EP4041693A1

EP4041693A1 - Storage stable curing composition for a reaction resin

Info

Publication number: EP4041693A1
Application number: EP20780702.5A
Authority: EP
Inventors: Memet-Emin Kumru; Thomas Bürgel
Original assignee: Hilti AG
Current assignee: Hilti AG
Priority date: 2019-10-10
Filing date: 2020-09-30
Publication date: 2022-08-17
Also published as: EP3805301A1; JP2022550704A; WO2021069270A1; CN114502624A; AU2020364730A1; CA3148343A1; KR20220079871A; US20220372247A1

Abstract

The invention relates to a storage-stable curing composition for a reaction resin based on a radically curable compound comprising water, a peroxide and a rheological additive, wherein the rheological additive is a layered silicate-based rheological additive, and a reaction resin system containing said curing composition as a curing component and a resin component comprising a reaction resin based on radically curable compounds. The reaction resin system can be used in a thread-forming screw.

Description

Storage-stable hardener composition for a reaction resin

DESCRIPTION

The invention relates to a hardener composition for a reaction resin for use with thread-forming screws, in particular a storage-stable hardener composition based on a peroxide-water system.

The at least two-component mortar compounds used for chemical fastening technology generally contain in one component, i.e. the resin component, a resin curable by radical polymerization, for example an unsaturated polyester resin, an epoxy acrylate resin or a urethane methacrylate resin, which resins are in copolymerizable reactive thinners such as styrene or monomeric methacrylates can be solved. In addition to the resin, this resin component usually contains further additives such as accelerators, inhibitors and the like, as well as fillers or thickeners. The second necessary component of such a mortar mass for chemical fastening technology, that is to say the hardener component, contains the radical generator necessary for the polymerization of the hardenable resin, for example a peroxide. Since the The amount of free radical generator required for the radical polymerization of the resin component is much less than the amount of resin in the resin component and, in addition, the free radical generator, namely the peroxides, can decompose explosively, the hardener component usually contains a carrier material or phlegmatizer with which the volume the hardener component is brought to a reasonable value and the risk of explosion of the radical generator is reduced. The hardener component thus consists of or contains a hardener composition.

Finally, it is possible to provide further constituents which chemically react with the resin component and the hardener component in one or more further components in which these constituents are present separately from one another, so that no premature reaction can occur.

When used as intended, the spatially separated components, namely the resin component and the hardener component, are mixed in separate containers, e.g. multi-chamber bags, during use by inserting the multi-chamber bag into the borehole and inserting a corresponding fastening element in a rotating manner, For example, a thread-forming screw crushes the container and mixes the components contained therein.

This type of use of a reaction resin results in different requirements for the properties of both the individual components and the mixture thereof than for use with injection devices, in which the compound is mixed before it is introduced into the borehole.

Problems arise from the fact that, as a rule, the amount of hardener, i.e. the radical generator such as the peroxide, is much less than the amount of resin in the resin component, which makes the homogeneous mixing necessary to achieve consistently good and reproducible strength values both components made considerably more difficult. On the other hand, certain radical formers, for example dibenzoyl peroxide, are solid, so that the hardener composition usually contains a diluent in order to either dissolve or disperse the radical generator and present it in a larger volume overall, which can be mixed more easily with the resin component. In this context, volume ratios of resin component to hardener component of 7: 1 to 1: 1 are common, which, however, has the consequence that not negligible amounts of liquid carrier materials have to be added to the hardener composition and thus to the hardener component in order to set this volume ratio.

If the reaction resin system is used as intended, i.e. with a thread-forming screw, the screw is placed in a drill hole previously filled with a hardenable compound. Here, the annular gap between the outer surface of the base body and the wall of the borehole is too small for most types of hardenable masses that are very highly filled with inorganic fillers. It is thus only possible to use low-viscosity, curable masses, which are relatively expensive and have a lower strength compared to curable masses with fillers.

The cartridge systems known for anchor rods, such as those known from EP 0431 302 A2, EP 0432 087 A1, EP 0 312 776 A1 or EP 0638 705 A1, are not suitable for use with self-tapping screws due to the very small annular gap suitable because they either contain too coarse-grained fillers or the cartridges cannot be crushed with conventional thread-forming screws or the cartridges produce particles that are too large even when crushed. Since in this application only a few turns of the screw are possible before the screw is set, rapid mixing of the hardenable mass must be ensured so that it hardens reliably, which has not been possible with the known masses up to now. Sufficiently thin components are required for this.

According to the prior art, so-called phlegmatizers are used to adjust the flowability and the concentration of the radical generator in the hardener composition or the volume of the hardener composition, which serve on the one hand as a diluent and on the other hand to avoid undesired decomposition of the radical generator. As such Various types of non-reactive plasticizers, for example dicarboxylic acid esters, such as dioctyl phthalate, dioctyl adipate, liquid polyesters or polyalkylene glycol derivatives, have already been used, for which reference can be made to DE 3226602 A1, EP 0 432 087 A1 and EP 1 371 671 A1. The disadvantage of the phlegmatizers is that they act as plasticizers in the hardened mortar.

An organic / inorganic hybrid system is also known from DE 42 31 161 A1, which makes it possible to use water as a phlegmatizer. This has the advantage that after the components have been mixed, the water is bound by the hydraulically condensable compounds present and thus no longer has a softening function in the hardened mass.

A disadvantage of the aqueous hybrid system, however, is that the production of a hardener composition formulated on this basis is complex, since the peroxides desensitized with water are not stable to sedimentation. The hardener compositions must be stirred up and thickening additives added before filling. The hardener compositions obtained in this way, however, are too viscous for use with thread-forming screws, so that the usual thickeners, such as fumed silicas, cannot be used.

It has now been shown that the conventional approaches to the formation of the hardener composition as a hardener component of such an at least two-component mortar mass for use with thread-forming screws are not able to fully satisfy, because either the viscosity of the conventional hardener compositions is too high to be used with thread-forming screws or, if the viscosity is sufficiently low, the stability is unsatisfactory, particularly with regard to the sedimentation of the solid peroxides.

The object of the present invention is therefore to provide a hardener composition for use as a hardener component for at least one Provide two-component mortar mass with which it is possible not only to achieve the required flowability of the hardener component for use with thread-forming screws in a simple manner, but also to ensure high stability of the hardener component.

It has been shown that this object can be achieved in that the hardener composition contains, in addition to the radical generator, water and a rheology additive based on a sheet silicate.

For a better understanding of the invention, the following explanations of the terminology used herein are believed to be useful. For the purposes of the invention:

- “Reaction resin mixture” a mixture of at least one reaction resin and / or at least one reactive thinner, wherein the mixture can optionally contain an accelerator and / or an inhibitor;

- "Reaction resin based on a radically curable compound", also called "Reaction resin" or "base resin" for short, a usually solid or highly viscous "radically curable", i.e. radically polymerizable compound, which hardens through polymerization and forms a resin matrix; the reaction resin is the reaction product of a bulk reaction per se; this also includes the reaction batch for producing the base resin after the reaction has ended, which is present without isolation of the product and therefore, in addition to the free-radically curable compound, can contain the reaction resin, a reactive diluent, a stabilizer and a catalyst, if used;

- "Reactive thinners" liquid or low-viscosity monomers and oligomers, which dilute the reaction resin and thereby give it the viscosity necessary for its application, contain functional groups capable of reacting with the reaction resin and become predominantly part of the cured mass during polymerization (curing); - "Inhibitor" a compound capable of inhibiting the polymerisation reaction (hardening), which serves to avoid the polymerisation reaction and thus an undesired premature polymerisation of the reaction resin during storage (in this function often also referred to as a stabilizer) and / or the start of the Delaying the polymerization reaction immediately after the addition of the curing agent; the task of the inhibitor depends on the quantities in which it is used;

- "Hardening agent" e in substance which causes or initiates the polymerization (hardening) of the radical hardenable compound, such as the reaction resin;

- "Accelerator" a compound capable of accelerating the polymerization reaction (hardening), which serves to accelerate the formation of radicals, in particular from the hardening agent, i.e. to activate the hardening agent more quickly;

- "Solid peroxide", a substance (hardening agent) which has a solid state of aggregation at a temperature of 20 ° C and contains a peroxy group -O-O- that is homolytic with low energy expenditure, e.g. B. can be split by exposure to light (photolytic) or supply of heat (thermolytic); here two radical fragments are formed, which can start a radical reaction (e.g. polymerization);

- "Resin component" a mixture of the reaction resin and inorganic and / or organic additives (fillers and additives), such as an inhibitor and / or an accelerator;

- "Hardener composition" a mixture of the hardener and inorganic and / or organic additives (fillers and additives), such as a phlegmatizer, i.e. stabilizer for the hardener;

- "Hardener component" the component of a two- or multi-component reaction resin system, which consists of the hardener composition or contains it as a component; - "Filler" means an organic or inorganic, in particular inorganic compound, which can be passive and / or reactive and / or functional; "Passive" means that the connection is surrounded unchanged by the hardening resin matrix; “Reactive” means that the compound polymerizes into the resin matrix and forms an expanded network with the resin components; “Functional” means that the compound is not polymerized into the resin matrix but fulfills a certain function in the formulation;

- “Two-component reaction resin system” a reaction resin system which comprises two components stored separately from one another, generally a resin component and a hardener component, so that the reaction resin does not harden until the two components have been mixed;

- “Multi-component reaction resin system” a reaction resin system that comprises several components stored separately from one another, so that the reaction resin does not harden until all components have been mixed;

- "(Meth) acryi ... / ... (meth) acryi ..." that both the "Methacryl ... / ... methacryl ..." and the "Acryl ... /. .. acrylic ... “compounds are to be included; "Methacryl ... / ... methacryl ..." compounds are preferred in the present invention;

- "a", "an", "an" as an article in front of a chemical compound class, e.g. in front of the word "reactive thinner", that one or more compounds falling under this chemical compound class, e.g. various "reactive thinners", can be meant;

- “at least one”, “at least one”, “at least one” numerically “one or more” in a preferred embodiment, this term numerically means “one”, “one”, “one”;

“Contain”, “comprise” and “contain” mean that, in addition to the components mentioned, there may be more. These terms are meant to be inclusive and therefore also include “consist of”. “Consist of” is finally meant and means that no other components can be present. In a preferred embodiment, the terms “contain”, “comprise” and “include” mean the term “consist of”.

A first subject of the invention is the hardener composition according to claim 1. The subclaims 2 to 9 relate to preferred embodiments of this subject matter of the invention.

A second subject matter of the invention is also a multi-component reaction resin system according to claim 10, with a resin component comprising a free-radically curable compound, and with a hardener composition comprising a hardener composition according to claim 1. The further dependent claims 11 to 16 relate to preferred embodiments of this subject matter of the invention.

A third object of the invention is also the use of the multi-component mortar mass according to claim 17 for fastening and / or reinforcing thread-forming screws in solid substrates, in particular in stone or concrete.

In addition to water as a phlegmatizer, the hardener composition according to the invention contains a solid peroxide as a radical generator, preferably an organic peroxide. Particularly preferred solid peroxides are selected from the group consisting of alkyl peroxides, dialkyl peroxides, diacyl peroxides, alkyl hydroperoxides, hydroperoxides, perocarbonates, perketals and inorganic peroxides, provided these are solid. According to a most preferred embodiment, the hardener composition contains diacetyl peroxide, di-p-chlorobenzoyl peroxide, phthaloyl peroxide, succinyl peroxide, dilauryl peroxide, acetylcyclohexanesulphonyl peroxide, cyclohexane percarbonate, bis (4-f-butylcyclohexyl peroxide, dilenzoyl peroxide and cyclohexyl percarbonate, a silicon peroxide, dibanoyl peroxide and cyclohexyl peroxide) peroxide, di-p-chlorobenzoyl peroxide, di-p-chlorobenzoyl peroxide, di-p-chlorobenzoyl peroxide, a silicon peroxide. The use of diacyl peroxides, such as dibenzoyl peroxide or dilauroyl peroxide, is particularly preferred for processing in a temperature range from -25 ° C to + 60 ° C and thus on the usual outdoor construction sites. The peroxide is preferably present as a suspension together with the water. Corresponding suspensions are commercially available in different concentrations, such as, for example, the aqueous dibenzoyl peroxide suspensions from United Initiators (BP20SAQ, BP40SAQ). Perkadox 40L-W (from Nouryon), Luperox® EZ-FLO (from Arkema), Peroxan BP40W (from Pergan).

The peroxide can be contained in the reaction resin system in an amount of 2 to 50% by weight, preferably 5 to 45% by weight, particularly preferably 10 to 40% by weight, based on the resin component.

The hardener composition according to the invention contains, as rheology additive, a rheology additive based on a sheet silicate, in particular an activated or swellable sheet silicate. The swellable sheet silicate is particularly preferably a magnesium aluminum silicate or a sodium aluminum silicate.

In a preferred embodiment, the rheology additive consists of the swellable sheet silicate or contains this as the main component. “Main constituent” here means that the swellable sheet silicate makes up more than half of the rheology additive, that is to say more than 50% by weight, in particular 60 to 80% by weight. The rest are made up of other minerals, such as clay minerals, in particular accompanying minerals.

The rheological additive montmorillonite is particularly preferred or contains this as the main component, for example bentonite.

The amount of rheological additive to be used depends essentially on the amount of water, the skilled person being able to easily select the correct ratio of these components and also the components to be used, if necessary, such that the hardener composition has the required viscosity and flowability. The hardener composition preferably contains the rheological additive in an amount of 0.15 to 5% by weight, particularly preferably 1 to 3% by weight, based on the total weight of the hardener composition. ok

In an alternative embodiment, a further inorganic thickener, in particular based on silica, such as, for example, a hydrophilic pyrogenic silica, can be added to the rheology additive.

Apart from the rheology additive based on a sheet silicate, the hardener composition according to the invention preferably contains no further additives, such as fillers and / or additives.

The rheology additive is very particularly preferably free from organic thickeners, in particular polysaccharides such as xanthan or cellulose.

In addition to the ingredients just listed, the hardener composition can also contain other additives such as surfactants, emulsifiers, antifreeze agents, buffers and the like.

Nevertheless, in addition to the rheological additive based on a sheet silicate, the hardener composition can contain the fillers described below for the resin component in small amounts. The quantities are to be selected so that the properties, such as viscosity or flowability and the like, of the hardener composition or a hardener component containing it and in particular the stability of the hardener composition or a hardener component containing it are not adversely affected.

The water is contained in such an amount that, depending on the components of the hardener composition, the weight percent adds up to 100.

The hardener composition according to the invention can be used as the hardener component in a multi-component reaction resin system, which also includes two-component reaction resin systems.

The invention accordingly also relates to a multicomponent reaction resin system comprising a resin component and the hardener composition described above as the hardener component. The resin component contains at least one free-radically curable compound. The free-radically curable compound can be a reaction resin. Alternatively, the one compound that can be cured by free radicals can be a reactive diluent. According to a further alternative, the free-radically curable compound can also comprise a mixture of at least one reaction resin and at least one reactive diluent, a reaction resin mixture.

Suitable free-radically curable compounds as reaction resin are ethylenically unsaturated compounds, compounds with carbon-carbon triple bonds and thiol-Yn / ene resins, as are known to the person skilled in the art.

The free-radically curable compound, the reaction resin, an unsaturated compound based on urethane (meth) acrylate, epoxy (meth) acrylate, a (meth) acrylate of an alkoxylated bisphenol or a compound based on further ethylenically unsaturated compounds is particularly preferred.

Of these compounds, the group of ethylenically unsaturated compounds is preferred, which includes styrene and derivatives thereof, (meth) acrylates, vinyl esters, unsaturated polyesters, vinyl ethers, allyl ethers, itaconates, dicyclopentadiene compounds and unsaturated fats, of which unsaturated polyester resins and vinyl ester resins are particularly suitable are described, for example, in the applications EP 1 935 860 A1, DE 195 31 649 A1, WO 02/051903 A1 and WO 10/108939 A1. Vinyl ester resins (synonym: (meth) acrylate resins) are most preferred because of their hydrolytic resistance and excellent mechanical properties. Vinyl ester urethane resins, in particular urethane methacrylates, are very particularly preferred. These include, as preferred resins, the urethane methacrylate resins described in DE 102011 017 626 B4. In this regard, DE 10 2011 017 626 B4, and above all its description of the composition of these resins, in particular in the examples of DE 10 2011 017 626 B4, is incorporated herein by reference. Examples of suitable unsaturated polyesters which can be used in accordance with the invention are divided into the following categories, as described by M. Malik et al. in JMS - Rev. Macromol. Chem. Phys., C40 (2 and 3), p.139-165 (2000):

(1) Ortho resins: these are based on phthalic anhydride, maleic anhydride or fumaric acid and glycols, such as 1,2-propylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol or hydrogenated bisphenyl glycol;

(2) Iso-resins: these are made from isophthalic acid, maleic anhydride or fumaric acid and glycols. These resins can contain higher proportions of reactive thinners than the ortho resins;

(3) bisphenol A fumarates: these are based on ethoxylated bisphenol A and fumaric acid;

(4) HET acid resins (hexachloro-endo-methylene-tetrahydrophthalic acid resins): are resins obtained from anhydrides or phenols containing chlorine / bromine in the production of unsaturated polyester resins.

In addition to these resin classes, the so-called dicyclopentadiene resins (DCPD resins) can also be distinguished as unsaturated polyester resins. The class of DCPD resins is obtained either by modifying one of the above resin types by Diels-Alder reaction with cyclopentadiene, or alternatively they are obtained by a first reaction of a dicarboxylic acid, e.g. maleic acid, with dicyclopentadienyl, and then by a second reaction, the conventional production of an unsaturated polyester resin, the latter being referred to as a DCPD maleate resin.

The unsaturated polyester resin preferably has a molecular weight Mn in the range from 500 to 10,000 Dalton, more preferably in the range from 500 to 5000 and even more preferably in the range from 750 to 4000 (according to ISO 13885-1). The unsaturated polyester resin has an acid value in the range from 0 to 80 mg KOH / g resin, preferably im Range from 5 to 70 mg KOH / g resin (according to ISO 2114-2000). If a DCPD resin is used as the unsaturated polyester resin, the acid value is preferably 0 to 50 mg KOH / g resin.

For the purposes of the invention, vinyl ester resins are oligomers, prepolymers or polymers with at least one (meth) acrylate end group, so-called (meth) acrylate-functionalized resins, which also include urethane (meth) acrylate resins and epoxy (meth) acrylates.

Vinyl ester resins which only have unsaturated groups in the terminal position are, for example, by reacting epoxy oligomers or polymers (e.g. bisphenol A digylcidyl ether, epoxides of the phenol novolak type or epoxy oligomers based on tetrabromobisphenol A) with, for example (Meth) acrylic acid or (meth) acrylamide obtained. Preferred vinyl ester resins are (meth) acrylate-functionalized resins and resins obtained by reacting an epoxy oligomer or polymer with methacrylic acid or methacrylamide, preferably with methacrylic acid, and optionally with a chain extender such as diethylene glycol or dipropylene glycol. Examples of such compounds are known from the applications US 3297 745 A, US 3 772 404 A, US 4618 658 A, GB 2 217 722 A1, DE 3744 390 A1 and DE 41 31 457 A1.

Particularly suitable and preferred vinyl ester resins are (meth) acrylate-functionalized resins, which are produced, for example, by reacting di- and / or higher-functional isocyanates with suitable acrylic compounds, optionally with the help of hydroxy compounds that contain at least two hydroxyl groups, as described, for example, in DE 3940309 A1 can be obtained. The urethane methacrylate resins described in DE 10 2011 017 626 B4 (which are also referred to as vinyl ester urethane resins), the composition of which is incorporated herein by reference, are very particularly suitable and preferred.

Aliphatic (cyclic or linear) and / or aromatic di- or higher-functional isocyanates or prepolymers thereof can be used as isocyanates. The use of such compounds serves to increase the wettability and thus to improve the adhesive properties. Aromatic di- or higher-functional isocyanates or prepolymers thereof, aromatic difunctional or higher-functional prepolymers being particularly preferred. Toluylene diisocyanate (TDI), diisocyanatodiphenylmethane (MDI) and polymeric diisocyanatodiphenylmethane (pMDl) to increase chain stiffening and hexane diisocyanate (HDI) and isophorone diisocyanate (IPDI), which improve flexibility, may be mentioned (among which polymeric diisocyanatodiphenylmethane is particularly preferred)

Acrylic compounds are acrylic acid and acrylic acids substituted on the hydrocarbon radical, such as methacrylic acid, hydroxyl-containing esters of acrylic or methacrylic acid with polyhydric alcohols, pentaerythritol tri (meth) acrylate, glycerol di (meth) acrylate, such as trimethylolpropane di (meth) acrylate, neopentyl glycol mono (meth) acrylate suitable. Acrylic or methacrylic acid hydroxyalkyl esters, such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate, are preferred, especially since such compounds serve to sterically prevent the saponification reaction. Because of its lower alkali stability, acrylic acid is less preferred than acrylic acids substituted on the hydrocarbon radical.

As optionally replaceable hydroxy compounds, dihydric or higher alcohols are suitable, for example secondary products of ethylene or propylene oxide, such as ethanediol, di- or triethylene glycol, propanediol, dipropylene glycol, other diols, such as 1,4-butanediol, 1,6-hexanediol, Neopentyl glycol, diethanolamine, further bisphenol A or F or their ethox / propoxylation and / or hydrogenation or halogenation products, higher alcohols such as glycerol, trimethylolpropane, hexanetriol and pentaerythritol, hydroxyl-containing polyethers, for example oligomers of aliphatic or aromatic oxiranes and / or higher cyclic ethers, such as ethylene oxide, propylene oxide, styrene oxide and furan, polyethers which contain aromatic structural units in the main chain, such as those of bisphenol A or F, hydroxyl group-containing polyesters based on the above-mentioned alcohols or polyethers and dicarboxylic acids or their anhydrides, such as adipic acid, phthalic acid, tetra- or hexahydrophthalic acid, heteric acid, maleic acid acid, fumaric acid, itaconic acid, sebacic acid and the like. Hydroxy compounds with are particularly preferred aromatic structural units for chain stiffening of the resin, hydroxy compounds that contain unsaturated structural units, such as fumaric acid, to increase the crosslinking density, branched or star-shaped hydroxy compounds, in particular trihydric or higher-valent alcohols and / or polyethers or polyesters, which contain their structural units, branched or Star-shaped urethane (meth) acrylates for achieving lower viscosity of the resins or their solutions in reactive thinners and higher reactivity and crosslinking density.

The vinyl ester resin preferably has a molecular weight Mn in the range from 500 to 3000 Dalton, more preferably from 500 to 1500 Dalton (according to ISO 13885-1). The vinyl ester resin has an acid value in the range from 0 to 50 mg KOH / g resin, preferably in the range from 0 to 30 mg KOH / g resin (according to ISO 2114-2000).

All of these reactive resins, which can be used according to the invention as free-radically curable compounds, can be modified according to methods known to the person skilled in the art, for example to achieve lower acid numbers, hydroxide numbers or anhydride numbers, or made more flexible by introducing flexible units into the basic structure, and like that.

In addition, the reaction resin can also contain other reactive groups which can be polymerized with a radical initiator such as peroxides, for example reactive groups which are derived from itaconic acid, citraconic acid and allylic groups and the like.

In one embodiment, the resin component of the reaction resin system contains, in addition to the reaction resin, at least one further low-viscosity, free-radically polymerizable compound as a reactive diluent. This is expediently added to the reaction resin and is therefore contained in the resin component.

Suitable, in particular low-viscosity, free-radically curable compounds as reactive diluents are described in the applications EP 1 935 860 A1 and DE 195 31 649 A1. The reaction resin system preferably contains a (meth) acrylic acid ester as reactive diluent, the following being particularly preferred (Meth) acrylic acid esters can be used: hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate; Alkanediol (meth) acrylates such as ethanediol-1, 2-di (meth) acrylate, propanediol-1, 3-di (meth) acrylate, butanediol-1, 2- di (meth) acrylate, butanediol-1, 3-di ( meth) acrylate, butanediol 1, 4-di (meth) acrylate, hexanediol 1, 6-di (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenylethyl (meth) acrylate,

Tetrahydrofurfuryl (meth) acrylate; Trimethylolpropane tri (meth) acrylate;

Ethyl triglycol (meth) acrylate; N, N-dimethylaminoethyl (meth) acrylate; N, N-

Dimethylaminomethyl (meth) acrylate; Acetoacetoxyethyl (meth) acrylate;

Alkylene (meth) acrylates such as ethylene and diethylene glycol di (meth) acrylate; Oligo- and polyalkylene glycol di (meth) acrylates such as PEG200 di (meth) acrylate; Methoxypolyethylene glycol mono (meth) acrylate; Trimethylcyclohexyl (meth) acrylate;

Dicyclopentenyloxyethyl (meth) acrylate; Tricyclopentadienyl di (meth) acrylate;

Dicyclopentenyloxyethyl crotonate; Bisphenol A (meth) acrylate;

Novolak epoxidi (meth) acrylate; Di - [(meth) acryloyl-maleoyl] -tricyclo-decane 5.2.1 0. ^26; 3- (meth) acryloyl-oxymethyl-tricylo-5.2.1.0. ²⁶ decane; 3- (meth) cyclopentadienyl (meth) acrylate; isobornyl (meth) acrylate; Decalyl 2- (meth) acrylate; Tetrahydrofurfuryl (meth) acrylate; and alkoxylated tri-, tetra- and pentamethyl acrylates.

In principle, other conventional free-radically polymerizable compounds can also be used, alone or in a mixture with the (meth) acrylic acid esters described in the previous paragraph, e.g. styrene, α-methylstyrene, alkylated styrenes such as tert-butylstyrene, divinylbenzene and vinyl and allyl compounds. Examples of such vinyl or allyl compounds are hydroxybutyl vinyl ether, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, trimethylol propane divinyl ether, trimethylol propane trivinyl ether, mono-, di-, tri-, tetra- and polyalkylene glycol vinyl ethers, mono-, di-, tri-, tetra-allycol and polyalkylene glycols , Divinyl adipate, trimethylolpropane diallyl ether and trimethylolpropane triallyl ether.

Preferred reactive diluents are the further reactive diluents used in the examples.

The free-radically curable compound can be used in an amount of 10 to 99.99% by weight, preferably 15 to 97% by weight, particularly preferably 30 to 95% by weight, based on the Resin component to be contained in the reaction resin system. The free-radically curable compound can either be a reaction resin based on a free-radically curable compound or a reactive thinner or a mixture of a reaction resin with two or more reactive thinners.

In the event that the free-radically curable compound is a reaction resin mixture, the amount of the mixture that can be contained in the reaction resin system corresponds to the amount of the free-radically curable compound, namely from 10 to 99.99% by weight, preferably 15 to 97% by weight, particularly preferably 30 to 95% by weight, based on the resin component, with the proportion of the reaction resin being 0 to 100% by weight, preferably 30 to 65% by weight and the The proportion of the reactive diluent or a mixture of several reactive diluents is 0 to 100% by weight, preferably 35 to 70% by weight.

The total amount of the free-radically curable compound depends on the degree of filling, i.e. the amount of inorganic fillers, including the fillers listed below, in particular the hydrophilic fillers, the other inorganic additives and the hydraulically setting or polycondensable compounds.

In a further embodiment, the resin component of the reaction resin system according to the invention also contains at least one accelerator. This accelerates the hardening reaction.

Suitable accelerators are known to the person skilled in the art. These are conveniently amines.

Suitable amines are selected from the following compounds, which are described, for example, in application US 2011071234 A1: dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-propylamine, isopropylamine, diisopropylamine, triisopropylamine , n-butylamine, isobutylamine, tert-butylamine, di-n-butylamine, diisobutylamine, tri-isobutylamine, pentylamine, isopentylamine, diisopentylamine, hexylamine, octylamine, dodecylamine, laurylamine, stearylamine, aminoethanol, diethanolamine, triethanolamine, Dimethyl- (2-chloroethyl) amine, 2-ethylhexylamine, bis- (2-chloroethyl) amine, 2-ethylhexylamine, bis- (2-ethylhexyl) amine, N-methylstearylamine, dialkylamines, ethylenediamine, N, N'-dimethylethylenediamine, Tetramethylethylenediamine,

Diethylenetriamine, permethyldiethylenetriamine, triethylenetetramine, tetraethylene pentamine, 1,2-diaminopropane, di-propylenetriamine, tripropylenetetramine, 1,4-diaminobutane, 1,6-diaminohexane, 4-amino-1-diethylaminopentane, 2,5-diamino-2,5- dimethylhexane, trimethylhexamethylenediamine, N, N-dimethylaminoethanol, 2- (2-

Diethylaminoethoxy) ethanol, bis (2-hydroxyethyl) oleylamine, tris [2- (2-hydroxyethoxy) ethyl] amine, 3-amino-1-propanol, methyl (3-aminopropyl) ether, ethyl - (3-aminopropyl) ether, 1,4-butanediol bis (3-aminopropyl ether), 3-dimethylamino-1-propanol, 1-amino-2-propanol, 1-diethylamino-2-propanol, diisopropanolamine, methyl bis - (2-hydroxypropyl) amine, tris (2-hydroxypropyl) amine, 4-amino-2-butanol, 2-amino-2-methylpropanol, 2-amino-2-methyl-propanediol, 2-amino-2- hydroxymethylpropanediol, 5-diethylamino-2-pentanone, 3-methylaminopropiononitrile, 6-aminohexanoic acid, 11-aminoundecanoic acid, 6-aminohexanoic acid ethyl ester, 11-aminohexanoic acid isopropyl ester, cyclohexylamine, N-methylcyclohexylamine, N, N-dimethylcyclohexylaminyl, cyclohexylaminyl, cyclohexylaminyl N- (2-hydroxyethyl) -cyclohexylamine, N, N-bis- (2-hydroxyethyl) -cyclohexylamine, N- (3-aminopropyl) -cyclohexylamine,

Aminomethylcyclohexane, hexahydrotoluidine, hexahydrobenzylamine, aniline, N-methylaniline, N, N-dimethylaniline, N, N-diethylaniline, N, N-di-propylaniline, isobutylaniline, toluidine, diphenylamine, hydroxyethylaniline) aniline (chloroethylaniline), bis- , Aminophenols, aminobenzoic acids and their esters, benzylamine, dibenzylamine, tribenzylamine, methyldibenzylamine, a-phenylethylamine, xylidine, diisopropylaniline, dodecylaniline, aminonaphthalene, N-methylaminonaphthalene, N, N-

Dimethylaminonaphthalene, N, N-dibenzylnaphthalene, diaminocyclohexane, 4,4'-diamino-dicyclohexylmethane, diamino-dimethyl-dicyclohexylmethane, phenylenediamine, xylylenediamine, diaminobiphenyl, naphthalenediamines, benzidines, aminopropyl) - (aminophen) -thiophenols, aminodiphenyl ethers, aminocresols, morpholine, N-methylmorpholine, N-phenylmorpholine, hydroxyethylmorpholine, N-methylpyrrolidine, pyrrolidine, piperidine, hydroxyethylpiperidine, pyrroles, pyridines, quinolines, indoles, indiazolenines, carbazoles, pyrazoles, imidazoles , Aminomorpholine, dimorpholine ethane, [2,2,2] -diazabicyclooctane and N, N-dimethyl-p-toluidine. Preferred amines are aniline and toluidine derivatives and N, N-bisalkylarylamines, such as N, N, -dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, N, N-

Bis (hydroxyalkyl) arylamines, N, N-bis (2-hydroxyethyl) aniline, N, N-bis (2-hydroxyethyl) toluidine, N, N-bis (2-hydroxypropyl) aniline, N, N-bis (2- hydroxypropyl) toluidine, N, N-bis (3-methacryloyl-2-hydroxypropyl) -p-toluidine, N, N-dibutoxyhydroxypropyl-p-toluidine and 4,4'-bis (dimethylamino) diphenylmethane.

Polymeric amines, such as those obtained by polycondensation of N, N-bis (hydroxyalkyl) aniline with dicarboxylic acids or by polyaddition of ethylene oxide and these amines, are also suitable as accelerators.

Preferred accelerators are N, N-bis (2-hydroxypropyl) toluidine, N, N-bis (2-hydroxyethyl) toluidine and para-toluidine ethoxylate (Bisomer ^® PTE).

The accelerator can be contained in the reaction resin system in an amount of 0 to 10% by weight, preferably 0.01 to 5% by weight, particularly preferably 0.5 to 3% by weight, based on the resin component.

In yet another embodiment, the resin component of the reaction resin system according to the invention furthermore contains an inhibitor both for the storage stability of the resin component and for setting the gel time. The inhibitor can be contained in the reaction resin system alone or together with the accelerator. A correspondingly coordinated accelerator-inhibitor combination is preferably used to set the processing time or gel time.

The inhibitors usually used for free-radically polymerizable compounds, as known to the person skilled in the art, are suitable as inhibitors. The inhibitors are preferably selected from phenolic compounds and non-phenolic compounds, such as stable radicals and / or phenothiazines. 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-tri-methylphenol, 2,4,6-tris (dimethylaminomethyl) phenol, 4,4'-thio-bis (3-methyl-6-tert-butylphenol), 4,4'-isopropylidenediphenol, 6, 6'-di-tert-butyl-4,4'-bis (2,6-di-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di- tert-butyl-4-hydroxybenzyl) benzene, 2,2'-methylene-di-p-cresol, pyrocatechol and butylpyrocatechols, such as 4-tert-butylpyrocatechol, 4,6-di-tert-butylpyrocatechol, hydroquinones, such as hydroquinone, 2 - methyl hydroquinone, 2-tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, 2,6-di-tert-butyl hydroquinone, 2,6-dimethyl hydroquinone, 2,3,5-trimethyl hydroquinone, benzoquinone, 2,3,5 , 6-tetrachloro-1,4-benzoquinone, methylbenzoquinone, 2,6-dimethylbenzoquinone, naphthoquinone, or mixtures of two or more thereof, are suitable.

Phenothiazines, such as phenothiazine and / or derivatives or combinations thereof, or stable organic radicals, such as galvinoxyl and N-oxyl radicals, are preferred as non-phenolic or anaerobic inhibitors, i.e. in contrast to the phenolic inhibitors also effective without oxygen.

Examples of N-oxyl radicals that can be used are those described in DE 199 56 509. Suitable stable N-oxyl radicals (nitroxyl radicals) can be selected from 1-oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol (also referred to as TEMPOL), 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one (also referred to as TEMPON), 1-oxyl-2,2,6,6-tetramethyl-4-carboxyl-piperidine (also known as 4-carboxy- TEMPO), 1-oxyl-2,2,5,5-tetramethylpyrrolidine, 1-oxyl-2, 2,5,5-tetramethyl-3-carboxylpyrrolidine (also referred to as 3-carboxy-PROXYL), aluminum-N- nitrosophenylhydroxylamine, diethylhydroxylamine can be selected. Furthermore, suitable N-oxyl compounds are oximes, such as acetaldoxime, acetone oxime, methyl ethyl ketoxime, salicyloxime, benzoxime, glyoximes, dimethylglyoxime, acetone-O- (benzyloxycarbonyl) oxime and the like.

These compounds are particularly useful and mostly necessary because otherwise the desired storage stability of preferably more than 3 months, in particular 6 months or more, cannot be achieved. The UV stability and, in particular, the storage stability can be increased considerably in this way. Furthermore, pyrimidinol or pyridinol compounds substituted in the para position to the hydroxyl group, as described in patent specification DE 102011 077248 B1, can be used as inhibitors.

Preferred inhibitors are 1-oxyl-2,2,6,6-tetramethylpiperidine (TEMPO) and 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol (TEMPOL), catechols, particularly preferably te / f-butyl - Pyrocatechol and Brenzk through the functional group, the desired properties are achieved (compared to the reactive thinners otherwise used), BHT and phenothiazine.

The inhibitors can, depending on the desired properties of the reaction resin system, be used either alone or as a combination of two or more thereof. The combination of the phenolic and the non-phenolic inhibitors enables a synergistic effect, as is also shown by the setting of an essentially drift-free setting of the gel time of the reaction resin composition.

The inhibitor can be contained in the reaction resin system in an amount of 0 to 5% by weight, preferably 0.001 to 3% by weight, particularly preferably 0.01 to 1% by weight, based on the resin component. If several inhibitors are contained, the amount just mentioned corresponds to the total amount of inhibitors.

According to one embodiment, the resin component contains inorganic additives, such as fillers and / or other additives.

Customary fillers, preferably mineral or mineral-like fillers, such as quartz, glass, sand, quartz sand, quartz powder, porcelain, corundum, ceramics, talc, silica (e.g. fumed silica), silicates, clay, titanium dioxide, chalk, barite, are used as fillers , Feldspar, basalt, aluminum hydroxide, granite or sandstone, polymeric fillers such as thermosets, hydraulically hardenable fillers such as gypsum, quicklime or cement (e.g. alumina or Portland cement), metals such as aluminum, carbon black, and also wood, mineral or organic fibers, or the like, or mixtures of two or more more of it, which can be added as a powder, in granular form or in the form of shaped bodies, use. The fillers can be in any form, for example as powder or flour or as shaped bodies, e.g. B. in cylinder, ring, ball, plate, rod, saddle or crystal form, or also in fiber form (fibrillar fillers), and the corresponding base particles preferably have a maximum diameter of 10 mm. However, the globular, inert substances (spherical shape) have a preferential and clearly reinforcing effect.

Fillers are preferably present in the resin component in an amount of 0.01 to 90, in particular 0.01 to 60, in particular 0.01 to 50% by weight.

Further conceivable additives are also rheology additives, such as, if necessary, organically aftertreated pyrogenic silica, bentonites, alkyl and methyl celluloses, castor oil derivatives or the like, plasticizers, such as phthalic or sebacic esters, stabilizers, antistatic agents, thickeners, flexibilizers, curing catalysts, rheological additives, wetting agents, such as dyes or, in particular, pigments, for example for differently coloring the components for better control of their mixing, or the like, or mixtures of two or more thereof. Non-reactive diluents (solvents) can also be present, preferably in an amount of up to 30% by weight, based on the respective component (reaction resin mortar, hardener), for example from 1 to 20% by weight, such as lower alkyl ketones, e.g. B. acetone, di-lower alkyl-lower alkanoylamides such as dimethylacetamide, lower alkylbenzenes such as xylenes or toluene, phthalic acid esters or paraffins, or water.

In one embodiment of the invention, in addition to the free-radically curable compound present, the resin component also contains a hydraulically setting or polycondensable inorganic compound, in particular cement. Such hybrid mortar systems are described in detail in DE 42 31 161 A1. The resin component preferably contains cement as a hydraulically setting or polycondensable inorganic compound, for example Portland cement or aluminate cement, cements free of transition metal oxides or low in transition metal being particularly preferred. As a hydraulically setting inorganic Plaster of paris can also be used as such or mixed with the cement. As a polycondensable inorganic compound, the resin component can also comprise silicate, polycondensable compounds, in particular substances containing soluble, dissolved and / or amorphous silicon dioxide, such as, for example, pyrogenic silica.

The hydraulically setting or polycondensable compound can be present in the reaction resin system in an amount of 0 to 30% by weight, preferably 1 to 25% by weight, particularly preferably 5 to 20% by weight, based on the resin component.

As already described, provided that the viscosity and storage stability of the hardener composition are not adversely affected, the hardener component can also contain fillers and / or inorganic additives, the fillers and additives being the same as those just mentioned.

In order to ensure fast and reliable mixing when using thread-forming screws and also to ensure clean and safe handling when using thread-forming screws, it is necessary to keep the viscosity not only of the hardener component but also of the resin component as low as possible, but at the same time to enable a high viscosity of the mass after mixing the resin component and the hardener component. This enables the screws to be set cleanly and safely, without the risk of contaminating the user or the immediate work environment.

Therefore, in a particularly preferred embodiment, the resin component contains an inorganic filler with hydrophilic properties.

In particular, the surfaces, but also the internal constituents of the fillers, can have hydrophilic properties. Hydrophilic properties mean that the fillers interact with water or can react with water. This ensures that immediately after the resin component and the water-containing hardener component have been mixed, the mass obtained becomes so viscous that it becomes stable and thus no longer runs out of the borehole, which is particularly advantageous for overhead fixings or wall fixings. In particular, the surfaces of the inorganic fillers can be modified by hydrophilic coatings, primers or seals.

Examples of inorganic fillers having hydrophilic properties include those whose surface is treated with a hydrophilic surface treating agent. Examples of such hydrophilic surface treatment agents include, among others, silane surface treatment agents, titanate surface treatment agents, aluminum surface treatment agents, zirconium aluminate surface treatment agents, Al2O3, PO2, ZrO2, silicone and aluminum stearate, among which a silane surface treatment agent is preferred.

According to a further preferred embodiment of the multicomponent reaction resin system according to the invention, the inorganic filler comprises minerals selected from a group consisting of alkaline earth metals and their salts, bentonite, carbonates, silicas, silica gel, salts of alkaline earth metals with silicic acid and silicates, in particular silicas.

The inorganic filler can be produced by a dry method such as vapor deposition or incineration, or by a wet method such as precipitation. A commercially available product can also be used. Taking into account the rheological properties of the reaction resin system of the hydrophilic inorganic filler is preferably a fine filler, having a surface area of more than 80m ² / g, preferably of more than 150 m ² / g and more preferably between 150 and 400 m ² / g.

According to a further preferred embodiment of the multicomponent reaction resin system according to the invention, the inorganic filler comprises a silicon oxide-based filler.

According to a further particularly preferred embodiment of the multicomponent reaction resin system according to the invention, the inorganic filler comprises a silica. The silica is not limited to any particular type or its manufacture. The silica can be a natural or a synthetic silica.

The silica is preferably an amorphous silica, which is selected from the group consisting of colloidal silica, wet-chemically produced silicas such as precipitated silicas, silica gels, silica sols, pyrogenic or thermally produced silicas, which are produced, for example, in an electric arc, plasma or by flame hydrolysis, silica smoke, silica glass ( Quartz glass), kieselgut (quartz material) and skeletons of radiolarians and diatoms in the form of kieselguhr is selected.

The proportion of the hydrophilic inorganic filler depends on the desired properties of the multi-component reaction resin system. The hydrophilic inorganic filler is usually used in an amount of 0 to 15% by weight, preferably 0.1 to 10% by weight and particularly preferably in the range of 1 to 7% by weight, based in each case on the resin component, the total filler content being in the abovementioned range, namely in the range from 0.01 to 90, in particular 0.01 to 60, especially 0.01 to 50% by weight, based on the resin component.

In the embodiments described below, the quantities (% by weight) relate in each case to the individual components, that is to say the resin component and the hardener component, unless otherwise stated. The actual amounts are such that the% by weight of the respective component adds up to 100.

In a preferred embodiment of the hardener composition according to the invention, it contains: at least one hardener which is a solid peroxide,

Water; and a layered silicate based rheology additive.

In a preferred aspect of this first embodiment, the solid peroxide is suspended in the water. In a further preferred embodiment of the hardener composition according to the invention, it contains: at least one hardener which is a solid peroxide,

Water, and one as a rheology additive based on a swellable sheet silicate.

In a preferred aspect of this embodiment, the solid peroxide is suspended in the water.

In an even more preferred embodiment of the hardener composition according to the invention, it contains: at least one hardener which is a solid peroxide,

Water, and a rheology additive based on a swellable magnesium-aluminum-silicate or sodium-aluminum-silicate.

In a particularly preferred embodiment of the hardener composition according to the invention, it contains: at least one hardener which is a solid peroxide, in particular dibenzoyl peroxide,

Water and

Bentonite as a rheology additive based on a swellable sheet silicate.

The hardener composition according to the invention can be used as hardener component in a reaction resin system.

In a first preferred embodiment of such a reaction resin system, the resin component contains:

- at least one free-radically curable compound and at least one inorganic filler, and the hardener component contains: at least one hardener which is a solid peroxide;

Water; and a layered silicate based rheology additive.

In a preferred aspect of this first embodiment, the solid peroxide is suspended in the water. In a further preferred aspect, the reaction resin is stabilized by an inhibitor and / or the gel time of the mixture of resin component and hardener component is adjusted with an - optionally further - inhibitor. In a further preferred aspect of this first embodiment, the resin component contains:

10 to 99.99% by weight, preferably 15 to 97% by weight, particularly preferably 30 to 95% by weight of the at least one free-radically curable compound, and

- 0.01 to 90 wt .-%, preferably 3 to 85 wt .-%, particularly preferably 5 to 70 wt .-% of the at least one inorganic filler, and the hardener component contains:

- 2 to 50 wt .-%, preferably 5 to 45 wt .-%, particularly preferably 10 to 40 wt .-% of the at least one curing agent, which is a peroxide, and

50 to 98% by weight, preferably 55 to 95% by weight, particularly preferably 60 to 90% by weight of water, as well as

0.15 to 5% by weight, preferably 1 to 3% by weight of the rheological additive based on layered silicate.

In a further preferred second embodiment of the reaction resin system, the resin component consequently contains:

- At least one reaction resin mixture of at least one reaction resin and at least one reactive diluent as a free-radically curable compound; and at least one inorganic filler, and the hardener component contains: at least one hardener which is a solid peroxide,

Water, and a layered silicate-based rheology additive. In a preferred aspect of this second embodiment, the solid peroxide is suspended in the water. In a further preferred aspect of this second embodiment, the resin component contains:

- 85 to 99.99% by weight, preferably 90 to 99.9% by weight, particularly preferably 93 to 99% by weight of a mixture, the reaction resin mixture, from 0 to 99.9% by weight, preferably 20 to 80% by weight, based on the total weight of the mixture, of the at least one reactive resin and 0 to 99.99% by weight, preferably 80 to 20% by weight, based on the total weight of the mixture, of the at least one reactive diluent as radically curable compound, and

- 0.01 to 15 wt .-%, preferably 0.1 to 10 wt .-%, particularly preferably 1 to 7 wt .-% of the at least one inorganic filler, and the hardener component contains:

- 2 to 50 wt .-%, preferably 5 to 45 wt .-%, particularly preferably 10 to 40 wt .-% of the at least one peroxide as curing agent and

50 to 98% by weight, preferably 55 to 95% by weight, particularly preferably 60 to 90% by weight of water

0.15 to 5% by weight, preferably 1 to 3% by weight, of the layered silicate-based rheological additive.

In a further preferred third embodiment of the reaction resin system, the resin component contains:

- a reaction resin mixture of at least one reaction resin and a reactive diluent as a free-radically curable compound, at least one inhibitor, at least one accelerator, and at least one inorganic filler, and the curing component contains: at least one curing agent which is a solid peroxide,

Water, and a layered silicate-based rheology additive. In a preferred aspect of this third embodiment, the solid peroxide is suspended in the water. In a further preferred aspect of this third embodiment, the resin component contains:

- 0.011 to 5 wt .-%, preferably 0.01 to 3 wt .-%, particularly preferably 0.1 to 1 wt .-% of the at least one inorganic filler,

- 0.01 to 10% by weight, preferably 0.5 to 5% by weight, more preferably 1 to 3% by weight of the at least one accelerator,

0.001 to 5% by weight, preferably 0.01 to 3% by weight, more preferably 0.1 to 1% by weight of the at least one inhibitor, and the hardener component contains:

- 2 to 50% by weight, preferably 5 to 45% by weight, particularly preferably 10 to 40% by weight of the at least one peroxide as curing agent,

- 50 to 98 wt .-%, preferably 55 to 95 wt .-%, particularly preferably 60 to 90 wt .-% water and

In a preferred aspect of this embodiment, the viscosity of the mixture of the resin component and the hardener component is adjusted by the inorganic additive in such a way that the mixture becomes stable immediately after mixing. In a further preferred fourth embodiment of the reaction resin system, the resin component consequently contains: at least one reaction resin mixture of at least one reaction resin and a reactive diluent as a free-radically curable compound, at least one inhibitor, at least one accelerator, and at least one inorganic filler with hydrophilic properties, and the hardener component contains: at least one hardener which is a solid peroxide,

Water, and a layered silicate-based rheology additive.

In a preferred aspect of this fourth embodiment, the solid peroxide is suspended in the water. In a further preferred aspect of this fourth embodiment, the reaction resin system contains the constituents specified in more detail in the amounts given in the third aspect.

In a particularly preferred fifth embodiment of the reaction resin system, the resin component contains: at least one compound based on urethane (meth) acrylate as reaction resin, at least one reactive diluent, at least one inhibitor, at least one accelerator, and at least one inorganic filler with hydrophilic properties, and the resin component contains: at least one curing agent, which is a solid peroxide,

Water, and one as a rheology additive based on a swellable sheet silicate.

In a preferred aspect of this embodiment, the solid peroxide is suspended in the water. In a further preferred aspect of this fifth embodiment, the reaction resin system contains the constituents specified in more detail in the amounts given in the third aspect.

In a further particularly preferred sixth embodiment of the reaction resin system, the resin component contains:

- at least one compound based on urethane (meth) acrylate reaction resin, at least one reactive diluent, at least one inhibitor, at least one accelerator, and at least one inorganic filler with hydrophilic properties, and the resin component contains: at least one curing agent which is a solid peroxide, in particular dibenzoyl peroxide,

Water, and a rheology additive based on a swellable magnesium-aluminum-silicate or a sodium-aluminum-silicate.

In a preferred aspect of this embodiment, the solid peroxide is suspended in the water. In a further preferred aspect of this sixth embodiment, the reaction resin system contains the constituents specified in more detail in the amounts given in the third aspect.

In a particularly preferred seventh embodiment of the reaction resin system, the resin component contains: at least one compound based on urethane (meth) acrylate as reaction resin, at least one reactive diluent, at least one inhibitor, at least one accelerator, and at least one inorganic filler with hydrophilic properties, a hydrophilic fumed silica as inorganic filler with hydrophilic properties, and the resin component contains: at least one curing agent which is a solid peroxide, in particular dibenzoyl peroxide,

Water and

Bentonite as a rheology additive based on layered silicate.

In a preferred aspect of this embodiment, the solid peroxide is suspended in the water. In a further preferred aspect of this seventh embodiment, the reaction resin system contains the constituents specified in more detail in the amounts given in the third aspect.

In a very particularly preferred eighth embodiment of the reaction resin system, the resin component adheres to: at least one compound based on urethane (meth) acrylate as reaction resin, at least one reactive diluent, at least one inhibitor, at least one accelerator, and at least one hydrophilic fumed silica as an inorganic filler with hydrophilic properties, and the resin component contains: at least one curing agent which is a solid peroxide, in particular dibenzoyl peroxide,

Water and

Bentonite as a rheology additive based on layered silicate.

In a preferred aspect of this embodiment, the solid peroxide is suspended in the water. In a further preferred aspect of this eighth embodiment, the reaction resin system contains the constituents specified in more detail in the amounts given in the third aspect.

According to the invention, the rheology additive based on a sheet silicate is used in a multi-component reaction resin system, typically a two-component system. This multi-component system can be in the form of a cartridge system or a foil pouch system. The reaction resin system is used with self-tapping screws in holes. The holes can be depressions of natural or non-natural origin, that is to say cracks, crevices, boreholes and the like. They are typically boreholes, in particular boreholes in various substrates, in particular mineral substrates, such as those based on concrete, aerated concrete, brickwork, sand-lime brick, sandstone, natural stone, glass and the like, and metallic substrates such as those made of steel.

The reaction resin system, in which the swellable sheet silicate is used according to the invention as a rheology additive, is used according to the invention with thread-forming screws in holes. The holes can be depressions of natural or non-natural origin, that is to say cracks, crevices, boreholes and the like. They are typically boreholes, in particular boreholes in various substrates, in particular mineral substrates, such as those on the basis of concrete, aerated concrete, brickwork, sand-lime brick, sandstone, natural stone, glass and the like, and metallic substrates such as those made of steel.

The reaction resin composition in which the swellable layered silicate is used according to the invention as a rheological additive is characterized by a low level

Viscosity of the component containing this additive and an increased storage stability of the component in comparison to embodiments without the rheology additive used or to embodiments with other rheology additives which do not contain layered silicate.

The invention is explained in more detail below with the aid of a number of examples and comparative examples. All examples support the scope of the claims. However, the invention is not limited to the specific embodiments shown in the examples.

DESIGN EXAMPLES

List of the components used in the examples and references (explanation of abbreviations) as well as their trade names and sources of supply:

Aerosil® 200 hydrophilic, fumed silica; Evonik (CAS-No .: 112945-

52-5; spec. Surface 200m ² / g; mean particle size 0.2-0.3 μm (aggregates)

Optigel-CK activated sheet silicate (bentonite); BYK-Chemie GmbH

(specific density 2.6 g / cm ³ , bulk density 550-750 kg / m ³ , moisture content 10% ± 2%)

Optigel-WX activated sheet silicate (bentonite) with xanthan; BYK-Chemie GmbH (specific density 2.2 g / cm ³ , bulk density 500-650 kg / m ³ , moisture content max. 13%)

Xanthan gum XGT TNAS xanthan gum; Jungbunzlauer Austria AG (CAS No. 11138-66-2)

BP20SAG dibenzoyl peroxide 20%, suspension in water; United Initiators GmbH & Co. KG

Mixtures of benzoyl peroxide, 20% aqueous suspension, with different thickeners in different concentrations, as indicated in Table 1, were prepared by initially introducing the benzoyl peroxide suspension and adding the respective additive. The mixture was first pre-stirred by hand and then mixed in a speed mixer (High Speed Mixer DAC 400 FVZ; Fa. Hauschild & Co. KG) according to the following program until the thickener was well incorporated:

Mixing program: 10 seconds at 1000 rpm,

20 seconds at 2500 rpm.

15 seconds at 1500 rpm. Measurement of the dynamic viscosity of the hardener-thickener mixtures

(Hardener compositions) The dynamic viscosity of the hardener-thickener mixtures according to the invention (hardener compositions) (Table 1) was measured with a plate-cone measuring system (HAAKE® RheoStress® RS600 with temperature control unit UTC-20,

Measuring geometry C20 / 1 Ti ⁰ L01 026) in accordance with DIN 53019. The diameter of the frustum was 20 mm, the angle 1 °, and the gap was 0.052 mm. It was measured at a constant shear rate of 25 rpm at a temperature of 23 ° C. The measurement time was 180s. To achieve the shear rate, the sample was first held at 23 ° C. for 30 s, then a ramp of 0-25 rpm with a duration of 120 s was connected upstream. Since the liquids are Newtonian, a linear evaluation was carried out over the measuring section with a constant shear rate of 100 / s and the viscosity was determined. Three measurements were made in each case, the mean values in each case being given in Table 1.

Table 1: Composition of the hardener compositions according to the invention and results of the viscosity measurements of the freshly prepared hardener compositions according to the invention and after storage at 40 ° C. for 16 weeks

5

Table 2: Composition of the comparative hardener compositions and results of the viscosity measurements of the freshly prepared comparative hardener compositions and after 16 weeks of storage at 40 ° C

¹ > 100% BP20SAQ

The results of the measurements of the dynamic viscosity shown in Table 1 show that the freshly prepared hardener compositions according to the invention have a viscosity in the range from 136 mPa · s to 249 mPa · s, depending on the amount used, and were thus still flowable. After storage for 16 weeks at 40 ° C., no sedimentation of the peroxide was observed and the hardener compositions were all flowable, even with a thickener content of 4% by weight.

The results of the measurements of the dynamic viscosity shown in Table 2 show that the freshly prepared comparative hardener compositions, depending on the amount of thickener used, were in some cases still flowable. Some of the comparison hardener compositions, however, had such a high viscosity that they were no longer flowable. After storage for 16 weeks at + 40 ° C., some of the comparison hardener compositions were very much thickened and the solid peroxide was observed to settle out. In the other part, sedimentation of the peroxide was observed. The storage stability was therefore not given.

From the results of the measurements of the dynamic viscosity of the hardener compositions according to the invention (Table 1) and the comparison hardener compositions (Table 2) shown in Tables 1 and 2 show that the hardener compositions according to the invention remained flowable after storage and showed no sedimentation compared with the comparison -Hardener compositions.

It was thus possible to develop a hardener composition which, when using aqueous peroxide suspensions, was able to ensure the storage stability of the component.

Claims

PATENT CLAIMS

1. Hardener composition for a reaction resin system based on a free-radically curable compound, comprising water, a solid peroxide and a rheology additive, the rheology additive being a rheology additive based on a sheet silicate.

2. Hardener composition according to claim 1, wherein the layered silicate is a swellable layered silicate.

3. Hardener composition according to claim 2, wherein the swellable sheet silicate is a magnesium-aluminum-silicate or a sodium-aluminum-silicate.

4. Hardener composition according to claim 2 or 3, wherein the rheological additive consists of the swellable layered silicate or this as essential

Contains component / main component.

5. hardener composition according to claim 4, wherein the rheology additive

Montmorillonite is or contains this as an essential component / main component.

6. Hardener composition according to claim 5, wherein the rheology additive is bentonite.

7. Hardener composition according to one of the preceding claims, wherein the rheological additive is contained in an amount of 0.15 to 5 wt .-%, based on the total weight of the hardener composition.

8. Hardener composition according to one of the preceding claims, wherein the water and the solid peroxide are in the form of a suspension.

9. hardener composition according to any one of the preceding claims, wherein the

Peroxide selected from the group consisting of diacetyl peroxide, di-p-chlorobenzoyl peroxide, phthaloyl peroxide, succinyl peroxide, dilauryl peroxide, acetylcyclohexanesulfonyl peroxide, cyclohexane percarbonate, bis (4-f-butylcyclohexyl) percarbonate, silicon peroxide, cyclohexanoneyl peroxide, dibaurium peroxide, cyclohexanoneyl peroxide.

10. Multi-component reaction resin system, with a resin component comprising a free-radically curable compound, and with a hardener composition comprising a hardener composition according to any one of claims 1 to 9.

11. Multi-component reaction resin system according to claim 10, characterized in that the free-radically curable compound comprises at least one reaction resin, at least one reactive thinner or a mixture of at least one reaction resin and one reactive thinner.

12. Multi-component reaction resin system according to claim 11, characterized in that the reaction resin is a compound based on urethane (meth) acrylate, epoxy (meth) acrylate, a methacrylate of an alkoxylated bisphenol or based on other ethylenically unsaturated compounds.

13. Multi-component reaction resin system according to one of claims 10 to 12, characterized in that the resin component further comprises an inorganic additive.

14 Multi-component reaction resin system according to claim 13, characterized in that the inorganic aggregate has hydrophilic properties.

15. Multi-component reaction resin system according to one of claims 10 to 14, characterized in that the resin component further comprises an inhibitor and / or an accelerator.

16. Multi-component reaction resin system according to one of claims 10 to 14, characterized in that it is a two-component bag system.

17. Use of a multi-component reaction resin system according to one of claims 10 to 16 for fastening and / or reinforcing thread-forming screws in solid substrates, in particular in stone or

Concrete.