CHEMICAL DOWEL BASED ON ISOCYANATE-AMINE WITH IMPROVED PERFORMANCE AND ITS USE

Description

[0001] The present invention relates to a multi-component resin system for producing a mortar composition based on isocyanate-amine adducts for the chemical fastening of structural elements. The invention further comprises a mortar composition based on isocyanate-amine adducts produced from the multi-component resin system. The present invention also relates to a method and the use of a mortar composition based on the isocyanate-amine adducts for the chemical fastening of structural elements in mineral substrates.

[0002] To securely fasten components such as anchor threaded rods, reinforcing iron, threaded sleeves, and screws in a mineral substrate such as concrete, natural stone, or plaster, drill holes of the appropriate dimensions are first drilled into the mineral substrate to accommodate the components to be fastened. The drill holes are then cleaned of drilling dust, and the two-component mortar is mixed with the hardener component and introduced into the drill hole. The component to be fastened is then inserted into the drill hole filled with the mortar and adjusted. Once the mortar has hardened, the resin component reacts with the hardener component to firmly hold the component in the mineral substrate.

[0003] The load-bearing behavior of the components fastened in this way depends on several influencing factors, which are usually classified as internal and external. Internal influencing factors include the chemical composition of the mortar mix, its manufacturing process, and the packaging of the mortar mix, which typically comprises components in two separate containers.

[0004] External factors include the type of borehole cleaning, the quality of the mineral subsoil, such as concrete, its humidity and temperature, and the type of borehole construction.

[0005] It is also known that the mechanical properties of the hardened mortar mass are significantly influenced by the quality of the borehole cleaning and the moisture content of the mineral substrate. In damp boreholes and / or boreholes poorly cleaned of drilling dust, a significant decrease in performance occurs, which is reflected in reduced load values ​​of the hardened mortar mass.

[0006] In addition to the further development and improvement of existing binder systems, efforts are also being made to investigate binder systems other than those mentioned above with regard to their suitability as a basis for mortar compounds for chemical fixing. For example, EP 3 447 078 A1 describes a chemical anchor made from a multi-component compound comprising a polyisocyanate component and a polyaspartic acid ester component. When the two components are mixed, a polyaddition reaction produces polyurea, which forms the binder of the mortar compound.

[0007] WO 2011 / 113533 A1 relates to a fixing mortar system for mortaring anchoring agents based on one or more curing epoxy-based reactive resins into holes or gaps. The mortar system contains one or more silanes, which optionally contain reactive groups capable of participating in polymerization with the epoxy-based reactive resin and in any case contain silicon-bonded hydrolyzable groups. Halogen, ketoximate, amino, aminoxy, mercapto, acyloxy, aryloxy, aralkyloxy, and especially alkyloxy groups are used as silicon-bonded hydrolyzable groups in the one or more silanes.

[0008] DE 10 2015 109 125 A1 relates to a hardener composition for an addition-polymerization-curable synthetic mortar system for mortaring anchoring agents into holes or gaps. The hardener composition comprises oligomeric siloxanes that have, on average, at least one organic radical per molecule. The organic radical carries one or more secondary and / or primary amino and / or thiol groups that are reactive in the addition reaction with isocyanate or epoxy groups. Furthermore, the siloxanes also contain one or more hydrolyzable groups bonded to silicon. The hardener composition may also contain one or more other conventional additives.

[0009] These mortar compounds known from the prior art already demonstrate an improvement in load values ​​in wet boreholes, but hardly any in dry boreholes. However, the production of the silane and siloxane additives used in the prior art is complex and costly. Furthermore, monomeric silanes with hydrolyzable, particularly silicon-bonded, groups have the disadvantage that they release enormous amounts of volatile organic compounds (VOCs), such as alcohols, upon hydrolysis during use, and are complex and costly to produce.

[0010] Compared to the known state of the art, there is therefore a need for two-component mortar compounds with good adhesion in dry boreholes, especially in well-cleaned boreholes, which are easy to process and contain additives that are simple to produce and cost-effective.

[0011] The object underlying the invention is achieved by providing a multi-component resin system according to claim 1. Preferred embodiments of the multi-component resin system according to the invention are specified in the subclaims, which can optionally be combined with one another.

[0012] The invention further relates to a mortar composition for chemically fixing structural elements according to claim 23, produced from the multi-component resin system according to the invention.

[0013] The invention also relates to a method for chemically fixing structural elements in mineral substrates according to claim 24 and to the use of the multi-component resin system according to the invention or the mortar composition produced therefrom for chemically fixing structural elements in mineral substrates according to claim 25.

[0014] A first subject matter of the invention is a multi-component resin system containing an isocyanate component which comprises at least one aliphatic and / or aromatic polyisocyanate having an average NCO functionality of 2 or greater, and an amine component which comprises at least one amine reactive towards isocyanate groups and having an average NH functionality of 2 or greater, with the proviso that the multi-component resin system is free of polyaspartic acid esters, wherein the isocyanate component and / or the amine component comprises at least one filler and at least one rheology additive, and the total filler content of a mortar composition produced by mixing the isocyanate component and the amine component is in a range from 30 to 80%, which is characterized in that the isocyanate component and / or the amine component contains at least one additive, wherein the additive a compound of the formula I A n (L) m (X) p (formula I), where A is phosphorus, boron, aluminum, titanium or zirconium, X can be the same or different and is an alkoxy, aryloxy or acyloxy radical, L can be the same or different and is at least one ligand, n is the valence of A, and p is an integer from 1 to n, m is 0 or an integer from 1 to n-1 and n = m+p, or a siloxane which has at least one functional radical which is capable of addition reaction with isocyanates, but does not have any hydrolyzable groups bonded to a silicon atom.

[0015] Surprisingly, it has been found that the use of organometallic compounds of formula I or of siloxanes as additives in isocyanate-amine-based chemical anchors increases the bond stresses in dry concrete in the same way as silanes with hydrolyzable groups bonded to a silicon atom.

[0016] It is also essential to the invention that the multi-component resin system and in particular the amine component of the multi-component resin system is free of polyaspartic acid esters. The expression "free of polyaspartic acid esters" For the purposes of the present application, this means that the proportion of polyaspartic acid esters in the multicomponent resin system is preferably less than 2 wt. %, more preferably less than 0.5 wt. %, and even more preferably less than 0.1 wt. %, in each case based on the total weight of the multicomponent resin system. The presence of polyaspartic acid esters in the aforementioned weight percentage ranges can be attributed to potential impurities. However, the proportion of polyaspartic acid esters in the multicomponent resin system is particularly preferably 0.0 wt. %, based on the total weight of the multicomponent resin system.

[0017] For a better understanding of the invention, the following explanations of the terminology used herein are considered useful. For the purposes of the invention: 'Multi-component resin system' a reactive resin system comprising several components stored separately from one another, generally a resin component and a hardener component, so that curing only occurs after all components have been mixed. "Isocyanates" are compounds that have a functional isocyanate group -N=C=O and are characterized by the structural unit RN=C=O. "Polyisocyanates" are compounds that have at least two functional isocyanate groups -N=C=O; diisocyanates, which also fall under the definition of polyisocyanate, are characterized, for example, by the structure O=C=NRN=C=O and thus have an NCO functionality of 2. "medium NCO functionality",describes the number of isocyanate groups in the compound; in a mixture of isocyanates, the "average NCO functionality" describes the average number of isocyanate groups in the mixture and is determined according to the formula: average NCO functionality (mixture) = Σ average NCO functionality (isocyanate i) / ni , i.e. the sum of the average NCO functionality of the individual component divided by the number of individual components. "Isocyanate component" or A component, describes a component of the multi-component resin system which comprises at least one polyisocyanate and optionally at least one filler and / or at least one rheology additive and / or further additives. "Amine"are compounds with a functional NH group derived from ammonia by replacing one or two hydrogen atoms with hydrocarbon groups and having the general structures RNH 2 (primary amines) and R 2 NH (secondary amines) (see: IUPAC Compendium of Chemical Terminology, 2nd ed. (the "Gold Book"), Compiled by A.D. McNaught and A. Wilkinson, Blackwell Scientific Publications, Oxford (1997)). The term "amines" explicitly excludes the compound class of polyaspartic acid esters for the purposes of the present invention. These are defined separately under the term "polyaspartic acid esters." "NH functionality" describes the number of active hydrogen atoms that can react with an isocyanate group in an amino group. "medium NH functionality"Describes the number of active hydrogen atoms that can react with an isocyanate group in an amine and is determined from the number and NH functionality of the amino groups contained in the compound, the amine. For a mixture of amines, the "average NH functionality" describes the average number of active hydrogen atoms in the mixture and is determined according to the formula: average NH functionality (mixture) = Σ average NH functionality (amine i) / ni, i.e., the sum of the average NH functionality of the individual components divided by the number of individual components. "Polyaspartic acid ester" refers to compounds of the general formula: in which R 1< and R 2< may be the same or different and represent an organic radical which is inert towards isocyanate groups, X represents an n-valent organic radical which is inert towards isocyanate groups, and n represents an integer of at least 2, preferably from 2 to 6, more preferably from 2 to 4 and particularly preferably 2. "amine component" or B component, describes a component of the multi-component resin system which comprises at least one amine and optionally at least one filler and / or at least one rheology additive and / or further additives. "Isocyanate-amine adducts" are polymers formed by the polyaddition reaction of isocyanates with amines. The isocyanate-amine adducts according to the invention are preferably polyureas which have at least one structural element of the form -[-NH-R-NH--NH-R'-NH-]. "aliphatic compounds"are acyclic or cyclic, saturated or unsaturated carbon compounds, excluding aromatic compounds. "alicyclic compounds" are compounds with a carbocyclic ring structure, excluding benzene derivatives or other aromatic systems. "araliphatic compounds" are aliphatic compounds with an aromatic backbone, so that in the case of a functionalized araliphatic compound, an existing functional group is attached to the aliphatic and not the aromatic part of the compound. "aromatic compounds" are compounds that follow the Hückel (4n+2) rule. "two-component reaction resin system" means a reaction resin system which comprises two components stored separately from one another, in this case an isocyanate component and an amine component, so that curing only occurs after the two components have been mixed. "mortar mass"refers to the composition obtained by mixing the isocyanate component and the amine component and as such can be used directly for chemical fastening. "Filler" means an organic or inorganic, especially inorganic, compound. "Rheology additive" Describes additives capable of influencing the viscosity behavior of the isocyanate component, the amine component, and the multicomponent resin system during storage, application, and / or curing. The rheology additive prevents, among other things, sedimentation of the fillers in the polyisocyanate component and / or the amine component. Furthermore, it improves the miscibility of the components and prevents possible phase separation. "Temperature robustness"refers to the change in the bond stress of a cured mortar mass at an elevated temperature compared to the reference bond stress. In the context of the present invention, temperature robustness is specifically defined as the ratio of the bond stress at 80 °C to the reference stress. "a", "an", "one" as an article before a chemical class of compounds, e.g. before the word "filler", that one or more compounds falling within this chemical class of compounds, e.g. various "fillers", can be meant. "at least one", "at least one", "at least one" numerically "one or more"; In a preferred embodiment, this term is numerically "a", "an", "one" meant. "contain", "include" and "include", that in addition to the components mentioned, there may be other components; these terms are meant inclusively and therefore also include "consist of"; "consist of"is meant conclusively and means that no further components can be present; in a preferred embodiment, the terms "contain", "include" and "include" the term "consist of".

[0018] All standards mentioned in this text (e.g. DIN standards) were used in the current edition on the filing date of this application. Isocyanate compounds

[0019] The multicomponent resin system according to the invention comprises at least one isocyanate component and at least one amine component. The isocyanate component and the amine component are separated from each other prior to use to inhibit reaction.

[0020] The isocyanate component comprises at least one polyisocyanate. All aliphatic and / or aromatic isocyanates known to those skilled in the art with an average NCO functionality of 2 or greater, individually or in any desired mixtures, can be used as polyisocyanates. The average NCO functionality indicates how many NCO groups are present in the polyisocyanate. Polyisocyanate means that the compound contains two or more NCO groups.

[0021] Suitable aromatic polyisocyanates are those with aromatically bound isocyanate groups, such as diisocyanatobenzenes, toluene diisocyanates, diphenyl diisocyanates, diphenylmethane diisocyanates, diisocyanatonaphthalenes, triphenylmethane triisocyanates, but also those with isocyanate groups that are bound to an aromatic via an alkylene group, such as a methylene group, such as bis- and tris-(isocyanatoalkyl)-benzenes, -toluenes and -xylenes.

[0022] Preferred examples of aromatic polyisocyanates are: 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,5-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, tetramethyl-1,3-xylylene diisocyanate, tetramethyl-1,4-xylylene diisocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,4-bis(isocyanatomethyl)benzene, ethylphenyl diisocyanate, 2-dodecyl-1,3-phenylene diisocyanate, 2,4,6-triisopropyl-m-phenylene diisocyanate, 2,4,6-trimethyl-1,3-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, diphenylene methane 2,4'-diisocyanate, diphenylene methane 2,2'-diisocyanate, Diphenylenemethane-4,4'-diisocyanate, triphenylmethane-4,4',4"-triisocyanate, 5-(p-isocyanatobenzyl)-2-methyl-m-phenylene diisocyanate, 4,4-diisocyanato-3,3,5,5-tetraethyldiphenylmethane, 5,5'-ureylenedi-o-tolyl diisocyanate,4-[(5-Isocyanato-2-methylphenyl)methyl]-m-phenylendiisocyanat, 4-[(3-isocyanato-4-methylphenyl)methyl]-m-phenylendiisocyanat, 2,2'-Methylen-bis[6-(o-isocyanatobenzyl)phenyl]diisocyanat.,

[0023] Preference is given to using aliphatic isocyanates which have a carbon backbone (without the NCO groups contained) of 3 to 30 carbon atoms, preferably of 4 to 20 carbon atoms. Examples of aliphatic polyisocyanates are bis(isocyanatoalkyl) ethers or alkane diisocyanates, such as methane diisocyanate, propane diisocyanates, butane diisocyanates, pentane diisocyanates, hexane diisocyanates (e.g. hexamethylene diisocyanate, HDI), heptane diisocyanates (e.g. 2,2-dimethylpentane-1,5-diisocyanate, octane diisocyanates, nonane diisocyanates (e.g. trimethyl-HDI (TMDI) usually as a mixture of the 2,4,4- and 2,2,4-isomers), 2-methylpentane-1,5-diisocyanate (MPDI), nonane triisocyanates (e.g.4-Isocyanatomethyl-1,8-octane diisocyanate, 5-methylnonane diisocyanate), decane diisocyanates, decane triisocyanates, undecane diisocyanates, undecane triisocyanates, dodecane diisocyanates, dodecane triisocyanates, 1,3- and 1,4-bis-(isocyanatomethyl)cyclohexane (H 6 XDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), bis-(4-isocyanatocyclohexyl)methane (H 12 MDI), bis-(isocyanatomethyl)norbornane (NBDI) or 3(4)-isocyanatomethyl-1-methylcyclohexyl isocyanate (IMCI), octagydro-4,7-methano-1H-indenedimethyl diisocyanate, norbornene diisocyanate, 5-Isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane, ureylene bis(p-phenylene methylene-p-phenylene) diiscoyanate.

[0024] Particularly preferred isocyanates are hexamethylene diisocyanate (HDI), trimethyl-HDI (TMDI), pentane diisocyanate (PDI), 2-methylpentane-1,5-diisocyanate (MPDI), isophorone diisocyanate (IPDI), 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane (H 6 XDI), bis(isocyanatomethyl)norbornane (NBDI), 3(4)-isocyanatomethyl-1-methylcyclohexyl isocyanate (IMCI) and / or 4,4'-bis(isocyanatocyclohexyl)methane (H 12 MDI) or mixtures of these isocyanates.

[0025] Even more preferably, the polyisocyanates are present as prepolymers, biurets, isocyanurates, iminooxadiazinediones, uretdiones and / or allophanates, which can be prepared by oligomerization of difunctional isocyanates or by reaction of the isocyanate compounds with polyols or polyamines, individually or as a mixture, and which have an average NCO functionality of 2 or greater.

[0026] Examples of suitable, commercially available isocyanates are Desmodur@ N 3900, Desmodur ®< N 100, Desmodur@ Ultra N 3200, Desmodur@ Ultra N 3300, Desmodur@ Ultra N 3600, Desmodur ®< N 3800, Desmodur ®< XP 2675, Desmodur ®< 2714, Desmodur ®< 2731, Desmodur ®< N 3400, Desmodur ®< XP 2679, Desmodur ®< XP 2731, Desmodur ®< XP 2489, Desmodur ®< E 3370, Desmodur ®< XP 2599, Desmodur ®< XP 2617, Desmodur@ XP 2406, Desmodur@ XP 2551, Desmodur@ XP 2838, Desmodur@ XP 2840, Desmodur@ VL, Desmodur ®< VL 50, Desmodur@ VL 51, Desmodur@ ultra N 3300, Desmodur@ eco N 7300, Desmodur ®< E23, Desmodur ®< E XP 2727, Desmodur ®< E 30600, Desmodur ®< E 2863 XP, Desmodur ®< H, Desmodur@ VKS 20 F, Desmodur ®< 44V20I, Desmodur ®< 44P01, Desmodur ®< 44V70 L, Desmodur ®< N3400, Desmodur ®< N3500 (each available from Covestro AG), Tolonate ™< HDB, Tolonate ™< HDB-LV, Tolonate ™< HDT, Tolonate ™< HDT-LV, Tolonate ™< HDT-LV2 (available from Vencorex), Basonat ®< HB 100, Basonat ®< Hl 100,Basonat®< HI 2000 NG (available from BASF), Takenate®< 500, Takenate®< 600, Takenate®< D-132N(NS), Stabio®< D-376N (each available from Mitsui), Duranate®< 24A-100, Duranate®< TPA-100, Duranate®< TPH-100 (each available from Asahi Kasai), Coronate®< HXR, Coronate®< HXLV, Coronate®< HX, Coronate®< HK, (each available from Tosoh).

[0027] One or more polyisocyanates are preferably present in the isocyanate component in a proportion of 20 to 100 wt.%, preferably in a proportion of 30 to 90 wt.% and more preferably in a proportion of 35 to 65 wt.%, based on the total weight of the isocyanate component. Amine compounds

[0028] The amine component, which is present in the multi-component resin system separately from the isocyanate component to inhibit reaction, comprises at least one isocyanate-reactive amine which comprises one amino group, preferably at least two amino groups, as functional groups. According to the invention, the amine has an average NH functionality of 2 or greater. The average NH functionality indicates the number of hydrogen atoms bonded to a nitrogen atom in the amine. Accordingly, for example, a primary monoamine has an average NH functionality of 2, a primary diamine has an average NH functionality of 4, an amine with three secondary amino groups has an average NH functionality of 3, and a diamine with one primary and one secondary amino group has an average NH functionality of 3.The average NH functionality can also be determined according to the information provided by the amine suppliers, whereby the actually stated NH functionality may differ from the theoretical average NH functionality as understood herein. The term "average" indicates that this refers to the NH functionality of the compound and not the NH functionality of the amino group(s) contained in the compound. The amino groups can be primary or secondary amino groups. The amine can contain either only primary or only secondary amino groups, or both primary and secondary amino groups.

[0029] According to a preferred embodiment, the amine reactive towards isocyanate groups is selected from the group consisting of aliphatic, alicyclic, araliphatic and aromatic amines, particularly preferably selected from the group consisting of alicyclic and aromatic amines.

[0030] Amines reactive toward isocyanate groups are generally known to those skilled in the art. Examples of suitable amines reactive toward isocyanate groups are given below, but without limiting the scope of the invention. These can be used individually or in any desired mixtures with one another. Examples are: 1,2-diaminoethane(ethylenediamine), 1,2-propanediamine, 1,3-propanediamine, 1,4-diaminobutane, 2,2-dimethyl-1,3-propanediamine(neopentanediamine), diethylaminopropylamine (DEAPA), 2-methyl-1,5-diaminopentane, 1,3-diaminopentane, 2,2,4- or 2,4,4-trimethyl-1,6-diaminohexane and mixtures thereof (TMD), 1,3-bis(aminomethyl)cyclohexane, 1,2-bis(aminomethyl)cyclohexane, hexamethylenediamine (HMD), 1,2- and 1,4-diaminocyclohexane (1,2-DACH and 1,4-DACH), bis(4-amino-3-methylcyclohexyl)methane, diethylenetriamine (DETA), 4-azaheptane-1, 7-diamine, 1,11-diamino-3, 6,9-trioxundecane, 1,8-diamino-3, 6-dioxaoctane, 1,5-diamino-methyl-3-azapentane, 1,10-diamino-4,7-dioxadecane,Bis(3-aminopropyl)amin, 1,13-Diamino-4,7, 10-trioxatridecan, 4-Aminomethyl-1, 8-diaminooctan, 2-Butyl-2-ethyl-1, 5-diaminopentan, N, N-Bis-(3-aminopropyl)methylamin, Triethylentetramin (TETA), Tetraethylenpentamin (TEPA), Pentaethylenhexamin (PEHA), 1,3-Benzoldimethanamin (m-Xylylendiamin, mXDA), 1,4-Benzoldimethanamin (p-Xylylendiamin, pXDA), 5-(Aminomethyl)bicyclo[[2.2.1]hept-2-yl]methylamin (NBDA, Norbornandiamin), Dimethyldipropylentriamin, Dimethylaminopropyl-aminopropylamin (DMAPAPA), 2,4-Diamino-3,5-dimethylthiotoluol (Dimethylthio-toluoldiamin, DMTDA) 3-Aminomethyl-3,5,5-trimethylcyclohexylamin (Isophorondiamin (IPDA)), Diaminodicyclohexylmethan (PACM), Diethylmethylbenzoldiamin (DETDA), 3,3'-Diaminodiphenylsulfon (33Dapson), 3,3'-Diaminodiphenylsulfon (Dapson), 4,4'-Diaminodiphenylsulfon (44Dapson), 3,3'-Diaminodiphenylsulfon (Dapson) gemischte polycyclische Amine (MPCA) (z.B. Ancamine 2168), Dimethyldiaminodicyclohexylmethan (Laromin C260), 2,2-Bis(4-aminocyclohexyl)propan,(3(4),8(9)Bis(aminomethyldicyclo[5.2.1.0 2,6< ]decan (Isomerengemisch, tricyclischer primärer Amine; TCD-Diamin), Methylcyclohexyl-diamin (MCDA), N,N'-Diaminopropyl-2-methyl-cyclohexan-1,3-diamin, N,N'-Diaminopropyl-4-methyl-cyclohexan-1,3-diamin, N-(3-Aminopropyl)cyclohexylamin, und 2-(2,2,6,6-tetramethylpiperidin-4-yl)propan-1,3-diamin.,

[0031] Particularly preferred amines are diethylmethylbenzenediamine (DETDA), 2,4-diamino-3,5-dimethylthiotoluene (dimethylthiotoluenediamine, DMTDA), 4,4'-methylene-bis[N-(1-methylpropyl)phenylamine], an isomer mixture of 6-methyl-2,4-bis(methylthio)phenylene-1,3-diamine and 2-methyl-4,6-bis(methylthio)phenylene-1,3-diamine (Ethacure ®< 300), 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylenebis(N-sec-butylcyclohexanamine) (Clearlink ®< 1000), 3,3'-diaminodiphenylsulfone (33Dapsone), 4,4'-diaminodiphenylsulfone (44Dapsone), N,N'-Di-sec-butyl-p-phenylenediamine and 2,4,6-trimethyl-m-phenylenediamine, 4,4'-methylenebis(N-(1-methylpropyl)-3,3'-dimethylcyclohexanamine (Clearlink ®< 3000), the reaction product of 2-propenenitrile with 3-amino-1,5,5-trimethylcyclohexanemethanamine (Jefflink ®< 745) and 3-((3-(((2-cyanoethyl)amino)methyl)-3,5,5-trimethylcyclohexyl)amino)propiononitrile (Jefflink ®< 136 or Baxxodur PC136).

[0032] Very particularly preferred amines are 4,4'-methylene-bis[N-(1-methylpropyl)phenylamine], an isomer mixture of 6-methyl-2,4-bis(methylthio)phenylene-1,3-diamine and 2-methyl-4,6-bis(methylthio)phenylene-1,3-diamine (Ethacure 300), 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylenebis(N-sec-butylcyclohexanamine) (Clearlink 1000), 3,3'-diaminodiphenylsulfone (dapsone), N,N'-di-sec-butyl-p-phenylenediamine and 2,4,6-trimethyl-m-phenylenediamine.

[0033] One or more amines are preferably present in the amine component in a proportion of 20 to 100 wt.%, preferably in a proportion of 30 to 70 wt.% and more preferably in a proportion of 35 to 70 wt.% based on the total weight of the amine component.

[0034] The quantitative ratios of the polyisocyanate and the amine are preferably chosen such that the ratio of average NCO functionality of the polyisocyanate to average NH functionality of the amine is between 0.3 and 2.0, preferably between 0.5 and 1.8, more preferably between 0.5 and 1.5, even more preferably between 0.7 and 1.5 and even more preferably 0.7 to 1.3.

[0035] To adjust the curing rate, a mixture of different isocyanates and / or different amines can be used. In this case, their proportions are selected such that the ratio of the average NCO functionality of the isocyanate mixture to the average NH functionality of the amine mixture is between 0.3 and 2.0, preferably between 0.5 and 1.8, more preferably between 0.5 and 1.5, more preferably between 0.7 and 1.5, and even more preferably between 0.7 and 1.3. Fillers and additives

[0036] According to the invention, the multi-component resin system contains as additive a compound of the formula IA n (L) m (X) p or a siloxane which has at least one functional radical capable of addition reaction with isocyanate groups, but does not have any hydrolyzable groups bonded to a silicon atom, in particular no alkoxy radicals.

[0037] The additive according to the invention can be present individually or as a mixture of additives.

[0038] The additives according to the invention eliminate the need for silanes or siloxanes with silicon-bonded hydrolyzable residues or can completely or partially replace the known hydrolyzable silanes and siloxane oligomers. This surprisingly leads to good and rapid curing of the chemical mortars, even at the interface, despite the absence of silicon-bonded substituted residues.

[0039] With the additives according to the invention, it is possible to improve mortar performance in dry concrete for hammer-drilled and diamond-drilled boreholes, especially for well-cleaned boreholes, compared to mortar compounds without corresponding additives. The fastening of components using the multi-component resin system according to the invention results in high load values ​​in dry, cleaned boreholes, which are higher than those of siloxane-free or, in some cases, silane-containing compounds, without resorting to state-of-the-art silanes or siloxane oligomers.

[0040] Surprisingly, it was found that even with low additive contents in the mortar masses, improved adhesion of the hardened mortar to the concrete surface as well as improved load values ​​of cast-in fasteners commonly used in the construction sector, such as dowels, anchors, threaded screws and bolts in wet and dry concrete, can be achieved.

[0041] According to the invention, the multi-component resin system contains, in a first alternative, as an additive a compound of the formula I A n (L) m (X) p (Formula I) where A represents phosphorus, boron, aluminum, titanium, or zirconium; X may be the same or different and represents an alkoxy, aryloxy, or acyloxy radical; L may be the same or different and represents at least one ligand; n represents the valence of A; and p represents an integer from 1 to n; m represents 0 or an integer from 1 to n-1; and n = m+p.

[0042] The ligand L can be selected from the group consisting of acetoacetate, alkyl, halide, phosphate, pyrophosphate, phosphite, sulfate, sulfite, CN, cyclopentadienyl and pentamethylcyclopentadienyl, ethers such as tetrahydrofuran, pyridine, and morpholine. The terms phosphate, pyrophosphate, phosphite, sulfate, and sulfite also include their esters and half-esters with alcohols, especially alkoxy compounds with 1 to 24 carbon atoms.

[0043] In a preferred embodiment of the compound of formula I A n (L) m (X) p (formula I), X represents an alkoxy radical -OR 1< or an acyloxy radical -O(C=O)R 1<, wherein R 1< in each case represents an optionally substituted, linear or branched alkyl group having 1 to 24 C atoms, preferably having 1 to 18 C atoms and particularly preferably having 1 to 8 C atoms.

[0044] Particularly preferably, X represents an alkoxy or acyloxy radical selected from the group consisting of -O-CH 3 , -OC 2 H 5 , -OC 3 H 7 , -OC 4 H 9 , -OC 5 H 11 , -O-(CO)-CH 3 , -O-(CO)-C 2 H 5 , -O-(CO)-C 3 H 7 , -O-(CO)-C 4 H 9 and -O-(CO)-C 5 H 11 , preferably from the group consisting of -O-CH 3 , -OC 2 H 5 , -OC 3 H 7 and -OC 4 H 9 .

[0045] The radical X may be the same or different. In a preferred embodiment of the invention, X is the same.

[0046] Preferably m = 0 and n = p.

[0047] In a further preferred embodiment, the compound of formula I is selected from the group consisting of trimethyl phosphate, triethyl phosphate, triethyl borate, triisopropyl borate, tributyl borate, triethyl aluminate, tetraethyl titanate, tetraisopropyl titanate, tetraethyl zirconate, tetrabutyl zirconate, tris(isooctadecanoato-o)(propan-2-olato)titanate (CAS No.: 61417-49-0), isopropyl dimethacryloyl isostearoyltitanate (CAS No.: 61548-33-2), tris(dodecylbenzenesulfonate)isopropoxide titanate (CAS No.: 61417-55-8), isopropyl tri(dioctylphosphato)titanate (CAS No.: 65345-34-8), trimethacrylate methoxyethoxyethoxide titanate (CAS No.: 61436-48-4), isopropyl titanium tri(dioctylpyrophosphate) (CAS No.: 68585-78-4), isopropyl triacryloyl titanate (CAS No.: 61436-49-5), Bis(2-((2-aminoethyl)amino)ethanolato)(2-((2-aminoethyl)amino)ethanolato-O)(propane-2-olato)titanate (CAS No.: 65380-84-9), tetraisopropoxytitanium (CAS No.: 68585-67-1), tetraoctyl di(ditridecylphosphite) titanate (CAS No.: 68585-68-2) and Tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecylphosphite)titanate (CAS No.: 64157-14-8).

[0048] Particularly suitable complex compounds of formula I are isopropyl tri(dioctyl pyrophosphate) titanate or tetraoctyl titanate bis(di-tridecyl phosphite), which are available from Kenrich Chemicals Inc., among others.

[0049] In a preferred embodiment, the at least one compound of formula I is present in a proportion of 0.01 to 10 wt.%, more preferably in a proportion of 0.01 to 5 wt.%, even more preferably in a proportion of 0.1 to 5 wt.% and particularly preferably in a proportion of 0.1 to 3 wt.%, based on the total weight of the multi-component resin system.

[0050] According to the invention, in a second alternative, the multi-component resin system contains as an additive at least one siloxane which has at least one functional radical capable of addition reaction with isocyanate groups, but does not have any hydrolyzable groups bonded to a silicon atom, in particular no alkoxy radicals.

[0051] The multi-component resin system according to the invention preferably contains no siloxanes with silicon-bonded hydrolyzable groups. Silicon-bonded hydrolyzable groups are understood to be radicals such as halogen atoms, ketoximate, amino, aminoxy, mercapto, acyloxy, aryloxy, aralkyloxy (= arylalkoxy), or, in particular, alkyloxy (alkoxy) radicals that are bonded to a silicon atom via a heteroatom.

[0052] For the purposes of the present invention, siloxanes are chemical compounds composed of siloxane units. In these siloxane units, the silicon atoms that do not reach their octet (electron shell) by forming bonds with oxygen are saturated with organic residues. In contrast to (poly)silanes, the silicon atoms are not bonded to each other, but rather to their neighboring silicon atom through exactly one oxygen atom: Si-O-Si.

[0053] A siloxane unit can have one to four additional substituents, depending on the number of remaining valences on the oxygen atom: R n SiO (4-n) / 2 (n=0, 1, 2, 3), i.e., a siloxane unit can have one to four additional substituents, depending on the number of remaining valences on the oxygen atom. The siloxane units can therefore be mono-, di-, tri-, and tetrafunctional, with the following abbreviations commonly used: [M] = R 3 SiO 1 / 2 , [D] = R 2 SiO 2 / 2 , [T] = RSiO 3 / 2 , and [Q] = SiO 4 / 2 .

[0054] Linear (poly)siloxanes have the structural form [MD n M], corresponding to the general formula R 3 Si-[O-SiR 2 ] n -O-SiR 3 , where R can be hydrogen atoms or organic groups, for example alkyl groups, and n represents 0 or an integer. An example of a linear polysiloxane is poly(dimethylsiloxane).

[0055] Branched polysiloxanes, which have trifunctional or tetrafunctional siloxane units as branching elements, have the structural form [M n D m ​​T n ], where n and m are integers. The branching points are incorporated either in a chain or a ring. Cyclic polysiloxanes are ring-shaped and composed of difunctional siloxane units, with the structural form [D n ], where n is an integer greater than or equal to 3. Crosslinked polysiloxanes in this group are chain- or ring-shaped molecules that are linked to planar or three-dimensional networks using trifunctional and tetrafunctional siloxane units.

[0056] The siloxane backbone may contain various hydrocarbon radicals, and silicon-bonded functional groups and organofunctional groups may be present. However, the siloxanes used according to the invention do not contain any silicon-functional groups. Therefore, functional groups or radicals within the meaning of the present invention always refer to organofunctional radicals, i.e., functional radicals bonded to carbon.

[0057] The siloxanes according to the invention eliminate the need for silanes or siloxanes with silicon-bonded hydrolyzable residues or can completely or partially replace the known hydrolyzable silanes and siloxanes. It is assumed that the siloxanes used according to the invention sufficiently hydrophobize the mortar surface to reduce water absorption by the mortar or the diffusion of hardeners such as amines into the water layer at the mortar-borehole interface. This surprisingly leads to good curing of the chemical mortars even at the interface, despite the absence of silicon-bonded hydrolyzable residues.

[0058] With the siloxanes according to the invention, which are free of hydrolyzable silicon-bonded residues, it is possible to improve mortar performance under critical borehole conditions in both dry and water-saturated concrete for hammer-drilled and diamond-drilled boreholes, without the formation of undesirable VOCs. The fastening of components using the two-component mortar compound according to the invention results in high load values, particularly in dry, cleaned boreholes and especially in very well-cleaned boreholes. These values ​​are increased compared to siloxane-free or, in some cases, silane-containing compounds, without resorting to state-of-the-art silanes or siloxane oligomers, which pollute the environment through the formation of VOCs.

[0059] In a preferred embodiment, the two-component mortar composition contains at least one siloxane having at least one functional terminal radical capable of addition reaction with isocyanate groups. More preferably, the siloxane has two or more identical or different, particularly preferably two identical, terminal functional radicals capable of addition reaction with isocyanate groups. By functionalizing the siloxanes according to the invention, they can be firmly incorporated into the polymer structure and, if appropriate, also serve as a curing agent for the resin, for example, if the functional radical is an amino group.

[0060] Preferred functional radicals capable of addition reaction with isocyanate groups in one of the above-mentioned embodiments of the invention are selected from the group consisting of hydroxy, carboxy, amino, secondary amino, mercapto, isocyanato, alkenyl, (meth)acryloyl, anhydrido, epoxide, urethane and urea radicals, preferably from the group consisting of isocyanato and amino radicals.

[0061] In a further preferred embodiment of the two-component mortar composition according to the invention, the siloxane has the structure R 3 Si-[O-Si(R 1< ) 2 ] n -O-SiR 3 , where n is 0 or an integer from 1 to 1000 inclusive, preferably 0 or 1 to 5; R and R 1< each independently of one another represent a C 1 -C 20 alkyl radical or aralkyl radical which may contain heteroatoms, may be substituted and may have at least one radical capable of addition reaction with isocyanate groups. R 1< is preferably an unsubstituted C 1 -C 4 alkyl radical, in particular a methyl radical.

[0062] The heteroatoms are preferably oxygen atoms. The radicals R and R 1< are each bonded to silicon via a carbon atom.

[0063] In this embodiment, the siloxane preferably has one and more preferably two or more substituted C 1 -C 20 alkyl or aralkyl radicals, wherein the substituents are selected from the group consisting of trialkylsilyl (e.g. trimethylsilyl), hydroxy, carboxy, amino, sec. amino, mercapto, isocyanato, alkenyl, (meth)acryloyl, anhydrido and epoxy radicals, preferably from the group consisting of isocyanato, (meth)acryloyl, trimethylsilyl and amino radicals and particularly preferably from the group consisting of isocyanato and amino radicals.

[0064] Insbesondere sind die Siloxane aus der Gruppe bestehend aus 1,3-Bis(2-aminoethylaminoethyl)tetramethyldisiloxan, 1,3-Bis(glycidoxypropyl)tetramethyl-disiloxan, Tris(glycidoxypropyldimethylsiloxy)phenylsilan, 3-Methacryloxypropylpentamethyldisiloxan, Poly(acryloxypropylmethyl)siloxan, 1,3-Bis-[(acryloxypropylmethyl)siloxan, 1,3-Bis(3-methacryloxypropyl)tetrakis-(trimethylsiloxy)disiloxan, 1,3-Bis(3-methacryloxypropyl)tetramethyldisiloxan, Momomethacryloxypropyl-terminiertes Polydimethylsiloxan, Poly[dimethylsiloxan-co-(3-(monomethacryloxy)propyl)methylsiloxan], 1,3,-Bis(4-methacryloxybutyl)-tetramethyldisiloxan, (Methacryloxypropyl)methylsiloxan / Dimethylsiloxan Copolymer, Dodecamethylpentasiloxan, 1,1,1,3,5,7,7,7-Octamethyl-3,5-bis(trimethylsilanyloxy)tetrasiloxan, Trimethylsilyl-terminiertem Poly(methylhydro-siloxan), Bis(hydroxyalkyl)-terminiertem Poly(dimethylsiloxan), Poly[di-methylsiloxan-co-(2-(3,4-epoxycyclohexyl)ethyl)methylsiloxan],Diglycidyl ether-terminated poly(dimethylsiloxane), poly[dimethylsiloxane-co-[3-(2-(3-hydroxy-ethoxy)ethoxy)propyl]methylsiloxane and monoglycidyl ether-terminated poly(dimethylsiloxane) and mixtures thereof.

[0065] Particularly preferred examples are 1,3-bis(2-aminoethylaminoethyl)tetramethyldisiloxane, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane and tris(glycidoxypropyldimethylsiloxy)phenylsilane and mixtures thereof.

[0066] The siloxanes used according to the invention can be present individually or as a mixture and, based on the entire multi-component resin system, can be provided in a weight proportion of 0.5 to 10 wt.%, preferably 0.5 to 8 wt.% and more preferably 1.5 to 5 wt.%.

[0067] Both the isocyanate component and the amine component can contain at least one filler and at least one rheology additive, whereby it is essential to the invention that at least one of the two components contains both a filler and a rheology additive. It is preferred that both the isocyanate component and the amine component each contain at least one filler and at least one rheology additive.

[0068] According to the invention, the total filler content of a mortar composition produced by mixing the isocyanate component and the amine component of the multi-component resin system is in a range from 30 to 80 wt.% based on the total weight of the mortar composition, preferably in a range from 35 to 65, more preferably in a range from 35 to 60 wt.%. The total filler content of the mortar composition refers to the weight percentage of filler and rheology additive based on the total weight of the isocyanate component and the amine component. In a preferred embodiment, the filler content of the isocyanate component is up to 80 wt.%, preferably 10 to 70 wt.%, more preferably 35 to 65 wt.%, based on the total weight of the isocyanate component. The filler content of the amine component is preferably up to 80 wt.%, preferably 10 to 70 wt.%, more preferably 35 to 65 wt.%, in each case based on the total weight of the amine component.

[0069] Preferred fillers are inorganic fillers, particularly cements such as Portland cement or aluminate cement, as well as other hydraulically setting inorganic materials, quartz, glass, corundum, porcelain, earthenware, barite, light spar, gypsum, talc, and / or chalk, as well as mixtures thereof. The inorganic fillers can be added in the form of sands, flours, or molded bodies, preferably in the form of fibers or spheres. By appropriately selecting the fillers in terms of type and grain size distribution / (fiber) length, application-relevant properties such as rheological behavior, extrusion forces, internal strength, tensile strength, pull-out forces, and impact strength can be controlled. Suitable fillers include, in particular, non-surface-treated quartz flours, fine quartz flours, and ultrafine quartz flours, such as Millisil®< W3, Millisil®< W6, Millisil®< W8, and Millisil®< W12, preferably Millisil®< W12.Silanized quartz flours, fine quartz flours, and ultrafine quartz flours can also be used. These are available, for example, under the Silbond ®< product series from Quarzwerke. The Silbond ®< EST (epoxysilane-modified) and Silbond ®< AST (aminosilane-treated) product series are particularly preferred. Furthermore, aluminum oxide-based fillers such as ultrafine aluminum oxide fillers of the ASFP type from Denka, Japan, (d50 = 0.3 µm) or grades such as DAW or DAM with the type designations 45 (d50 < 0.44 µm), 07 (d50 > 8.4 µm), 05 (d50 < 5.5 µm), and 03 (d50 < 4.1 µm) can be used. Furthermore, surface-treated fine and ultrafine fillers such as Aktisil AM (aminosilane-treated, d50 = 2.2 µm) and Aktisil EM (epoxysilane-treated, d50 = 2.2 µm) from Hoffman Mineral can be used. The fillers can be used individually or in any desired mixture.

[0070] The flow properties are adjusted by adding rheology additives, which are used according to the invention in the isocyanate component and / or the amine component. Suitable rheology additives include: phyllosilicates such as Laponite, bentone, or montmorillonite; Neuburg Siliceous Earth; fumed silica; polysaccharides; polyacrylate, polyurethane, or polyurea thickeners; and cellulose esters. For optimization, wetting and dispersing agents, surface additives, defoamers and deaerators, wax additives, adhesion promoters, viscosity reducers, or process additives can also be added.

[0071] The proportion of one or more rheology additives in the isocyanate component is preferably 0.1 to 3 wt.%, more preferably 0.1 to 1.5 wt.%, based on the total weight of the isocyanate component. The proportion of one or more rheology additives in the amine component is preferably 0.1 to 5 wt.%, more preferably 0.5 to 3 wt.%, based on the total weight of the amine component.

[0072] In one embodiment, the multi-component resin system contains a molecular sieve, in particular a zeolite as filler.

[0073] As zeolites, synthetic or natural zeolites can be used, which are generally characterized by the composition Mn +< x / n [(AlO 2 ) -< x (SiO 2 ) y ]·zH 2 O where n is the charge of M, usually 1 or 2, and M is a cation of an alkali or alkaline earth metal, in particular Na +< , K +< , Ca 2+< and Mg 2+<.

[0074] The following zeolites can be used: Zeolite A (Na 12[ (AlO 2 )12(SiO 0 ) 12 ] · 27 H 2 O; K 12 [(AlO 2 ) 12 (SiO 2 ] 12 ] · 27 H 2 O), Zeolite X (Na 86 [(AlO 2 ) 86 (SiO 2 ) 106 ] · 264 H 2 O), zeolite Y (Na 56 [(AlO 2 ) 56 (SiO 2 ) 136 ] · 250 H 2 O), zeolite L (K 9 [(AlO 2 ) 9 (SiO 2 ) 27 ] · 22 H 2 O), modernite (Na 8.7 [(AlO 2 ) 8.7 (SiO 2 ) 39.3 ] · 24 H 2 O), zeolite ZSM 5 (Na 0.3 H 3.8 [(AlO 2 ) 4.1 (SiO 2 ) 91.9 ]) and zeolite ZSM 11 (Na 0.1 H 1.7 [(AlO 2 ) 1.8 (SiO 2 ) 94.2 ]). Of these, zeolite A, zeolite X, zeolite Y and zeolite ZSM 5 and zeolite ZSM 11 are preferred.

[0075] The molecular sieve, especially the zeolite, can be used as a powder, granules or as a paste (e.g. 48-50% powder dispersed in castor oil).

[0076] The synthetic zeolite is preferably a synthetic zeolite comprising particles with a particle size of up to 250 µm, in particular 5 µm to 24 µm. The synthetic zeolite particularly preferably has a pore size of about 5 Å to about 10 Å, in particular about 3 Å to about 4 Å.

[0077] The specific surface area (BET) of the zeolite particles is preferably between 800 m 2 < / g and 1000 m 2 < / g.

[0078] The residual water content of the zeolite is below 2.5% w / w, preferably below 1.5% w / w, and the water absorption capacity is below 22 - 24% w / w.

[0079] It is possible to use a mixture of two or more different types of zeolite.

[0080] The molecular sieve, in particular the zeolite, is preferably used in an amount of 0.1 to 60 wt.%, more preferably in an amount of 1 to 35 wt.%, and most preferably in an amount of 2 to 5 wt.%, based on the total weight of the multicomponent resin system. These amounts are taken into account in the general, above-mentioned quantities for the fillers, with the amounts of the molecular sieve being taken into account in the quantities of the fillers.

[0081] The molecular sieve can be contained in one of the two components of the multi-component resin system or in both components.

[0082] A further object is a mortar composition which is produced by mixing the isocyanate component and the amine component of the multi-component resin system.

[0083] The multi-component resin system is preferably present in cartridges, cartridges or foil bags, which are characterized in that they comprise two or more separate chambers in which the isocyanate component and the amine component are arranged separately from each other in a reaction-inhibiting manner.

[0084] For the intended use of the multi-component resin system, the isocyanate component and the amine component are emptied from the separate chambers and mixed in a suitable device, such as a static mixer or a dissolver. The mixture of isocyanate component and amine component (mortar mass) is then injected into the previously cleaned borehole using a known injection device. The component to be fixed is then inserted into the mortar mass and adjusted. The reactive components of the isocyanate component react with the amino groups of the amine component under polyaddition, so that the mortar mass cures under ambient conditions within a desired time, preferably within a few minutes or hours.

[0085] The mortar composition or the multi-component resin system according to the invention is preferably used for construction purposes. The term "for construction purposes" means the construction bonding of concrete / concrete, steel / concrete, or steel / steel, or one of the aforementioned materials, to other mineral materials; the structural reinforcement of components made of concrete, masonry, and other mineral materials; the reinforcement applications of building objects with fiber-reinforced polymers; the chemical fastening to surfaces made of concrete, steel, or other mineral materials, in particular the chemical fastening of structural elements and anchoring devices, such as anchor rods, anchor bolts, (threaded) rods, (threaded) sleeves, reinforcing bars, screws, and the like, in drilled holes in various substrates, such as (reinforced) concrete, masonry, other mineral materials, metals (e.g., steel), ceramics, plastics, glass, and wood.The mortar compositions according to the invention and the multi-component resin systems according to the invention are particularly preferably used for the chemical fixing of anchoring agents.

[0086] A further object of the present invention is a method for the chemical fastening of construction elements in boreholes, wherein a mortar composition according to the invention or a multi-component resin system according to the invention as described above is used for the chemical fastening of the construction elements.The method according to the invention is particularly suitable for the construction bonding of concrete / concrete, steel / concrete or steel / steel or one of the aforementioned materials to other mineral materials, the structural reinforcement of components made of concrete, masonry and other mineral materials, the reinforcement applications with fiber-reinforced polymers of building objects, the chemical fastening to surfaces made of concrete, steel or other mineral materials, in particular the chemical fastening of structural elements and anchoring means, such as anchor rods, anchor bolts, (threaded) rods, (threaded) sleeves, reinforcing bars, screws and the like, in drill holes in various substrates, such as (reinforced) concrete, masonry, other mineral materials, metals (e.g. steel), ceramics, plastics, glass and wood. The method according to the invention is very particularly preferably used for the chemical fastening of anchoring means.

[0087] A further object of the present invention is also the use of a mortar composition according to the invention or a multi-component resin system for the chemical fixing of construction elements in mineral substrates.

[0088] A further subject matter is the use of a mortar composition according to the invention or a multi-component resin system according to the invention for improving the pull-out forces of a chemical anchor produced from a multi-component resin system according to the invention. This particularly includes an increase in the pull-out strength in well-cleaned boreholes, where well-cleaned means that the boreholes were repeatedly blown out with compressed air, then brushed to loosen any drilling dust and debris adhering to the borehole walls, and then repeatedly blown out with compressed air.

[0089] The invention is further described below with reference to exemplary embodiments, which, however, should not be understood in a limiting sense. Examples of implementation

[0090] The following compounds were used to prepare the comparative composition and the composition according to the invention: Hexamethylene-1,6-diisocyanate homopolymers Low-viscosity, aliphatic polyisocyanate core based on hexamethylene diisocyanate (equivalent weight approx. 179; NCO content according to M105-ISO 11909 23.5 ± 0.5 wt.%, monomeric HDI according to M106-ISO 10283 < 0.25%; viscosity (23°C) M014-ISO 3219 / A.3 730 ± 100 mPa s; Desmodur™< N 3900) Covestro AG Mixture of 6-methyl-2,4-bis(methylthio)phenylene-1,3-diamine and 2-methyl-4,6-bis(methylthio)phenylene-1,3-diamine Ethacure ®< 300 Curative (Dimethylthiotoluenediamine 95-97%, Monomethylthiotoluenediamine 2-3%; equivalent weight with isocyanates 107) Albermale Corporation 3-Glycidyloxypropyltrimethoxysilane Dynasylan ®< GLYMO Evonik Resource Efficiency GmbH Tris(isooctadecanoato-O-)(propane-2-olato)titanium Ken-React ®< KR ®< TTS FARRL GmbH Hydrogentetrakis[2,2-bis(allyloxy)-methyl]butane-1-olato-O1]bis(ditridecylphosphito-O")titanate(2-) Ken-React ®< KR ®< 55 FARRL GmbH 1,3-Bis(glycidyloxypropyl)-tetramethyldisiloxane ABCR GmbH quartz flour Millisil™< W12 Quartz works Frechen Silica Cab-O-Sil™< TS-720 Cabot

[0091] The comparative composition and the inventive compositions of the isocyanate component and the amine component are given in Table 1 below.

[0092] To produce the mortar mixtures, the isocyanate component and the amine component were first prepared separately. For this purpose, the components listed in Table 1 were homogenized in a dissolver (PC Laborsystem GmbH, 8 min; 3500 rpm) under vacuum (80 mbar) to form a bubble-free, pasty mass. The isocyanate component and the amine component were then combined and mixed in a speed mixer for 30 s at 1500 rpm. The resulting mortar mixture was filled into a one-component hard cartridge and injected into a borehole using a dispenser.

[0093] To determine the bond stresses (load values) of the cured fastening compounds, Hilti HAS-M12 anchor threaded rods were inserted into hammer-drilled holes in dry C20 / 25 concrete with a diameter of 14 mm and a hole depth of 72 mm. The holes were first cleaned twice with compressed air (6 bar), then twice with a cleaning brush, and again twice with compressed air (6 bar). The cleaned holes were then half-filled with the reference composition and the compositions according to the invention, and the anchor threaded rods were inserted to an embedment depth of 60 mm. The bond stresses were determined by centrally withdrawing the anchor threaded rods. Five anchor threaded rods were inserted in each case, and the bond stress was determined after 24 hours of curing at approximately 21°C.The fixing compounds were pressed out of the cartridges using a static mixer (mixer HIRT-RE-M; Hilti Aktiengesellschaft) and injected into the drill holes.

[0094] The bond stresses obtained for dry and well-cleaned boreholes using the mortar formulations described above are listed in Table 2 below. Table 2: Results of the determination of bond stresses Comparison 1 Comparison 2 1 2 3 Bond stress [N / mm 2< ] 28,8 33,2 31,1 33 32,7

[0095] The results demonstrate that the compositions of the invention exhibit superior performance in well-cleaned, dry boreholes compared to the compositions containing no coupling agent. Furthermore, the results show that the claimed additives exhibit comparable values ​​to the silane additives of Comparative Example 2.

Claims

1. Multi-component resin system containing - an isocyanate component which comprises at least one aliphatic and / or aromatic polyisocyanate having an average NCO functionality of 2 or more, and - an amine component comprising at least one amine which is reactive to isocyanate groups and has an average NH functionality of 2 or more, with the proviso that the multi-component resin system is free of polyaspartic acid esters, the isocyanate component and / or the amine component comprising at least one filler and at least one rheology additive and the total filling level of a mortar composition produced by mixing the isocyanate component and the amine component being in a range from 30 to 80 wt.%, characterized in that the isocyanate component and / or the amine component contains at least one additive, the additive being - a compound of formula I         An(L)m(X)p     (formula I), wherein A represents phosphorous, boron, aluminum, titanium or zirconium, X can be the same or different and represents an alkoxy, aryloxy or acyloxy functional group, L can be the same or different and represents at least one ligand, n represents the valency of A, and p represents an integer from 1 to n, m represents 0 or an integer from 1 to n-1 and n = m+p, or - a siloxane having at least one functional group which is capable of addition reaction to isocyanates, but which has no hydrolyzable groups bonded to a silicon atom.

2. Multi-component resin system according to claim 1, characterized in that in the compound of formula I, X is an alkoxy functional group -OR1 or an acyloxy functional group -O(C=O)R1, wherein R1 is in each case an optionally substituted, linear or branched alkyl group having 1 to 24 carbon atoms.

3. Multi-component resin system according to claim 2, characterized in that X is a functional group selected from the group consisting of -O-CH3, -O-C2H5, -O-C3H7, -O-C4H9, -O-C5H11, -O-(CO)-CH3, -O-(CO)-C2H5, -O-(CO)-C3H7, -O-(CO)-C4H9 and -O-(CO)-C5H11.

4. Multi-component resin system according to claim 3, characterized in that X is a functional group selected from the group consisting of -O-CH3, -O-C2H5, -O-C3H7 and -O-C4H9.

5. Multi-component resin system according to any of the preceding claims, characterized in that in the compound of formula I, X is the same.

6. Multi-component resin system according to any of the preceding claims, characterized in that in the compound of formula I, the ligand L is selected from the group consisting of acetoacetate, phosphate, phosphite, sulfate, sulfite, CO, CN, cyclopentyl and pentamethylcyclopentyl.

7. Multi-component resin system according to any of the preceding claims, characterized in that the compound of formula I is selected from the group consisting of trimethyl phosphate, triethyl phosphate, triethyl borate, triethyl aluminate, triisopropyl borate, tributyl borate, tetraethyl titanate, tetraisopropyl titanate, tetraethyl zirconate and tetrabutyl zirconate.

8. Multi-component resin system according to any of the preceding claims, characterized in that the compound of formula I is present in an amount of 0.001 - 10 wt.%, based on the total weight of the multi-component resin system.

9. Multi-component resin system according to claim 1, characterized in that in the siloxane, the functional group capable of addition reaction with isocyanate groups is a terminal functional group.

10. Multi-component resin system according to claim 9, characterized in that the functional group is selected from the group consisting of hydroxy, carboxy, amino, sec. amino, mercapto, isocyanato, alkenyl, (meth)acryloyl, anhydrido and epoxy functional groups, preferably from the group consisting of epoxy and amino functional groups.

11. Multi-component resin system according to any of claims 1, 9 or 10, characterized in that the siloxane has the structure         R3Si-[O-Si(R1)2]n-O-SiR3 wherein n represents 0 or an integer from 1 to 1000, inclusive, R and R1 each independently represent a C1-C20-alkyl functional group or aralkyl functional group optionally containing heteroatoms and optionally comprising at least one functional group capable of addition reaction with isocyanate groups.

12. Multi-component resin system according to any of preceding claims 9 to 11, characterized in that the siloxane comprises two or more identical or different, preferably two identical terminal functional groups capable of addition reaction with isocyanate groups.

13. Multi-component resin system according to any of claims 1 or 9 to 12, characterized in that the siloxane is selected from the group consisting of 1,3-bis(2-aminoethylaminoethyl)tetramethyldisiloxane, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, tris(glycidoxypropyldimethylsiloxy)-phenylsilane, 3-methacryloxypropylpentamethyldisiloxane, poly(acryloxypropylmethyl)siloxane, 1,3-bis[(acryloxypropylmethyl)siloxane, 1,3-bis(3-methacryloxypropyl)tetrakis-(trimethylsiloxy)disiloxane, 1,3-bis(3-methacryloxypropyl)tetramethyldisiloxane, monomethacryloxypropyl terminated polydimethylsiloxane, poly[dimethylsiloxane-co-(3-(monomethacryloxy)propyl)methylsiloxane], 1,3,-bis(4-methacryloxybutyl)tetramethyldisiloxane, (methacryloxypropyl)methyl siloxane / dimethylsiloxane copolymer, dodecamethylpentasiloxane, 1,1,1,3,5,7,7,7-octamethyl-3,5-bis(trimethylsilanyloxy)tetrasiloxane, trimethylsilyl terminated poly(methylhydro-siloxane), bis(hydroxyalkyl)-terminated poly(dimethylsiloxane), poly[dimethylsiloxane-co-(2-(3,4-epoxycyclohexyl)ethyl)methylsiloxane], diglycidyl ether terminated poly(dimethylsiloxane), poly[dimethylsiloxane-co-[3-(2-(3-hydroxyethoxy)ethoxy)propyl]methylsiloxane and monoglycidyl ether terminated poly(dimethylsiloxane).

14. Multi-component resin system according to any of claims 1 or 9 to 13, characterized in that the proportion of the siloxane is from 0.5 to 20 wt.%, based on the total weight of the multi-component resin system.

15. Multi-component resin system according to any of the preceding claims, characterized in that both the isocyanate component and the amine component comprise at least one filler and at least one rheology additive.

16. Multi-component resin system according to claim 15, characterized in that the filling level of the isocyanate component and the filling level of the amine component is 10 to 70 wt.%, based in each case on the total weight of the isocyanate component and the amine component, respectively.

17. Multi-component resin system according to any of the preceding claims, characterized in that the isocyanate component and the amine component are present in a quantity ratio in which the equivalent ratio of NCO groups to amine groups which are reactive to the NCO groups is between 0.3 and 2.0.

18. Multi-component resin system according to any of the preceding claims, characterized in that the isocyanate component comprises at least one aromatic polyisocyanate selected from the group consisting of 1,4-phenylene diisocyanate, 2,4- and / or 2,6-toluylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, 1,5-naphthylene diisocyanate, diphenylene methane-2,4'- and / or -4,4'-diisocyanate, triphenylmethane-4,4',4"-triisocyanate, bis- and tris-(isocyanatoalkyl)-benzene, -toluene and -xylene, and mixtures thereof.

19. Multi-component resin system according to any of claims 1 to 17, characterized in that the isocyanate component comprises at least one aliphatic polyisocyanate selected from the group consisting of hexamethylene diisocyanate (HDI), trimethyl HDI (TMDI), pentane diisocyanate (PDI) 2-methylpentane-1,5-diisocyanate (MPDI), isophorone diisocyanate (IPDI), 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane (H6XDI), bis(isocyanatomethyl)norbornane (NBDI), 3(4)-isocyanatomethyl-1-methylcyclohexyl isocyanate (IMCI) and 4,4'-bis(isocyanatocyclohexyl)methane (H12MDI), and mixtures thereof.

20. Multi-component resin system according to any of the preceding claims, characterized in that the total filling level is in a range from 35 to 65 wt.%, based on the total weight of the multi-component resin system.

21. Multi-component resin system according to any of the preceding claims, characterized in that the amine which is reactive to isocyanate groups is selected from the group consisting of 4,4'-methylene-bis[N-(1-methylpropyl)phenylamine], an isomer mixture of 6-methyl-2,4-bis(methylthio)phenylene-1,3-diamine and 2-methyl-4,6-bis(methylthio)phenylene-1,3-diamine (Ethacure 300), 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylenebis(N-sec-butylcyclohexanamine) (Clearlink 1000), 3,3'-diaminodiphenylsulfone (dapsone), N,N'-di-sec-butyl-p-phenylenediamine and 2,4,6-trimethyl-m-phenylenediamine, and mixtures thereof.

22. Multi-component resin system according to any of the preceding claims, characterized in that the multi-component resin system is a two-component resin system.

23. Mortar composition produced by mixing the isocyanate component and the amine component of the multi-component resin system according to any of the preceding claims.

24. Method for chemically fastening construction elements in boreholes, wherein a mortar composition according to claim 23 or a multi-component resin system according to any of claims 1 to 22 is used for the chemical fastening.

25. Use of a mortar composition according to claim 23 or a multi-component resin system according to any of claims 1 to 22 for improving the pull-out values of a chemical anchor.

26. Use according to claim 25 for improving the pull-out strength in cleaned boreholes.