imine structural units of the formula I-containing imines is 2000 daltons (g / mol) or lower, for example 1000 daltons or lower. The aldehydes and / or ketones each preferably have molecular weights in these ranges.

Said hardener system can be present as a finished hardener composition (for example with microencapsulated components a) and b)) or preferably only when mixed with further constituents of a synthetic resin composition (as a kind of composition (mixture)), for example when used.

• c) mindestens eine radikalisch polymerisierbare Verbindung

beinhaltet. A further and particularly noteworthy embodiment of the invention relates to the use of such a hardener system as an initiator system for a resin composition containing a free-radically polymerizable compound which is further included as constituent

• c) at least one free-radically polymerizable compound

includes.

The synthetic resin composition containing free-radically polymerizable compounds is used in particular as an adhesive, coating material or molding compound, in particular for fixing anchoring agents in substrates, such as masonry or concrete, or for fastening fibers, layers, fabrics or composites for reinforcing structures, so that in particular the (further) use of the hardener system is preferably carried out as part of such a synthetic resin composition as mentioned below for the purposes mentioned.

• a) mindestens einen Aktivator in Form eines Metallsalzes und als Radikalstarter
• b1) mindestens ein Aldehyd und/oder Keton und mindestens ein primäres Amin, und/oder
• b2) mindestens ein Imin, welches mindestens ein Imin-Strukturinkrement der oben gezeigten Formel (I) beinhaltet; und
• c) mindestens eine radikalisch polymerisierbare Verbindung.

Another embodiment relates to a synthetic resin composition containing the ingredients

• a) at least one activator in the form of a metal salt and as a radical initiator
• b1) at least one aldehyde and / or ketone and at least one primary amine, and / or
• b2) at least one imine, which contains at least one imine structure increment of the formula (I) shown above; and
• c) at least one free-radically polymerizable compound.

The ratio of the molar amounts (n) of double bonds to carbonyl (aldehyde or keto groups) or imino groups (n (C = C): n (N = C) or n (O = C)) is preferably 4000 in synthetic resin compositions according to the invention : 1 to 1:10, especially at 3000: 1 to 1: 2.

The ratio of the molar amounts (n) of carbonyl (aldehyde or keto groups) or imino groups to metal is preferably at n (N = C) or n (O = C): n (Me) = 1000: 1 to 1:50 , especially from 500: 1 to 1:10.

In a further embodiment, the invention also relates to the use of a synthetic resin composition as described above or below as an adhesive, coating material or molding compound, in particular in the fastening area or system, here primarily for fastening anchoring means in (construction) substrates, such as masonry or Concrete, or for fixing fibers, mats, fabrics or composites for reinforcing structures. The use takes place in particular in the form of a multi-component, such as two-component kit, whereby the reactive components can only come into contact and react with one another at the point of use.

Also corresponding methods or methods, in particular for fastening anchoring elements (anchoring means) in holes or columns, in which a one-component or multi-component synthetic resin composition according to the invention is used for mortaring (gluing) anchoring agents, wherein the synthetic resin composition and an anchoring agent successively, in particular first the synthetic resin composition, then the anchoring means, or (at least substantially) at the same time, into a hole or a gap in a substrate (also in a cracked substrate, such as cracked concrete) are introduced, or mixed forms of these two variants each with partial introduction, form an embodiment of Invention.

Also, corresponding methods or methods for fixing fibers, layers, fabrics or composites for reinforcing structures, in which the one- or multi-component synthetic resin compositions according to the invention are used as fastening means (adhesive), are an embodiment of the invention.

Embodiments of the invention can also be found in the claims, which are incorporated herein by reference, the dependent claims being preferred embodiments of the invention. The examples also relate to preferred embodiments.

Above and below, more general terms or features may be replaced by specific definitions (in particular below) individually, in several or all, resulting in specific preferred embodiments of the invention.

Where "a" or "an" is used, this is (unless otherwise indicated, for example, by prefixing "at least") primarily to be understood as the indefinite article and includes "one (in numbers: 1) or more" as well as only one (in numbers: 1). In other words, "a" or "an" means one or more, e.g. two or three or four ". "At least one" means one or more. Where the plural is used (e.g., "double bonds", "heteroatoms", etc.), this also includes the singular ("double bond", "heteroatom", etc.).

Above and below, percentages or percentages by weight mean in each case percent by weight ("% by weight") or the relative weight fraction, unless stated otherwise, based on all the constituents of a resin composition according to the invention (without packaging material), unless stated otherwise or apparent.

"To include" or "to embrace" means that other than the named constituents or components or features may be present, so an incomplete enumeration, as opposed to "persist", is a final enumeration of those enumerated in its use Components / components / features means. Preferably, instead of "include" it is possible to use "consist of", in particular in connection with the term "molecular structure (s)".

Where the attribute "further" is mentioned, it means that features without this attribute are 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.

By "resin composition" is meant a synthetic resin composition, for the sake of brevity the term "resin composition" will be widely used.

Where "(meth) acrylates" or "(meth) acrylates" are mentioned, this means acrylates, methacrylates or mixtures thereof.

Alkyl (also in alkylene or alkyloxy) and / or aliphatic preferably denotes an unbranched or mono- or polysubstituted - optionally unsaturated - hydrocarbon chain with, for example, 12 carbon atoms.

Cycloalkyl (also in cycloalkylene) and / or (ali) cyclic means preferably a cycloaliphatic radical having 3 to 18, for example having 3 to 8 carbon atoms in the ring.

Aryl (also in arylene) and / or aromatic means in particular aryl of 6 to 22, e.g. having 6 to 10 carbon atoms, especially phenyl (or phenylene).

The prefix "hetero" preferably means that one or more carbon atoms are independently represented by heteroatoms, e.g. by 1 to 3 heteroatoms (for example, selected from O, N, such as NH or N-alkyl, S and Si) are replaced.

Aliphatic-aromatic means in particular an arylalkyl, arylalkylene, arylenealkyl or alkyl-arylene-alkyl radical with aryl, alkyl, alkylene and arylene as just defined.

Where "substituted" or "substituent" is used, this refers to an atom or atomic group (for example, hydroxy) which replaces a hydrogen atom in a molecule. The and / or the substituents (in the case of "substituted") may be along the main chain and / or branched along the side chain. Correspondingly characterized radicals, increments or molecular structures may preferably be saturated or unsubstituted.

In all embodiments of the invention, it is preferred to dispense with any addition (admixing) of prior art initiators, especially peroxides as such, of azides, azo compounds and photoinitiators as radical initiators, i. the subjects of the invention do without such compounds (they are free). It is not excluded that occasionally occur peroxide during storage or the reaction incidentally (for example, by reaction with atmospheric oxygen), but there is no active addition "from the outside".

"Initiators" from the prior art are radical starters, as mentioned. Examples of such peroxides are alkyl hydroperoxides, dialkyl peroxides, peracetals, perketals, peracids, aldehyde peroxides and ketone peroxides; Peroxycarbonates, peroxyesters, diacyl peroxides, and the like, eg as in WO 2007/042199 and US 2002/0091214 called. Examples of non-peroxide compounds are azo compounds such as AIBN and tetrazene.

The aldehydes, ketones, amines, aldimines or ketimines which are contained or used according to the invention are known or can be prepared / obtained according to processes known per se or are preferably obtained therefrom. The imines can be synthesized or obtained before use (eg for attachment of anchoring elements) or even "in situ". Possible processes according to the invention are therefore (t) the separate previous preparation and / or (tt) the "in situ" preparation, in which the aldehyde / ketone and the primary amine are divided into different components of the fastening system and mixed, for example, at the site of use and / or (ttt) the "in situ" preparation in a component of the attachment system in which the aldehyde / ketone and the primary amine are mixed together in the preparation of the particular component. In particular, the imines according to (t) are by condensation under Removal of water from one or more amines with one or more aldehydes or ketones obtained. Corresponding reaction conditions for the separate previous reaction (t) are known to the person skilled in the art.

Examples of suitable amines and aldehydes or ketones can be found in particular in DE 10 2004 035 542 A1 . EP 1 329 469 A1 . EP 1 975 190 A1 and the EP 2 017 260 , which are hereby incorporated by reference for the amines, aldehydes, ketones, aldimines and ketimines generally and specifically mentioned therein.

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 usable mono-, di- and / or polyamines can be both linear and branched. The molecular skeleton of the mono- and / or di- and / or polyamines may contain aliphatic, heteroaliphatic, alicyclic, heterocyclic, aromatic, aliphatic-aromatic and silane / siloxane molecular structures or two or more independently selected thereof. Primary and / or secondary and tertiary amino groups may be present in the molecule, but at least one primary amino group (-NH ₂ ) must be present to form the 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), the Heteroalkyl or heteroalkylene (mono or di) amines (for example 1,13-diamino-4,7,10-trioxatridecane, commercially available amine-functionalized polyoxyalkylenes [Jeffamine] from Huntsman Corp. or, for example: triethylenetetramine and / or higher homologs), the cycloalkyl or cycloalkylene (mono or di) amines (such as: isophorone diamine, 1,3-bisaminomethylcyclohexane, TCD-diamine), the heterocycloalkyl or heterocycloalkylene (mono or di) amines (such as: aminoethylpiperazine), the aminole or Amino alcohols (such as 1,3-diaminopropan-2-ol), and the aliphatic-aromatic (mono or di) amine (such as 1,3- or 1,4-benzenedimethanamine), selected and / or from the group of amino silanated fillers ,

Furthermore, preference may be given to the mono-, di- or polyamines from the group of the aminoamides, polyaminoamides, Mannich bases and the amine adducts (epoxide-amine adducts such as, for example, in US Pat EP 0 387 418 A2 Isocyanate-amine adducts [for example from unreacted amino groups of the imine synthesis or from the abovementioned aminols - when using the aminols, preference is given first to the conversion to imine and then to the isocyanate], Bucherer adducts and Michael addition Adducts).

Also of particular interest as amines are aminoalkyl silanes which contain at least one hydrolyzable group, such as alkoxy, e.g. Methoxy or ethoxy - bound to the silicon - include. These can hydrolyze and condense (due to the water of reaction or water supplied) to form oligomers that carry multiple amino groups and meet the REACH definition for polymers. Imines of such aminoalkylsilanes therefore form the basis for particularly preferred embodiments of the invention. Preferred such aminoalkylsilanes are, for example, selected from the group comprising one or more of the following compounds: aminoalkyltri- or -dialkoxysilanes, such as 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane, and N- (aminoalkyl) amino-alkyltri- or -dialkoxysilanes, such as N- (2-aminoethyl) -3-aminopropyltrimethoxysilane or N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, further ureidoalkyltrimethoxysilanes such as 3-ureidopropyltrimethoxysilane.

In a further particular embodiment of the subject invention may aminosilanized as polyamines fillers carrying primary amino groups, such as aminosilanbehandeltes quartz powder (eg Silbond AST ^® Fa. Quarzwerke GmbH), aminosilanbehandelte silica (eg Aktisil AM ^® Hoffmann Mineral), or aminosilane-treated pyrogens Silica, provided and includes.

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 used as such or suitable or suitable for the synthesis of the aldimines and / or ketimines are, in particular, those of the formula (II):

wherein:
R ₂ , R _{3 are} independently hydrogen and / or an unsubstituted or substituted and / or one or more double bonds and / or heteroatoms having mono- or polysubstituted or straight-chain organic radical which aliphatic, heteroaliphatic, alicyclic, heterocyclic molecular structures and / or combinations of may include the aforementioned molecular structures means.

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 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). As such ketones may be mentioned here by way of example also 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 to the carbonyl group. As a result, the particularly preferred aldehydes and / or ketones have only one (tertiary) hydrogen atom on the α-carbon atom 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 tetrahydropyran-3-carbaldehyde. As particularly preferred ketones may be mentioned here by way of example diisopropyl ketone, 3-methyl-2-pentanone, 2-methylcyclohexanone or β-ionones.

The abovementioned examples of suitable amines, preferred and particularly preferred aldehydes and / or ketones are not intended to limit the scope of suitable amines, aldehydes and / or ketones, but merely some example compounds with the above-mentioned, as preferred, preferred and as particularly preferred defined, structural features to illustrate.

Particular preference is also given to the aldehydes, ketones or synthesized aldimines and / or ketimines mentioned in the examples and the specific amines, ketones and aldehydes added as such and / or for the synthesis of the aldimines and / or ketimines, or mixtures of two or more more of that.

The at least one radically polymerizable compound is a non-aromatic unsaturated group-containing compound, preferably a radical-curing unsaturated reaction resin preferably having at least 2 or more reactive non-aromatic unsaturated bonds, or a mixture of two or more reactive resins.

As free-radically curing reaction or synthetic resin, ethylenically unsaturated compounds and compounds having carbon-carbon triple bonds are suitable according to the invention.

Particularly suitable is the group of ethylenically unsaturated compounds containing styrene and derivatives; Vinyl esters, such as (meth) acrylates, urethane (meth) acrylates or itaconates, or epoxy (meth) acrylates; also unsaturated polyesters, vinyl ethers, allyl ethers, dicyclopentadiene compounds and unsaturated fats.

Particularly preferred are, above all, one or more such reactive resins, the (free-radically) curable esters having one or more unsaturated carboxylic acid radicals (such as in DE 10 2014 103 923 A1 described); preferably in each case propoxylated or in particular ethoxylated aromatic diol, such as bisphenol A, bisphenol F or novolak (especially di) (meth) acrylates; Epoxy (meth) acrylates, in particular in the form of reaction products of di- or polyepoxides, for example bisphenol A, bisphenol F or novolak di- and / or polyglycidyl ethers, with unsaturated carboxylic acids, for example C ₂ -C ₇ -Alkenecarboxylic acids, in particular (meth) acrylic acid; Urethane and / or urea (meth) acrylates - in particular urethane (meth) acrylates, for example, by reacting di- and / or polyisocyanates (higher functional isocyanates) with suitable (meth) acrylic compounds (such as: hydroxyethyl or hydroxypropyl methacrylate), optionally with the participation of hydroxy compounds containing at least two hydroxyl groups, as described for example in the DE 39 40 309 A1 and or DE 4111828 A1 are obtained; or unsaturated polyester resins, or the like, or two or more of these curable unsaturated organic components.

The proportion by weight of this or these reactive resins is preferably in the range from 0.1 to 90% by weight, for example between 0.5 and 75% by weight or between 1 and 40% by weight or in particular from 15 to 60, for example 20 to 50% by weight.

Important examples of other (in particular in the attachment area usual) ingredients are co-accelerators, inhibitors, reactive thinners, thixotropic agents, fillers and / or other additives.

Suitable co-promoters may be amino co-promoters such as, in particular (preferably tertiary, especially hydroxyalkylamino) substituted aromatic amines selected from the group consisting of epoxyalkylated anilines, toluidines or xylidines, e.g. ethoxylated toluidine, aniline or xylidine, such as N, N-bis (hydroxyethyl) -p-toluidine and especially also correspondingly higher alkoxylated technical products includes. Mixtures of two or more co-promoters, in particular those mentioned, are possible. The co-accelerator (s) preferably has a content (concentration) of 0.005 to 10, in particular of 0.1 to 5,% by weight.

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

As phenolic inhibitors (which may be provided as an already admixed constituent of commercial free-radically curing reaction resins but may also be absent) come (optionally alkylated) hydroquinones, such as hydroquinone, mono-, di- or trimethylhydroquinone, (optionally alkylated) phenols, such as 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 , or 4-methoxyphenol, (optionally alkylated) catechols such as tert-butyl catechol or 3,5-di-tert-butyl-1,2-benzenediol, or mixtures of two or more thereof in question. Their proportion is preferably up to 1% by weight, in particular between 0.0001 and 0.5% by weight, e.g. between 0.01 and 0.1 wt .-%.

As non-phenolic or anaerobic inhibitors are preferably phenothiazines or other stable organic radicals, such as galvinoxyl and N-oxyl radicals into consideration. As organic nitroxyl radicals (especially "HALS"), for example, those from DE 199 56 509 , in particular 1-oxyl-2,2,6,6-tetra-methylpiperidin-4-ol ("4-OH-TEMPO" or "TEMPOL"). The weight fraction of the non-phenolic inhibitors is preferably, based on the reaction resin formulation in the range of 1 ppm (wt.) To 2 wt .-%, in particular, for example, in the range of 10 ppm (by weight) to 1 wt .-%.

As the thixotropic agent, usual thixotropy-causing rheological aids such as fumed silica, bentonites, alkyl and methylcelluloses, castor oil derivatives or the like, e.g. in a weight proportion of 0.01 to 50 wt .-%, for example from 0.1 to 5 wt .-%.

Other additives may also be added, such as plasticizers, non-reactive diluents, other silanes, flexibilizers, stabilizers, antistatic agents, thickeners, curing catalysts, rheology aids, wetting and dispersing agents, coloring additives, such as dyes or in particular pigments, for example, for different staining of the components better control of their mixing, or the like, or mixtures of two or more thereof. Such additives may e.g. in total, in proportions by weight of from 0 to 90% by weight, for example from 0 to 40% by weight, may be added. They may be added in single or multiple components in multi-component systems in a manner which is obvious and known to the person skilled in the art.

As reactive diluents for free-radically curing reaction or synthetic resins, it is additionally possible for one or more low-viscosity free-radically polymerizable compounds to be added, such as, for example, in US Pat EP 1 935 860 A1 and DE 195 31 649 A1 described. Preferably, the synthetic resin contains as "reactive diluents" (meth) acrylic esters ((meth) acrylates) of the formula (H ₃ C or H) -C (= CH ₂ ) -C (= O) -OX, wherein X is an optionally substituted or polysubstituted alkyl radical (including hydroxyalkyl (meth) acrylates, such as (eg 2-) hydroxypropyl (meth) acrylate or hydroxyethyl (meth) acrylate), alkyl (meth) acrylates having 1 to 10 (meth) acrylate groups, such as mono-, Di-, tri-, tetra-, penta-, hexa- or poly (meth) acrylates, for example alkyldi- or tri (meth) acrylates, such as 1,2-ethanediol di (meth) acrylate, 1,3- or especially 1, 4-butanediol di (meth) acrylate, hexanediol di (meth) acrylate, diethyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, polyglycerol poly (meth) acrylate, polyethylene glycol di (meth) acrylate, cycloalkyl, bicycloalkyl or Heterocycloalkyl (meth) acrylates wherein cycloalkyl or bicycloalkyl has 5 to 7 ring carbon atoms and heterocyclyl has 5 or 6 ring atoms and selects 1 or 2 ring heteroatoms t of N, O and S, such as tetrahydrofurfuryl (meth) acrylate or isobornyl (meth) acrylate, or acetoacetoxyalkyl (meth) acrylate. Further, styrenes such as styrene, α-methylstyrene, vinyltoluene, tert-butylstyrene and / or divinylbenzene, or mixtures of two or more thereof, when the components curing in parallel with the radical-curing unsaturated reaction resin are provided. The one or more reactive diluents are added, for example, in a weight fraction of 0.1 to 90 wt .-%, for example between 0.5 and 75 wt .-% or between 1 and 40 wt .-%.

The activators in the form of a metal salt, which also includes metal complexes and metal oxides, used constituents are preferably one or more metal salts or in particular one or more salts of organic and / or inorganic acids with metals, for example selected from copper, iron, Vanadium, manganese, cerium, cobalt, zirconium, or bismuth, or mixtures of two or more thereof. In particular, the metal salts are selected from the group consisting of vanadium, iron, manganese and copper, in particular in the form of salts or complexes with inorganic acid radicals, such as sulfate and / or carbonate radicals and / or organic acid radicals, for example carboxylate radicals; the organic acids preferably being saturated - such as carboxylates with CH ₃ , C ₂ -C ₂₀ -alkyl, a C ₆ -C ₂₄ -aryl radical or C ₇ -C ₃₀ -aralkyl radical, for example octoate, for example 2-ethylhexanoate (isooctanoate), Neodecanoate, or acetylacetonate. Particular preference is given to manganese carboxylates, such as Mn acetate or mn octoate, copper carboxylates, such as copper octoate 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 include, for example, iron chloride, iron sulfate, copper sulfate and Includes copper chloride.

Such activators are known or can be prepared by methods known per se and are preferably present in a proportion of from 0.01 to 20, e.g. 0.1 to 5 wt .-%, before.

Fillers may be contained in one or more multi-component compositions in a plurality of components of a synthetic resin composition of the present invention, for example, in the form of a multicomponent kit. Their content is preferably 0 to 80% by weight, for example 5 to 80, e.g. 40 to 70 wt .-%.

Fillers are customary fillers, for example hydraulically hardenable fillers, such as gypsum, burnt lime, waterglasses or, in particular, cements, such as Portland cement or high-alumina cements; mineral or mineral-like fillers, such as chalk, sand, minerals, quartz, glass, porcelain, corundum, ceramics, silicates, clays, barite, aluminum hydroxide, or the like, which may be added as a powder, in granular form or in the form of moldings, use , or others, such as in WO 02/079341 and WO 02/079293 (referred to herein by reference), or mixtures of two or more thereof; wherein the fillers may be further or in particular also silanized as already mentioned or otherwise.

Further silanes are all monomeric silanes and / or oligomeric siloxanes which contain one or more hydrolyzable groups bonded to the silicon atom. For example, these are (meth) acryloxyalkyltri- or -dialkoxysilanes such as methacryloxypropyltrimethoxysilane, vinyltri- or dialkoxysilanes, e.g. Vinyltrimethoxysilane or vinyltriethoxysilane, (cyclo) alkyltri- or -dialkoxysilanes, such as methyltrimethoxysilane, (cyclohexyl) methyldimethoxysilane, tetraalkoxysilanes, such as tetraethoxysilane, tetramethoxysilane or tetrapropoxysilane or alkoxypolysilicates (esters of (poly) silicic acid), such as ethyl or propyl polysilicate, to name but a few call. The other silanes can also be present in the synthesis of the iminosilanes (aldimine and / or ketimine from aminoalkylsilane and aldehyde or ketone), with co-condensates possibly being formed by the resulting water of reaction.

As mentioned above, one embodiment of the invention relates to the use of a hardening system described above and below (optionally with storage components a) and b1) and / or b2)) for producing a synthetic resin composition, in particular as a hardener system of a multi-component kit containing the synthetic resin composition according to the invention , or a corresponding production method of such a hardener system, which includes the mixing of the components a) and b1) and / or b2) on site, optionally in the presence of further ingredients and the component c).

A multicomponent kit (or set) is to be understood in particular as a two-component kit (preferably a two-chamber or further multichamber device) in which the mutually reactive constituents a), b1) and / or b2) and c) are included during the Storage can not lead to undesirable reactions, ie present in spatially separated components. Possible are cartridges. Particularly suitable are cartridges with two components, in which the content is transferred to or mixed with the application site (in particular by means of a static mixer) in a recess, preferably a borehole. Corresponding uses are preferred.

In a possible preferred variant of a multicomponent kit according to the invention, constituents a) and c) are contained in one component (K1), while constituent b) (b1 and / or b2) is contained in another (immiscible, ie separated) component (K2 ), wherein in each case optionally one or more further additional ingredients may be present.

In the case of using radical initiators b1) (at least one aldehyde and / or ketone (carbonyl compound) and on the other hand at least one primary amine), the constituents carbonyl compound and primary amine can also be provided in separate components (K1) and (K2) and thus only in the Mixing when used in situ with each other in contact and possibly come to a reaction. Preference is given in this case to the carbonyl compound and the constituent c) in one component (K1), and the primary amine of the radical initiator b1) together with the constituent a) in another component (K2). One or more additional ingredients may optionally be present.

Component b1) and / or b2) may also be included with component c) or component a) in one component, but this does not lead to particularly preferred embodiments of the invention; wherein in each case optionally one or more further additional ingredients may be present and / or necessary.

In one embodiment of the invention, component c) may be present in both components (K1) and (K2), while components a) and b1) and / or b2) are then separated from one another (immiscible in the storage state) in each case as component c) into the individual components (K1) or (K2).

A variant of the use according to the invention provides that the components b1) and / or b2) and c) are introduced into a borehole while the anchor rod or further another material to be bonded is immersed in component a) (for example an activator metal salt solution) and then introduced into the wellbore provided with b1) and / or b2) and c).

Substrate (e.g., for boreholes) are e.g. Materials for walls, ceilings or floors in the construction sector, e.g. Masonry, concrete, wood, metal or plastic.

The following examples illustrate the invention without limiting its scope. In the following examples, the respective unlabelled components of the model formulations are mixed in advance. Addition and mixing in of the component marked " ^X " initiates the polymerization.

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

Determination of the gel time

The gel time is determined manually with a commercially available stopwatch and a commercially available thermometer at room temperature (about 23 ° C). For this purpose, all ingredients are mixed and measured immediately after mixing the temperature of the sample. The sample itself is in a plastic cup. The evaluation is based on DIN 16945 , The gel time is the time when the temperature rises above 35 ° C. This corresponds to a temperature increase of approx. 10 K.

Determination of processing time

The determination of the processing time takes place in a plastic cup at room temperature by means of manual stirring. Upon reaching the gelling point, the previously liquid sample is highly viscous and gel-like, which is u.a. makes noticeable by clumping. At this time, the clock started after the start of the test is stopped. The processing time can be read directly.

Pull-out tests made of concrete

For pull-out tests with threaded rods M12, proceed as follows, according to ETAG 001 PART 5:
First, drill holes (diameter 14 mm, depth 95 mm) are placed in a horizontal concrete test specimen (concrete type C20 / 25) with a hammer drill. The holes are cleaned with a hand blower and a hand brush. The holes are then filled with the respective hardenable mass to be tested for fixing purposes for two-thirds. Each hole is a threaded rod by hand pressed. The mortar excess is removed by means of a spatula. After 24 hours at room temperature, the threaded rod is pulled to failure, measuring the failure load.

The following ingredients and abbreviations are used to prepare the following example formulations. Table 1: Components used and abbreviations abbreviation description MR resin formulation IPDA isophoronediamine DCH 1,2-diaminocyclohexane EDR148 Jeffamine EDR-148 (Huntsman Corporation, Woodlands, Texas, USA) D230 Jeffamine D230 (Huntsman Corporation, Woodlands, Texas, USA) MXDA Meta-xylylenediamine BAC 1,3-bis (aminomethyl) cyclohexane DETDA diethyl AT THE 3-aminopropyltrimethoxysilane BDDMA 1,4-butanediol dimethacrylate HPMA 2-hydroxypropyl methacrylate AROUND urethane SR210 PEG200DMA: polyethylene glycol 200 dimethacrylate (Sartomer) CN159 Epoxy methacrylate based on bisphenol A (Sartomer) VPLS2142 CSTICO ^® phen VP LS 2142 (csc Jäklechemie GmbH & Co. KG) SolCop8 Soligen Copper 8 (Cu-carboxylate, active content: 7,8-8,2%, OMG Borchers GmbH) Iro7 / 8 Octa Soligen Iron 7/8 (iron carboxylate, active content: 7,3-7,7%, OMG Borchers GmbH) Mn (III) Manganese (III) acetate 3% in HPMA oxyC Borchers Oxy Coat (highly activated iron, OMG Borchers GmbH) VP0132 Borchers VP0132 (vanadium carboxylate, active content: 4.9-5.1%, OMG Borchers GmbH) CF31 Nouryact CF31 (metal complex, Akzo Nobel Functional Chemicals BV) SolMn6 Soligen Manganese 6 (manganese naphthenate, active content: 6%, OMG Borchers GmbH) mn6 Octa Soligen Manganese 6 (manganese octoate, active content: 6%, OMG Borchers GmbH) t-BBC tert-butylcatechol t temp.> 35 ° C Time to exceed the temperature above 35 ° C [hh: mm: ss] (= gel time) T _max maximum temperature reached [° C] END15 Umicore Ecos ND15 (polymer dry matter, active content: 4%, Umicore Specialty Materials Brugge NV) DCER Duroct Cerium 6% (cerium carboxylate, active content: 6%, DURA Chemicals Inc.) NDryC Nuodex Dry Coat (highly activated manganese-amine complex, active content: 1%, Rockwood Pigments Durham) CuSO4H2O Copper sulphate 15% in water CuSO4MEG Copper sulphate 5% in monoethylene glycol LS2965 Desmophen LS 2965 (Bayer MaterialScience) isob isobutyraldehyde 2MVal 2-methyl valeraldehyde Val valeraldehyde MIBK methyl isobutyl ketone H18 Wacker HDK H18 (Synthetic, hydrophobic, amorphous, silicic acid produced by flame hydrolysis) H30RA Wacker HDK H30RA (amine-functionalized fumed silica)

Example 1: General Procedure I: Alternative Synthesis of Aldimines

In a round bottom flask, the corresponding amine is presented. With vigorous stirring, the aldehyde is added slowly from a dropping funnel, whereby the mixture heats up. After completion of the addition, the volatiles are not removed. The resulting water of reaction separates depending on the amine used ("hydrophobic" amines) from aldimine. The residual water present in the aldimine does not interfere with the use as an initiator. Using "hydrophilic" amines, no phase separation occurs. Optionally, the aldehyde may be initially charged and the amine may be added dropwise. The reaction (freedom from imine groups detectable by IR spectroscopy) is checked by means of FT-IR.

Example 2: Example recipe for an aldimine of isobutyraldehyde and Jeffamin D230

The recipe for an aldimine which can be prepared or prepared according to Example 1 (General Procedure I) is: TABLE 2 Recipe Aldimine from Isobutyraldehyde and Jeffamine D230 raw material m [g] M [g / mol] n [mol] Wt.% isobutyraldehyde 15.00 72.11 0.208 38.54 D230 23,92 230.00 0.104 61.46 total 38.92 100.00

The resulting water of reaction separates slowly from the aldimine and collects at the bottom of the piston.

The aldimines used below are prepared analogously to general procedure I, or are commercially available.

Example 3: Simplified resin formulations

The following raw materials are mixed for the simplified resin formulations: Table 3: simplified resin formulation I (HRI) raw material Wt.% Ethoxylated bisphenol A dimethacrylate * 88.76 BDDMA 7.14 HPMA 4.10 * technical product - different degrees of ethoxylation possible. Table 4: simplified resin formulation II (HRII) raw material Wt.% UM resin 54.86 BDDMA 40,00 HPMA 5.00 additives 0.14

The production of the UM resin takes place in a manner known to the person skilled in the art. It is an example of the patent DE 4111828 A1 directed. The isocyanate used is a polymeric diphenylmethane diisocyanate with isomers and higher homologs. Table 5: simplified resin formulation III (HRIII) raw material Wt.% Ethoxylated bisphenol A dimethacrylate * 80,00 SR210 20.00 * technical product - different degrees of ethoxylation possible.

The simplified resin formulation III is of particular interest for the production of label-free reaction resins or fastening systems and represent particularly preferred embodiments of the invention.

Example 4 Determination of the Gel Times with VPLS2142 as radical initiator b2)

To evaluate the applicability of the hardener system imine metal salt to cold curing vinyl ester resins, example formulations are prepared with the resin formulation I described above and various metal salts. Free-radical initiators an imine from isobutyraldehyde and isophorone diamine is used (phen CSTICO ^® VP LS 2142). Table 6 below lists the gel times and the maximum temperatures achieved during the polymerizations: TABLE 6 Gel times of VPLS2142 initiator systems and varying metal salts description HRI [g] VPLS2142 [g] Metal salt [g] Sum [g] metal t Temp.> 35 ° C [hh: mm: ss] _Tmax [° C] VPLS2142-004 9.75 0.25 ^X 0.10 10.10 SolCop8 0:00:57 89.1 VPLS2142-006 9.75 0.25 ^X 0.10 10.10 Mn (III) 0:02:06 74.9 VPLS2142-007 9.75 0.25 ^X 0.10 10.10 oxyC 0:02:17 71.0 VPLS2142-008 9.75 0.25 ^X 0.10 10.10 VP0132 0:00:20 100.0 VPLS2142-010 9.75 0.25 ^X 0.10 10.10 CF31 0:01:23 88.7 Cf. Ex-01 9.75 0.25 - 10.00 - > 04:00:00 - Cf. Ex-02 9.75 - 0.10 9.85 SolCop8 > 18:00:00 - ^X added as a hardener

It can be seen from Table 6 that the example formulations achieve exothermic and partially rapid polymerizations of vinyl ester resins at room temperature. In addition, Table 6 shows that the hardener system imine metal salt works with all metals. The comparative examples Vgl-Bsp-01 and Vgl-Bsp-02, which are not according to the invention, show that no effective polymerizations are triggered without the presence of constituent a) or b2).

Example 5 Determination of Processing Times with VPLS2142 as Initiator b2)

Table 7 shows the processing times of the initiator system consisting of CSTICO phen ^® VP LS 2142 in combination with Octa Soligen Manganese 6 at different initiator and metal salt contents: Table 7: Processing times of the initiator systems of VPLS2142 and Mn6. description HRI [g] VPLS2142 [g] Mn6 [g] Sum [g] t _time (hh: mm: ss] n (C = C): n (N = C) n (N = C): n (Mn) VPLS2142-013 9.75 0.10 0,10 ^X 9.95 0:01:14 74 6 VPLS2142-015 9.75 0.50 0,10 ^X 10.35 0:00:34 15 29 VPLS2142-017 9.75 0.10 0.02 ^X 9.87 0:01:54 74 29 VPLS2142-018 9.75 0.05 ^0.01X 9.81 0:03:22 147 29 VPLS2142-020 9.75 0.10 0.20 ^X 10.05 0:01:04 74 3 VPLS2142-021 9.75 0.25 0,10 ^X 10,20 * ¹ 0:08:15 VPLS2142-023 9.75 7.37 0,10 ^X 17.22 0:00:20 1 430 VPLS2142-026 9.75 0.0025 * ² 0,10 ^X 10.10 0:56:30 2950 0.15 ^X added as a hardener
* ¹ additional 0.1 g t-BBC weighed 10% in BDDMA.
* Weigh ² 0.25 g of a 1% solution of VPLS2142 in BDDMA.

The model mixtures from Table 7 show that both the initiator b2) and the metal salt can be varied within wide limits (see also the molar ratios n (C = C): n (N = C) (imine increment) and n (N = C): n (metal) The use of an aerobic inhibitor and its retarding effect are shown by model mixture VPLS2142-021.

Example 6: Determination of the gel times with SolCop8 or SolMn6 and varying aldimines as free radical initiators b2) - Variation of the amines and the aldehydes

The following Tables 8a and 8b illustrate the gel times and the maximum temperatures reached during the polymerizations of the hardener systems consisting of Soligen Copper 8 or Soligen Manganese 6 and different imines: Table 8a: Gel times of the initiator systems of SolCop8 and various aldimines (prepared in each case from isobutyraldehyde and varying amines) description HRI [g] Aldimine [g] SolCop8 [g] Sum [g] Amin t Temp.> 35 ° C [hh: mm: ss] _Tmax [° C] Isob MXDA 9.75 0.25 ^X 0.10 10.10 MXDA 0:00:52 87.6 Isob-BAC 9.75 0.25 ^X 0.10 10.10 1,3-BAC 0:00:46 95.9 Isob-EDR148 9.75 0.25 ^X 0.10 10.10 EDR148 0:01:17 97.0 Isob-DCH 9.75 0.25 ^X 0.10 10.10 DCH 0:01:13 93.2 Isob-DETDA 9.75 0.25 ^X 0.10 10.10 DETDA 0:20:07 39.6 ^X added as a hardener Table 8b: Gel times of the initiator systems of SolMn6 and various aldimines (prepared in each case from Jeffamine D230 and varying aldehydes). description HRI [g] Aldimine [g] SolMn6 [g] Sum [g] Aldehyde / ketone t Temp.> 35 ° C [hh: mm: ss] _Tmax [° C] Isob-D230-005 9.75 0.25 ^X 0.10 10.10 isob 0:01:47 96.6 2MVal-D230 9.75 0.25 ^X 0.10 10,10 2MVal 0:01:43 94.8 Val-D230 9.75 0.25 ^X 0.10 10.10 Val 0:12:25 42.8 LS2965 9.75 0.25 ^X 0.10 10.10 MIBK - * - * ^X added as a hardener
* hardened the next day

Tables 8a and 8b clearly show that the vinyl ester resin formulation can be polymerized very well with a wide variety of radical initiators b2). In addition, Table 8a should emphasize that all types of primary amines can be used for the production of the imines without suffering any loss or deterioration of the polymerization-inducing effect. From Table 8b it can be seen that the - for imine synthesis - particularly preferred aldehydes polymerize much faster and with greater exotherm. Table 8a further illustrates that any residual (residual) water of reaction (e.g., isob-DCH) or even homogeneously dispersed water of reaction (e.g., isob-EDR148) has no effect on the polymerization.

Example 7 Determination of the Gel Times with the Aldimine Isob-AM as Initiator b2) The aldimine isob-AM is prepared from the two educts isobutyraldehyde and 3-aminopropyltrimethoxysilane. Silanes are reactive to water and react with hydrolysis and condensation. Due to this fact, in the aldimine synthesis by the reaction water in situ, an oligomerization of the silane units. This makes it possible to generate REACH-polymeric initiators. Table 9 shows the gel times and the associated maximum attained temperatures of the hardener systems Isob-AM with varying metal salts. Table 9: Gel times of the initiator systems of isob-AM and varying metal salts description HRI [g] Isob-AM [g] Metal salt [g] Sum [g] metal t Temp.> 35 ° C [hh: mm: ss] _Tmax [° C] Isob-AM-001 9.75 0.25 0,10 ^X 10.10 SolCop8 0:01:00 95.1 Isob-AM-003 9.75 0.25 0,10 ^X 10.10 oxyC 0:01:36 80.1 Isob-AM-004 9.75 0.25 0,10 ^X 10.10 VP0132 0:00:18 86.7 Isob-AM-010 9.75 0.25 0,10 ^X 10.10 CF31 0:00:58 90.5 Isob-AM-014 9.75 0.25 0,10 ^X 10.10 END15 0:01:53 85.3 Isob-AM-021 9.75 0.25 0,10 ^X 10.10 DCER 0:07:16 74.4 Isob-AM-029 9.75 0.25 0,10 ^X 10.10 NDryC 0:02:13 84.8 ^X added as a hardener

It can also be seen from the model formulations of Table 9 that an exothermic and partially rapid polymerization of methacrylates at room temperature can be achieved with different metal salts. Furthermore, Table 9 should emphasize that not only monomeric initiators but also oligomeric to polymeric (REACH polymers) initiators can be used. The model mixture Isob-AM-029 is of particular interest for coating applications, since the activator used here does not have any inherent color in the resin, ie it appears colorless.

Example 8: Pull-out Tests of Concrete with Free-Radical Starters b2)

Setting tests are carried out in accordance with the aforementioned parameters for "extraction tests made of concrete". Table 10: Formulations for carrying out setting experiments and determined bond stresses with free-radical initiators b2) description SV-ISOB MXDA-001 SV-ISOB-D230-001 SV-ISOB-AM-001 SV-VPLS2142-016 HRI [g] 29.13 28.85 29.13 29.07 Aldimine [g] 0.75 1.48 0.75 0.75 Metal salt [g] 0.30 ^X SolCop8 0.30 ^X Iro7 / 8 0.30 ^X OxyC 0.47 ^X CuSO ₄ Sand [g] 44.82 44.38 44.82 44.72 Sum [g] 75.00 75.00 75.00 75.00 Bond stress [N / mm ² ] 20.1 17.1 19.5 17.9 ^X added as a hardener

The educts of the aldimines can be assigned according to the abbreviations used in the designations and Table 1 above for abbreviations accordingly. Table 10 shows that the hardener system according to the invention is very efficient, and also shows the enormous potential of such initiator systems.

Example 9: Determination of gel times with radical initiators b1) and varying metal salts

To demonstrate the utility of radical initiators b1) in combination with metal salts, example formulations are prepared with the above-described Resin Formula I (HRI) and different metal salts. Table 11 below shows the gel times and the maximum temperatures attained during the curing reactions. Table 11: Gel times of the hardener systems consisting of isob and D230 in combination with different metal salts. description HRI [g] D230 [g] Metal [g] Isob [g] Sum [g] Metal t Temp.> ° C 35 [hh: mm: ss] _Tmax [° C] Ed metals-001 9.75 0.24 0.10 0.15 ^X 10.24 SolCop8 0:02:35 99.6 Ed metals-002 9.75 0.24 0.10 0.15 ^X 10.24 Iro7 / 8 0:07:16 69.6 Ed metals-003 9.75 0.24 0.10 0.15 ^X 10.24 oxyC 0:02:56 71.1 Ed metals-004 9.75 0.24 0.10 0.15 ^X 10.24 VP0132 0:00:52 82.4 Ed metals-005 9.75 0.24 0.10 0.15 ^X 10.24 SolMn6 0:03:30 92.3 Ed metals-011 9.75 0.24 0.10 0.15 ^X 10.24 END15 0:13:16 83.2 Ed metals-015 9.75 0.24 0.10 0.15 ^X 10.24 CuSO4 H2O 0:05:14 84.6 Ed metals-016 9.75 0.24 0.10 0.15 ^X 10.24 CuSO4 MEG 0:05:06 92.8 ^X added as a hardener

Table 11 illustrates that the free-radical initiators b1) according to the invention in combination with metal salts also trigger polymerizations of unsaturated reaction resins at room temperature. Furthermore, it can be seen from the model formulations that all metal salts can be used for this purpose. The possible use and the functionality of metal salts of inorganic or organic acids is shown in the formulations Verf-Metals-001 (metal salt of organic acids) or Verf-Metals-015 and Verf-Metals-016 (metal salt of inorganic acids).

Example 10: Determination of the gel times with radical initiators b1) and SolMn6 / SolCop8 as metal salts

Table 12 below illustrates the gel times and the maximum temperatures achieved by the free-radical initiators b1) according to the invention using different amines and aldehydes. Table 12: Gel times of the radical initiators b1) with varying amines and aldehydes description HRI [g] Aldehyde [g] Metal [g] Amine [g] Sum [g] Amine / aldehyde t Temp.> 35 ° C [hh: mm: ss] _Tmax [° C] Ed-Amine-001 9.75 0.15 0,10 SolMn6 0.37 ^X 10.37 AMMO / ISOB 0:01:50 89.4 Ed-Amine-002 9.75 0.15 0,10 SolMn6 0.14 ^X 10.14 MXDA / ISOB 0:03:27 68.2 Ed-Amine-004 9.75 0.15 0,10 SolMn6 0.15 ^X 10.15 BAC / ISOB 0:03:37 91.3 Ed-Ald-001 9.75 0.15 ^X 0.10 SolCop8 0.24 10.24 D230 / ISOB 0:02:12 104.8 Ed-Ald-002 9.75 0.21 ^X 0.10 SolCop8 0.24 10.30 D230 / 2MVal 0:03:35 94.4 Cf. Ex-03 9.75 0.15 0.10 SolCop8 - 10.00 - / ISOB > 18:00:00 - Cf. Ex-04 9.75 0.15 - 0.24 10.14 D230 / ISOB > 04:00:00 - Cf. Ex-05 9.75 - 0.10 SolCop8 0.24 10.09 D230 / - > 18:00:00 - ^X added as a hardener

Table 12 shows that not only various primary amines but also various aldehydes can be used as radical initiator b1) according to the invention. This is evidenced by the rapid and exothermic polymerizations. The non-inventive comparative examples Vgl-Bsp-03 to Vgl-Bsp-05 illustrate that take place in the absence of a constituent of the hardener systems according to the invention no efficient polymerizations.

Example 11: Determination of Gel Times with Free-radical Initiators b1) using amine-functionalized fillers

The possible use of amine-functionalized or amine-silanized fillers as polyamines in radical initiators b1) is intended to illustrate Table 13 below. Table 13: Gel times of radical initiators b1) with amine-functionalized fillers as polyamines description HRI [g] H30RA [g] Metal [g] Isob [g] Sum [g] metal t Temp.> 35 ° C [hh: mm: ss] _Tmax [° C] H30RA-06 9.75 1.16 0.10 0.03 ^X 11.04 SolCop8 0:06:26 78.9 H30RA-07 9.75 1.16 0.10 0.03 ^X 11.04 CuSO4 MEG 0:08:44 72.1 H30RA-08 9.75 1.16 0.10 0.03 ^X 11.04 oxyC 0:05:41 61.1 ^X added as a hardener

The amine-functionalized silica used has an approximate nitrogen content of 0.5%. Table 13 demonstrates that amine-functionalized fillers can also be used as polyamines for free radical initiators b1) and the reaction resin can thus be polymerized very well.

Example 12: Pull-out Tests of Concrete with Free-Radical Starters b1)

In order to also show the performance potential of the radical starter b1) as close as possible to the application, setting experiments are carried out in accordance with the aforementioned parameters for "extraction tests of concrete". Table 14: Formulations for Carrying Tests and Determined Bond Tensions with Radical Starters b1). description SV-AV-01 SV-AV-02 SV-AV-03 SV-AV-04 SV-AV-05 SV-AV-06 SV-AV-08 SV-AV-16 HRI or II 28.97 28.97 28.97 28.97 28.97 28.91 28.82 28.97 Isob [g] 0.45 0.45 0.45 ^X 0.45 ^X 0.45 0.59 0.44 1.34 SolCop8 [g] 0.30 0.30 0.30 0.30 0.30 ^X 0.30 ^X 0.30 ^X 0.30 ^X Sand [g] 44.57 44.57 44.57 44.57 44.57 44.48 44.34 42,25 D230 [g] 0.71 ^X 0.71 ^X 0.71 0.71 0.71 ^X 0.71 ^X 1.09 ^X 2,14 ^X Sum [g] 75.00 75.00 75.00 75.00 75.00 75.00 75.00 75.00 Bond stress [N / mm ² ] 18.6 16.1 17.5 14.1 17.2 13.9 17.1 22.0 the raw materials marked with ^X are added as a hardener or hardener formulation.

In the formulations SV-Verf-02 and SV-Verf-04, instead of the simplified resin formulation I (HRI), the urethane methacrylate-based resin formulation II (HRII) according to Example 3 is used. In the formulation SV-Verf-06 2-methylvaleraldehyde is used instead of isobutyraldehyde. The metal salt SolCop8 and the amine D230 in the formulation SV-Verf-08 is replaced by OxyC and AM. Table 14 shows that the radical initiators b1) in combination with metal salts also form powerful hardener systems for unsaturated reaction resins and achieve suitable bond stresses. The formulations SV-Verf-01 and SV-Verf-02 show that also different base resins can be cured with the initiator system according to the invention. Furthermore, it can be seen in the formulations SV-Verf-01, SV-Verf-03 and SV-Verf-05 that the constituents of the radical initiator b1) or of the hardener systems according to the invention can each be used as hardeners or hardener formulations and thus various partitions to different components are possible.

Example 13: Gel times of radical initiators b1) and b2) using label-free reaction resins

Label-free reaction resins or fastening systems play an increasing role in the field of chemical fastening technology. Here, the initiator systems according to the invention show great advantages over the prior art and only allow the formulation of multi-component, multi-component reaction resin systems. Table 15 shows the gel times and the maximum temperatures reached during the polymerizations of label-free reaction resin formulations initiated by the radical initiators b1) and b2) according to the invention. Table 15: Gel times of radical initiators b1) and b2) in label-free reaction resins description KFR-01 KFR-06 KFR-03 KFR-04 KFR-05 HRIII [g] 9.85 9.95 9.75 9.75 9.85 VPLS2142 [g] 0,10 ^X 0,10 ^X - - 0,10 ^X Isob [g] - - 0.15 0.15 ^X - SolCop8 [g] 0.10 0.05 0.10 - - CuSO4 MEG [g] - - - 0.10 0.10 D230 [g] - - 0.24 ^X 0.24 - Sum [g] 10.05 10.10 10.24 10.24 10.05 t Temp> 35 ° C [hh: mm: ss] 0:01:50 0:02:37 0:09:35 0:09:29 0:03:41 _Tmax [° C] 110.0 82.3 80.4 92.4 95.7 the raw materials marked with ^X are added as hardeners.

In the example formulation KFR-01, a reaction resin based on an epoxy methacrylate (CN159) and a reactive diluent (SR210) - ratio 50:50 - is used instead of the simplified resin formulation HRIII. In addition, in formulation KFR-06, the reactive diluent (SR210) of the simplified resin formulation III is replaced by a bio-based reactive diluent (Sarbio6105). Table 15 illustrates that the hardener systems according to the invention also lead to an exothermic and effective polymerization of label-free and partially bio-based reaction resins.

Example 14: Referencing experiments with respect to EP 2 824 117 A1

To prove that the inventively usable imines (radical initiator b1) and / or b2)) in combination with metal salts to significantly more powerful initiator systems and higher bond stresses compared to those in the EP 2 824 117 A1 lead tertiary aliphatic amines claimed, the following Referencing (RefV) are carried out:

RefV-1: Evaluation on curing with PMDETA as initiator and varying metal salts

In order to assess the applicability of the initiator system PMDETA metal salt to cold-curing vinyl ester resins, example formulations with the resin formulation I described above and various metal salts are prepared analogously to Example 4. Table 16a: PMDETA as initiator with varying metal salts description HRI [g] DETA PM [g] Metal salt [g] Sum [g] metal comment PMDETA 001 9.75 0.25 0,10 ^X 10.10 SolCop8 liquid* PMDETA 009 9.75 0.50 0,10 ^X 10.35 SolCop8 gelled* PMDETA 002 9.75 0.25 0,10 ^X 10.10 Iro7 / 8 liquid* PMDETA 003 9.75 0.25 0,10 ^X 10.10 VP0132 liquid* PMDETA 004 9.75 0.25 0,10 ^X 10.10 oxyC liquid* PMDETA-005 9.75 0.25 0,10 ^X 10.10 mn6 liquid* ^X added as a hardener
* after 24 h

From Table 16a it is clear that the concentrations analogous to Example 4 in the hardener systems PMDETA - metal salts lead to any polymerization of the vinyl ester resin. Only by increasing the initiator concentration (PMDETA-009) was it possible to detect gelation.

RefV-2: Pull-out tests made of concrete with PMDETA as initiator

Example 1 and Example 4a of EP 2 824 117 A1 is subjected to a placement attempt. Table 16b shows the recipes for performing setting experiments and the determined bond stresses. Table 16b: Recipes for performing setting experiments for differentiation and determined bond stresses description SV-010 PMDETA SV-011 PMDETA SV-012 PMDETA SV-013 PMDETA BDDMA [g] 26.46 - 27.97 - HRI [g] - 26.84 - 28.37 PMDETA [g] 2.28 2.31 1.12 1.13 SolCop8 [g] 1.40 1.42 0.56 0.57 Sand [g] 43.81 44.43 44.29 44.92 H18 1.05 - 1.05 - Sum [g] 75.00 75.00 75.00 75.00 Bond stress [N / mm ² ] 0.37 1.56 1.02 0.10

As in Examples 1 and 4a of EP 2 824 117 A1 only BDDMA is used as the vinyl ester resin, further setting experiments are carried out using the resin formulation HRI. For reinforcement, sand is added in analogous amounts as in "Example 8: Excerpt from concrete". The determined bond stresses of the hardener system PMDETA - copper (II) salt are significantly lower than those of the hardener systems according to the invention (see Table 10).

In conclusion, it can be stated that the initiator system according to the invention imine metal salt leads to significantly more powerful and variable hardener systems than those described in US Pat EP 2 824 117 A1 claimed systems lead. This manifests itself both in the higher bond stresses, and in the wider potential selection of metal salts as accelerators, which is not limited to copper only. As an essential difference to EP 2 824 117 A1 It should again be noted that the radical starters which can be used according to the invention in the form of imines (aldimines and / or ketimines) contain an sp ² -hybridized nitrogen. The claimed in the EP nitrogen-containing ligands in the form of tertiary aliphatic amines have sp ³ -hybridized nitrogen atoms.

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

• DE 3226602 A1 [0002]
• EP 1586569 A1 [0002]
• EP 1329469 A1 [0005, 0040]
• EP 1975190 A1 [0005, 0040]
• EP 2017260 [0005, 0040]
• US 4348506 [0006]
• EP 2824117 A1 [0007, 0007, 0007, 0010, 0113, 0114, 0115, 0115]
• WO 2007/042199 [0038]
• US 2002/0091214 [0038]
• DE 102004035542 A1 [0040]
• EP 0387418 A2 [0043]
• DE 102014103923 A1 [0054]
• DE 3940309 A1 [0054]
• DE 4111828 A1 [0054, 0088]
• DE 19956509 [0060]
• EP 1935860 A1 [0063]
• DE 19531649 A1 [0063]
• WO 02/079341 [0067]
• WO 02/079293 [0067]

Cited non-patent literature

• DIN 16945 [0079]

Claims (18)

A hardener system for a synthetic resin composition comprising radically polymerizable compounds comprising the following components: a) at least one activator in the form of a metal salt and as free-radical initiator b1) at least one aldehyde and / or ketone and at least one primary amine, and / or b2) Imine which contains one or more imine structural units of the formula (I):

wherein independently of one another: the wavy line represents the organic radical of the amine used and has the meanings described below for suitable amines, or represents hydrogen; and R ₂ and R ₃ independently of one another are hydrogen and / or an unsubstituted or substituted, optionally double bonds and / or heteroatoms, mono- or polysubstituted or straight-chain organic radical which has at least one aliphatic, heteroaliphatic, alicyclic or heterocyclic molecular structure, or a combination of two or more of the aforementioned molecular structures, means, and / or salts thereof. The hardener system of claim 1, wherein (a) the activator is selected in the form of a metal salt from one or more salts of organic and / or inorganic acids with metals, eg selected from copper, iron, vanadium, manganese, cerium, cobalt, zirconium, or Bismuth, or mixtures of two or more thereof, in particular selected from vanadium, iron, manganese and copper, in particular in the form of salts or complexes with inorganic acid radicals, such as sulfate and / or carbonate radicals and / or organic acid radicals, for example carboxylate radicals, Wherein the organic acids are preferably saturated - such as carboxylates with CH ₃ , C ₂ -C ₂₀ -alkyl, a C ₆ -C ₂₄ -aryl radical or C ₇ -C ₃₀ -aralkyl radical, for example octoate, for example 2-ethylhexanoate (isooctanoate) , Neodecanoate, or acetylacetonate; in particular manganese carboxylates, such as Mn acetate or mn octoate, copper carboxylates, such as copper octoate 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 include, for example, iron chloride, iron sulfate, copper sulfate and copper chloride includes, are preferred; and / or (b2) the radical initiator at least one aldimine or ketimine selected from the group consisting of condensation with dehydration of a mono-, di or polyamine selected from aminols such as hydroxy-lower alkylamines, eg ethanolamine, diethanolamine, 1,3-diaminopropane 2-ol or 3-aminopropanol, or aromatic aminols such as 2-, 3- or 4-aminophenol; Alkyl / alkylene (mono or di) amines, in particular of the formula R ^a R ^b NE- (NR ^c R ^d ) where R ^a , R ^b , R ^c , R ^d independently of one another are H, alkyl or cycloalkyl radicals and E is a linear or branched, saturated or unsaturated alkylene chain having ≥ 2 C atoms, for example having a maximum of 40 carbon atoms, where the monoamines in the form of alkylamines are deleted from the parenthetical group and instead an H is present, preferably aminobutane, diaminoethane, Diaminopropane or other homologs such as 1,4-diaminobutane, 1,5-diaminopentane and 1,6-diaminohexane, 2-methyl-1,2-propanediamine, 2,2,4- or 2,4,4-trimethylhexamethylenediamine; Cycloalkyl / cycloalkylene (mono or di) amines or heterocycloalkyl / heterocycloalkylene (mono or di) amines, in particular of the formula R ^e R ^f NG- (NR ^g R ^h ), wherein R ^e , R ^f , R ^g , R ^h independently H, alkyl or cycloalkyl and G is a saturated or unsaturated cycloalkyl / cycloalkylene or heterocycloalkyl / Heterocycloalkylenrest with ≥ 4 ring atoms, and in particular with a maximum of 10, for example a maximum of 6 ring carbon atoms, wherein in the monoamines in the form of cycloalkylamines or heterocycloalkylamines, the parenthetical group is omitted and instead an H is present; wherein cyclohexylamines, diaminocyclohexanes, for example 1,4-cyclohexanediamine; 4,4`-methylene-bis-cyclohexylamine; Isophoronediamine, m-xylylenediamine, 2.5 (2.6) bis (aminomethyl) bicyclo [2.2.1] heptane (NBDA), octahydro-4,7-methanoindenes-1 (2), 5 (6) -dimethaneamines (TCD-diamine), 1,2-, 1-4 or especially 1,3-bis (aminomethyl) cyclohexane, or in Heterocycloalkylverbindungen aminoethylpiperazine, are preferred; polyfunctional amines, especially amino-functionalized polyoxyalkylenes such as 2-bis (aminoethoxy) ethane; or 1,13-diamino-4,7,10-trioxatridecane; Compounds of the formula H ₂ N- (CH ₂ ) _i -NH - [(CH ₂ ) _j -NH] _k - (CH ₂ ) ₁ -NH ₂ , wherein i, j and l are independently from 2 to 4 and k is 0, 1, 2, 3 or 4, such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and other homologs, dipropylenetriamine, bis (3-aminopropyl) amine; Aminoamides, polyaminoamides, Mannich bases or amine adducts or aminoalkyl silanes which contain at least one, preferably two hydrolyzable groups, such as alkoxy, for example methoxy or ethoxy bonded to the silicon, for example selected from the group comprising one or more of the following compounds: Aminoalkyltri- or -dialkoxysilanes, such as 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane, and N- (aminoalkyl) -amino-alkyltri- or -dialkoxysilanes, such as N- (2-aminoethyl) -3-aminopropyltrimethoxysilane or N- (2- Aminoethyl) -3-aminopropylmethyldimethoxysilane, further ureidoalkyltrimethoxysilanes such as 3-ureidopropyltrimethoxysilane; and mixtures of two or more thereof; with one or more aldehydes or ketones of the formula (II),

wherein: R ₂ , R _{3 are} independently hydrogen and / or an unsubstituted or substituted and / or optionally heteroatom-containing mono- or polysubstituted or straight-chain organic radical having at least one aliphatic, heteroaliphatic, alicyclic or heterocyclic molecular structure or a combination of two or more of the aforementioned molecular structures, means; wherein 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 to the carbonyl group, for example propanal, valeraldehyde, isovaleraldehyde, methoxyacetaldehyde, methyl isobutyl ketone, acetone or methyl ethyl ketone ; or in particular compounds which have only one (tertiary) hydrogen atom on the α-carbon atom to the carbonyl group is, for example, isobutyraldehyde, 2-ethylhexanal, 2-methylbutanal, 2-ethylbutanal, 2-methylvaleraldehyde, 2,3-dimethylvaleraldehyde, cyclohexylcarboxaldehyde or very preferably diisopropyl ketone, 3-methyl-2-pentanone or 2-methylcyclohexanone; or mixtures of two or more thereof.  Hardening system according to one of claims 1 or 2, wherein as radical starter in b2) only one or more aldimines are provided and no ketimine. The hardener system of claim 1, wherein (a) the activator is selected in the form of a metal salt from one or more salts of organic and / or inorganic acids with metals, eg selected from copper, iron, vanadium, manganese, cerium, cobalt, zirconium, or Bismuth, or mixtures of two or more thereof, in particular selected from vanadium, iron, manganese and copper, in particular in the form of salts or complexes with inorganic acid radicals, such as sulfate and / or carbonate radicals and / or organic acid radicals, for example carboxylate radicals, Wherein the organic acids are preferably saturated, such as carboxylates with CH ₃ , C ₂ -C ₂₀ -alkyl, a C ₆ -C ₂₄ aryl radical or C ₇ -C ₃₀ -aralkyl radical, for example octoate, for example 2-ethylhexanoate (isooctanoate), Neodecanoate, or acetylacetonate; in particular manganese carboxylates, such as Mn acetate or mn octoate, copper carboxylates, such as copper octoate 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 include, for example, iron chloride, iron sulfate, copper sulfate and copper chloride includes, are preferred; and / or b2) as radical initiator at least one of the mentioned in claim 2 and / or at least one aldehyde and / or ketone and as a primary amine one or more amino silanated fillers carrying primary amino groups, such as aminosilane treated quartz powder, or aminosilane-treated fumed silicas, are provided and included. Hardening system according to one of claims 1 or 2 or 3, wherein as free-radical initiator b2) one or more aldimines selected from the reaction products of isobutyraldehyde and 3-aminopropyl trimethoxysilane; of isobutyraldehyde and m-xylylenediamine; of isobutyraldehyde and 1,3-bis (aminomethyl) cyclohexane; of isobutyraldehyde and Jeffamine D230; of isobutyraldehyde and isophoronediamine; of isobutyric acid and Jeffamine DER-148; of isobutyraldehyde and diethyltoluenediamine; and isobutyraldehyde and cyclohexane-1,2-diamine; or mixtures of two or more of these reaction products; are provided. Hardening system according to one of claims 1 to 5, wherein (a) the activator is provided in the form of a metal salt of one or more salts of organic and / or inorganic acids with metals, for example selected from copper, iron, vanadium, manganese, cerium, cobalt , Zirconium, or bismuth, or mixtures of two or more thereof, in particular selected from vanadium, iron, manganese and copper, in particular in the form of salts or complexes with inorganic acid radicals, such as sulfate and / or carbonate radicals and / or organic acid radicals , For example, carboxylate radicals, - wherein the organic acids are preferably saturated - such as carboxylates with CH ₃ , C ₂ -C ₂₀ alkyl, a C ₆ -C ₂₄ aryl radical or C ₇ -C ₃₀ -Aralkylrest, for example octoate, for example 2-ethylhexanoate (Isooctanoate), neodecanoate, or acetylacetonate; in particular manganese carboxylates, such as Mn acetate or mn octoate, copper carboxylates, such as copper octoate 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 include, for example, iron chloride, iron sulfate, copper sulfate and copper chloride includes, are preferred; and / or (b1) the radical initiator at least one aldehyde or ketone of the formula (II),

wherein: R ₂ , R _{3 are} independently hydrogen and / or an unsubstituted or substituted and / or optionally heteroatom-containing mono- or polysubstituted or straight-chain organic radical having at least one aliphatic, heteroaliphatic, alicyclic or heterocyclic molecular structure or a combination of two or more of the aforementioned molecular structures, means; wherein 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 to the carbonyl group, for example propanal, valeraldehyde, isovaleraldehyde, methoxyacetaldehyde, 3,7- Dimethyl 6-octenal or 3,7-dimethyl-7-hydroxyoctanal, methyl isobutyl ketone, acetone or methyl ethyl ketone; or in particular to compounds which have only one (tertiary) hydrogen atom on the α-carbon atom to the carbonyl group is, for example, isobutyraldehyde, 2-ethylhexanal, 2-methylbutanal, 2-ethylbutanal, 2-methylvaleraldehyde, 2,3-dimethylvaleraldehyde, cyclohexylcarboxaldehyde, 3 , 7-dimethyl-2,6-octadienal, 3- (4-tert-butylphenyl) -2-methylpropanal, tetrahydrofuran-3-carboxaldehyde, tetrahydro-2-furancarboxaldehyde, 4-formyltetrahydropyran, tetrahydro-2H-pyran-2-carbaldehyde , Tetrahydro-pyran-3-carbaldehyde, diisopropyl ketone, 3-methyl-2-pentanone, 2-methylcyclohexanone, β-ionone or 6-methyl-5-hepten-2-one; or mixtures of two or more thereof, and at least one primary amine, preferably selected from the group comprising mono-, di-, and polyamines, especially 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, for example, 1,13-diamino-4,7,10-trioxatridecane, amine-functionalized polyoxyalkylenes [Jeffamine] or, for example: Triethylenetetramine and / or higher homologs, cycloalkyl or cycloalkylene (mono or di) amines, such as: isophorone diamine, 1,3-bisaminomethylcyclohexane, TCD-diamine, heterocycloalkyl or heterocycloalkylene (mono or di) amines, such as aminoethylpiperazine, aminol or ., such as: 1,3-diaminopropan-2-ol), and arylalkyl or arylalkylene (mono or di) amines, such as 1,3- or 1,4-benzenedimethanamine, selected and / or from the group of aminosilanized fillers ; Aminoamides, polyaminoamides, Mannich bases or amine adducts such as epoxide-amine adducts, isocyanate-amine adducts, Bucherer adducts and Michael addition adducts; Aminoalkylsilanes which contain at least one hydrolyzable group, such as alkoxy, for example methoxy or ethoxy bonded to silicon, for example selected from the group comprising one or more of the following compounds: aminoalkyltri- or -dialkoxysilanes, such as 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane, and N- (aminoalkyl) -amino-alkyltri- or -dialkoxysilanes, such as N- (2-aminoethyl) -3- aminopropyltrimethoxysilane or N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, further ureidoalkyltrimethoxysilanes such as 3-ureidopropyltrimethoxysilane; and aminosilanized fillers carrying primary amino groups, such as aminosilane-treated quartz flour, aminosilane-treated silica, or aminosilane-treated fumed silicas, and mixtures of two or more of said amines; the constituents aldehyde and / or ketone on the one hand and the constituent primary amine on the other hand preferably split separately into two components and only for mixing when using the hardener system when used in an adhesive, coating material or a molding compound, in particular in the attachment of anchoring agents in (Bau -) substrates, are provided. A hardener system according to claim 1, wherein (a) the activator is selected in the form of a metal salt from one or more salts of organic and / or inorganic acids with metals, for example selected from those recited in claim 2, and as radical initiator b1) at least one Aldehyde and / or ketone and at least one primary amine, wherein the aldehyde and / or ketone is preferably a compound which has at least one or more (primary and / or secondary) hydrogen atoms on the α-carbon atom to the carbonyl group, for example, propanal, valeraldehyde, isovaleraldehyde, methoxyacetaldehyde, 3,7-dimethyl-6-octenal or 3,7-dimethyl-7-hydroxyoctanal, methyl isobutyl ketone, acetone or methyl ethyl ketone; or in particular a compound which has only one (tertiary) hydrogen atom on the α-carbon atom to the carbonyl group is, for example, isobutyraldehyde, 2-ethylhexanal, 2-methylbutanal, 2-ethylbutanal, 2-methylvaleraldehyde, 2,3-dimethylvaleraldehyde, cyclohexylcarboxaldehyde, 3 , 7-dimethyl-2,6-octadienal, 3- (4-tert-butylphenyl) -2-methylpropanal (Lilial, Lysmeral), tetrahydrofuran-3-carboxaldehyde, tetrahydro-2-furancarboxaldehyde, 4-formyltetrahydropyran, tetrahydro-2H- pyran-2-carbaldehyde, tetrahydropyran-3-carbaldehyde, diisopropyl ketone, 3-methyl-2-pentanone, 2-methylcyclohexanone, β-ionones or 6-methyl-5-hepten-2-one; or mixtures of two or more thereof, and the primary amines are preferably those selected from the group consisting of mono-, di- and polyamines, especially 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-trioxatridecan, amine-functionalized polyoxyalkylenes [Jeffamine] or, for example: triethylenetetramine and / or higher homologs, cycloalkyl- or cycloalkylene (mono or di) amines, such as, for example: isophoronediamine, 1,3-bisaminomethylcyclohexane, TCD-diamine, heterocycloalkyl or heterocycloalkylene (mono or di) amines, such as, for example, aminoethylpiperazine, aminols or, for example: 1,3-diaminopropan-2-ol), and arylalkyl or arylalkylene (mono or di) amines, such as 1,3- or 1,4-benzenedimethanamine, and / or from the group of amino silanated fillers; Aminoamides, polyaminoamides, Mannich bases or amine adducts such as epoxide-amine adducts, isocyanate-amine adducts, Bucherer adducts and Michael addition adducts; Aminoalkylsilanes which contain at least one hydrolyzable group, such as alkoxy, for example methoxy or ethoxy-bonded to silicon, for example selected from the group comprising one or more of the following compounds: aminoalkyltri- or -di-alkoxysilanes, such as 3-aminopropyl- trimethoxysilane or 3-aminopropyltriethoxysilane, and N- (aminoalkyl) aminoalkyltri- or dialkoxysilanes such as N- (2-aminoethyl) -3-aminopropyltrimethoxysilane or N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, further ureidoalkyltrimethoxysilanes such as 3-ureidopropyltrimethoxysilane; and aminosilanized fillers bearing primary amino groups, such as aminosilane-treated quartz flour, aminosilane-treated silica, or aminosilane-treated fumed silicas; and mixtures of two or more of said amines; the constituents aldehyde and / or ketone on the one hand and the constituent primary amine on the other hand preferably split separately into two components and only for mixing when using the hardener system when used in an adhesive, coating material or a molding compound, in particular in the attachment of anchoring agents in (Bau -) substrates, are provided. and / or b2) an imine which contains one or more imine structural units of the formula (I) shown in claim 1, in particular obtainable by reacting at least one aldehyde and / or ketone with at least one primary amine, wherein the aldehyde and or ketone, preferably a compound which has at least one or more (primary and / or secondary) hydrogen atoms on the α-carbon atom to the carbonyl group, for example propanal, valeraldehyde, isovaleraldehyde, methoxyacetaldehyde, 3,7-dimethyl-6-octenal or 3 , 7-dimethyl-7-hydroxyoctanal, methyl isobutyl ketone, acetone or methyl ethyl ketone; or in particular a compound which has only one hydrogen atom on the α-carbon atom to the carbonyl group, for example isobutyraldehyde, 2-ethylhexanal, 2-methylbutanal, 2-ethylbutanal, 2-methylvaleraldehyde, 2,3-dimethylvaleraldehyde, cyclohexylcarboxaldehyde, 3, 7-dimethyl-2,6-octadienal, 3- (4-tert-butylphenyl) -2-methylpropanal, tetrahydrofuran-3-carboxaldehyde, tetrahydro-2-furancarboxaldehyde, 4-formyltetrahydropyran, tetrahydro-2H-pyran-2-carbaldehyde, Tetrahydro-pyran-3-carbaldehyde, diisopropyl ketone, 3-methyl-2-pentanone, 2-methylcyclohexanone, β-ionone or 6-methyl-5-hepten-2-one; or mixtures of two or more thereof, and the primary amines are preferably those selected from the group consisting of mono-, di-, and polyamines, especially 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, amine-functionalized polyoxyalkylenes [Jeffamine] or eg: triethylenetetramine and / or higher homologs, cycloalkyl- or cycloalkylene (mono or di) amines, such as, for example: isophoronediamine, 1,3-bisaminomethylcyclohexane, TCD-diamine, heterocycloalkyl or heterocycloalkylene (mono or di) amines, such as aminoethylpiperazine, aminol or, for example: 1,3-diaminopropan-2-ol), and arylalkyl or arylalkylene (mono or di) amines, such as 1,3- or 1,4-benzenedimethanamine, selected and / or from the group of amino silanated fillers; Aminoamides, polyaminoamides, Mannich bases or amine adducts such as epoxide-amine adducts, isocyanate-amine adducts, Bucherer adducts and Michael addition adducts; Aminoalkylsilanes which contain at least one hydrolyzable group, such as alkoxy, for example methoxy or ethoxy bonded to silicon, for example selected from the group comprising one or more of the following compounds: aminoalkyltri- or -dialkoxysilanes, such as 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane, and N- (aminoalkyl) -amino-alkyltri- or -dialkoxysilanes, such as N- (2-aminoethyl) -3-aminopropyltrimethoxysilane or N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, further ureidoalkyltrimethoxysilanes, such as 3-ureidopropyltrimethoxysilane; and aminosilanized fillers bearing primary amino groups, such as aminosilane-treated quartz flour, aminosilane-treated silica, or aminosilane-treated fumed silicas; and mixtures of two or more of said amines.  Use of a hardener system according to any one of claims 1 to 7 as an initiator system for a synthetic resin composition with free-radically polymerizable compounds, further as an ingredient d) at least one free-radically polymerizable compound. The use according to claim 8, wherein as the at least one radically polymerizable compound, a radical-curing unsaturated reaction resin having preferably at least 2 or more reactive non-aromatic unsaturated bonds, or a mixture of two or more reaction resins; in particular from the group of ethylenically unsaturated compounds comprising styrene and derivatives, vinyl esters, such as (meth) acrylates or urethane (meth) acrylates or itaconates, furthermore unsaturated polyesters, vinyl ethers, allyl ethers, dicyclopentadiene compounds and unsaturated fats; in particular one or more reactive resins comprising (free radically) curable esters having one or more unsaturated carboxylic acid residues; preferably in each case propoxylated or in particular ethoxylated aromatic diol, such as bisphenol A, bisphenol F or novolak (especially di) (meth) acrylates; Epoxy (meth) acrylates, in particular in the form of reaction products of di- or polyepoxides, for example bisphenol A, bisphenol F or novolak di- and / or polyglycidyl ethers, with unsaturated carboxylic acids, for example C ₂ - C ₇ -alkenecarboxylic acids, in particular (meth) acrylic acid; Urethane and / or urea (meth) acrylates, which also includes oligomeric or polymeric variants; or unsaturated polyester resins, or the like, or two or more of these curable unsaturated organic components; is provided.  Resin composition containing the ingredients a) at least one activator in the form of a metal salt as in any one of claims 1 to 4, as a radical chain starter b1) at least one aldehyde and / or ketone and a primary amine as mentioned in any one of claims 1, 4, 6 or 7 or b2) at least one ketimine or, in particular, aldimine as claimed in one of claims 1 to 5; and c) at least one free-radically polymerizable compound as defined in claim 6 or 9. A synthetic resin composition according to claim 10, wherein as the radical chain initiator b2) at least one ketimine or, in particular, aldimine as defined in any of claims 1 to 3, claim 5 or claim 6 is provided.  Synthetic resin composition according to claim 10, wherein at least one aldehyde and / or ketone and a primary amine as mentioned in one of claims 1, 2, 4, 6 or 7, in particular as mentioned in claim 6, are provided as free-radical initiator b1). Synthetic resin composition according to claim 10 or 11, characterized in that (a) the activator is selected in the form of a metal salt from one or more salts of organic and / or inorganic acids with metals, for example selected from copper, iron, vanadium, manganese, cerium, Cobalt, zirconium, or bismuth, or mixtures of two or more thereof, in particular selected from vanadium, iron, manganese and copper, in particular in the form of salts or complexes with inorganic acid radicals, such as sulfate and / or carbonate residues and / or organic Acid radicals, for example carboxylate radicals, wherein the organic acids are preferably saturated, such as carboxylates with CH ₃ , C ₂ -C ₂₀ -alkyl, a C ₆ -C ₂₄ -aryl radical or C ₇ -C ₃₀ -aralkyl radical, for example octoate, for example 2- Ethylhexanoate (isooctanoate), neodecanoate, or acetylacetonate; in particular manganese carboxylates, such as Mn acetate or mn octoate, copper carboxylates, such as copper octoate 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 include, for example, iron chloride, iron sulfate, copper sulfate and copper chloride includes, are preferred; and / or the radical initiator b2) at least one aldimine or ketimine selected from the group consisting of condensation with dehydration of the mono-, di- or polyamines mentioned in claim 2 with one or more aldehydes or ketones of the formula (II),

as defined in claim 2 are obtainable. A resin composition according to claim 10, wherein (a) the activator is selected in the form of a metal salt from one or more salts of organic and / or inorganic acids with metals, eg selected from those mentioned in claim 13; and / or b1) as radical initiator at least one of the mentioned in claim 2 and / or at least one aldehyde and / or ketone and as a primary amine one or more amino silanated fillers carrying primary amino groups, such as aminosilanbehandeltes quartz powder (eg Silbond AST ^® Fa. Quarzwerke GmbH, are provided and includes) aminosilane silica (eg Aktisil AM ^® by Hoffmann mineral), or aminosilane fumed silicas. as a radical initiator, one or more amino silanated fillers carrying primary amino groups, such as amino silane-treated quartz flour, aminosilane-treated silica, or aminosilane-treated fumed silicas, are or are included as the primary amine.  A synthetic resin composition according to any one of claims 10 to 14 in the form of a multi-component system or kit.  Use of a synthetic resin composition according to any one of claims 10 to 15 as an adhesive, coating material or molding compound.  Use of a synthetic resin composition according to any one of claims 10 to 14 for fixing anchoring agents in building substrates. A method or method for fixing anchoring means in holes or columns, wherein a synthetic resin composition according to any one of claims 10 to 14 and an anchoring means are sequentially or simultaneously inserted into a hole or a gap in a building substrate, or for attachment of fibers, films, fabrics or composites for reinforcing structures, in which a synthetic resin composition according to any one of claims 10 to 14 is used as a fastening means.