Phthalate-free kit - use for fixing anchoring elements in the construction field

Abstract

This invention relates to the use of sleeves or film bags in the form of sockets for securing anchoring elements in holes, particularly in drilled holes, in which the sleeves or film bags have multiple, particularly two, compartments. One compartment contains a synthetic resin component comprising a synthetic resin that can be polymerized by free radicals, and the other compartment contains a desensitizing free radical initiator in a curing agent component. The free radical initiator is desensitized by a phthalate-free plasticizer in at least a partial coating, and the plasticizer has a melting point in the range of 40-90°C. The free radical initiator is present in solid form at room temperature, and the desensitizing free radical initiator is present in particulate form at room temperature and is implemented as a free-flowing powder, according to the relevant subject matter of the invention.

Description

[0001] This invention relates to the use of sleeves or film bags in the form of cassettes for securing anchoring elements in holes (particularly drilled holes) in building substrates, the sleeves or film bags having multiple, particularly two, compartments, one of which contains a synthetic resin component comprising a synthetic resin containing a free radical polymerizable synthetic resin, and the other compartment containing a desensitizing free radical initiator in a curing agent component, wherein the free radical initiator is desensitized by a phthalate-free plasticizer in at least a partial coating, and wherein the plasticizer has a melting point in the range of 40-90°C, preferably in the range of 60-75°C, the free radical initiator is present in solid form at room temperature and the desensitizing free radical initiator is present in particulate form at room temperature and is implemented as a free-flowing powder, and to a method for securing anchoring agents in holes in building substrates, in which the aforementioned uses occur.

[0002] Organic peroxides, such as benzoyl peroxide, dichlorobenzoyl peroxide, dichlorobenzoyl peroxide (2,4-dichlorobenzoyl), or cyclohexanone peroxide, are used in particular as initiators for the polymerization of free-radical curable synthetic resins. The free form of peroxides readily decomposes abruptly (even explosively) and is therefore "desensitized" by inert materials for use in the construction industry, making the use and storage of peroxides safe.

[0003] The desensitization can be achieved by water, by solid inorganic materials such as gypsum (see EP 0 508 183) or calcium phosphate, or by using a paste containing a plasticizer (see US 3,324,040).

[0004] DE 101 15 587 A1 describes the use of benzoyl peroxide inert with dicyclohexyl phthalate in one chamber (inner glass) of a two-chamber glass sleeve containing a urea carbamate resin based on diisocyanate diphenylmethane and tert-butylaminoethyl-methacrylate in the other chamber (ampoule), wherein the glass sleeve is then fed into a borehole and destroyed thereby by a screw, thereby causing the components to react and polymerize and thus cure in the presence of the screw.

[0005] In addition, dicyclohexyl phthalate (DCHP) and other phthalate esters are suspected to have significant health-damaging effects.

[0006] It has now been shown that other plasticizers can be used instead of dicyclohexyl phthalate in the field of fixing anchors in drilled holes in building substrates, provided that the plasticizer has a melting temperature in the range of 40-90°C, the initiator is in solid form at room temperature, and the desensitized free radical initiator is in particulate form at room temperature and is implemented as a free-flowing powder at room temperature (free-flowing, that is, non-caking, i.e., without clumping).

[0007] The following definitions are used to explain specific terms or symbols and to describe specific embodiments of the invention, wherein, in the context of the embodiments of the invention mentioned, a single, multiple or all terms or symbols may be specifically defined instead, which obtains the specific embodiments of the invention.

[0008] Room temperature should be understood as a range of 20±2℃, especially a range of 20±0.5℃.

[0009] "Beinhalten" or "umfassen" or "enthalten" or "enthalten" indicates that other components or features may exist in addition to those mentioned, meaning it is not exhaustive.

[0010] Where the attribute is mentioned as "in addition," it indicates that a feature that does not possess that attribute may be preferred.

[0011] "And / or" indicates that the mentioned features / substances may exist individually or in combination of two or more of the respective mentioned features / substances.

[0012] Where “(meth)acrylate” or “-(meth)acrylate” is used, it always means acrylate, methacrylate, or a mixture of acrylate and methacrylate.

[0013] Suitable boxes, especially sleeves or film bags, are used within the scope of this invention.

[0014] The sleeve is a sleeve having an outer ampoule (one of the compartments) and an inner ampoule (one or the other of the compartments) within the outer ampoule, the outer ampoule containing a free radical curable synthetic resin, and the inner ampoule containing a free-flowing, desensitizing free radical initiator present in particulate form at room temperature.

[0015] The outer ampoule is preferably made of a fusible, solid, and brittle material at room temperature, such as plastic or, in particular, glass. The inner ampoule may also be made of a fusible, solid, and brittle material at room temperature, such as plastic or, in particular, glass, or, in addition, as a two- or multi-chamber (with two or more compartments) film bag (in particular, a plastic film, which may be metallized or, if desired, a metal film).

[0016] In use or in the method according to the invention, in each case, the sleeve or film bag is broken by introducing an anchoring element, and the components of the sleeve according to the invention can contact each other and the anchoring element and the hole (especially the borehole) wall, and the anchoring element is fixed in the borehole under aggregation.

[0017] The desensitizing agent ("curing agent" in the narrow sense) of the free radical initiator is preferably a plasticizer selected from ortho- or meta-terphenyl and benzoic acid esters, such as phenyl benzoate, p-tert-butyl-phenyl benzoate, glyceryl tribenzoate, ethylene glycol dibenzoate (particularly preferred), or triethylene dibenzoate (preferably). All these substances share the characteristic that their melting points are above 40°C. Mixtures of two or more of these components may also be present, provided the melting point is between 40-90°C, particularly between 40-75°C.

[0018] A melting temperature in the range of 40-90°C is preferred, which is determined by melting the sample and reading the melting temperature on a thermometer, for example at a heating rate of 2°C / min, or by using an automatic melting point apparatus. A preferred melting point is 40-80°C, more preferably 50-75°C, for example 60-72°C.

[0019] The desensitized free radical initiator is free-flowing at room temperature (free-flowing, non-caking). This ensures that it is not dusty, as otherwise there would be a danger that the initiator (peroxide) adhering to the wall during melting of the sleeve or bag would decompose and potentially cause problems during melting (formation of bubbles, etc.).

[0020] Particularly advantageous is the average particle size d of the free-flowing powder. 50The particle size ranges from 100-500 μm, particularly 150-400 μm, and is most advantageous for processability and fillability, while maintaining good solubility in synthetic resins under application conditions. The range of 180-300 μm particles is also optimal, with a maximum proportion of fine particles <100 μm (maximum 5% by weight, particularly 1% by weight) and a maximum proportion of coarse particles >500 μm (maximum 5% by weight, particularly 2% by weight or 1% by weight) in each case. Powders with these particle size parameters allow for uniform distribution along the sleeve axis when filled into inner ampoules (curing agent tubes). Particle size and particle size distribution can be determined using conventional methods (sieving, laser diffraction, image analysis, etc.). The data given here in weight percent are based on curing agent powder (= curing agent composition).

[0021] As the free radical initiator for curing the casing according to the invention, radical-forming peroxides are used, such as organic peroxides, like diacyl peroxides, such as benzoyl peroxide (particularly preferred), di-(p-chlorobenzoyl) peroxide, di-(2,4-dichlorobenzoyl) peroxide, acetyl benzoyl peroxide; peroxide ketones, such as bis(1-hydroxyalkyl) peroxide, such as 1,1'-dihydroxydicyclohexyl peroxide, or diketone peroxide, such as 3,5-dimethyl-3,5-dihydroxy-1,2-dioxolane), methyl ethyl ketone peroxide or cyclohexanone peroxide, peroxide esters of mono- or dicarboxylic acids, such as mono-tert-butylperoxymaleate and di-tert-butyldisperoxyphthalate, or peroxyalkyl esters, such as tert-butylperphthalate, inorganic peroxides, such as persulfates or perborates, and mixtures thereof. These are solid substances at room temperature.

[0022] In a possible preferred embodiment of the invention, the proportion of the free radical initiator (curing agent in the narrow sense) is 0.5-90% by weight, for example 10-70% by weight, particularly 45-55% by weight, based on the curing agent composition.

[0023] Here, the proportion of the curing agent component in the kit to be used according to the invention is preferably 0.1-60% by weight, for example 0.5-30% by weight, especially in the range of 1-15% by weight, wherein the proportion of peroxide, also based on the mass (100%) of the entire associated reactive resin formulation, is 0.1% or more by weight, for example 0.5-15% by weight, especially 1-10% by weight, and in a particularly preferred embodiment it can be 0.1 to <1% by weight.

[0024] Other components of the curing agent are possible, such as fillers and / or other additives, such as thickeners and / or other additives, such as dyes, pigments, additives, etc. Based on the curing agent composition, the proportion of all additives can be, for example, a total of 0.1 (especially 10) to 99.5% by weight, or, for example, 1 (especially 10) to 70% by weight.

[0025] The preparation of a desensitizing radical initiator contained in a kit according to the invention, wherein the plasticizer has a melting temperature of 40-90°C or, particularly as described above, the initiator is in solid form at room temperature, and the desensitizing radical initiator is in particulate form at room temperature and exhibits a free-flow dynamic, can be achieved, for example, by mixing anhydrous or aqueous (e.g., 20-30% by weight based on the curing agent composition) organic peroxide (as described in the context) with a preferably powdered, or if desired, ground, solid plasticizer (as described in the context), or preferably by coating a solid organic peroxide with a solid plasticizer, wherein the coating is carried out by adding the plasticizer, either in melt form or dissolved in an easily (distilled) removed solvent, to a diluted organic peroxide suspension under vigorous stirring and heating, particularly at a temperature above the melting temperature of the plasticizer, for example 40-90°C or, particularly, as described above, followed by cooling and crystallization of the coated peroxide particles. The desired particle size can be adjusted by sieving if necessary, especially when it cannot be adjusted by process control.

[0026] The synthetic resin contained in the free radical polymerizable (= curable) synthetic resin (reactive resin) is preferably selected from vinyl ester urethane resin, vinyl ester resin, propoxylated or especially ethoxylated aromatic diol-(especially bisphenol-A) or linear phenolic varnish (Novolak)-(especially di-)(meth)acrylate, or otherwise selected from unsaturated polyester.

[0027] As a vinyl ester urethane resin, such as one of those disclosed in EP 0 508 183 A1, or one of those described below as preferred urethane (meth)acrylates.

[0028] EP 0 508 183 A1 describes vinyl ester urethane resins having the following groups:

[0029] a)

[0030]

[0031] b)

[0032]

[0033] c)

[0034] -O-R3-O

[0035] d)-NH-R4-NH

[0036] Each of R2 represents an aromatic, aliphatic, or alicyclic group, optionally containing an ether group, having 4 to 300 carbon atoms, preferably an aromatic group having 6 to 100 carbon atoms; R3 and R3 each independently represent an aliphatic, alicyclic, or aromatic group having 2 to 500 carbon atoms, preferably an aliphatic group having 4 to 100 carbon atoms, wherein the vinyl ester urethane resin is preferably (A) a multifunctional isocyanate (e.g., 4... The reaction product of (A): (B1*B2) is a mixture of isomers of 4'-diphenylmethane diisocyanate or 2,2'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate, (B1) optionally a polyol (e.g., dipropylene glycol, polypropylene glycol or a mixture of both), and / or (B2) optionally a polyamine (e.g., an aminobenzoate of polymethylene ether glycol), and (C) a hydroxyalkyl (meth)acrylate (e.g., hydroxypropyl (meth)acrylate), wherein the reaction has a weight ratio of (A):(B1*B2) of 100:0 to 100:300, and the equivalence ratio of the hydroxyalkyl (meth)acrylate to the free isocyanate groups of the reaction product A*B1*B2 is 3:1 to 1:2.

[0037] Preferred are urethane (meth)acrylates, which are obtained on the one hand by reacting pre-extended monomeric di- or polyisocyanates, and / or on the other hand by reacting polymerized di- or polyisocyanates (e.g., PMDI, MDI) with hydroxyalkyl (meth)acrylates, such as hydroxyethyl- or hydroxypropyl (meth)acrylates. The methods and approaches used to carry out the pre-extended reaction and the numerous possibilities for such reactions are known to those skilled in the art and will not be fully described herein. Reference is made, for example, to applications EP 0508183 A1, EP 0432087 A1, and the unpublished application DE 102014 101 861.3 dated February 14, 2014.

[0038] One particular embodiment relates to such a urethane (meth)acrylate resin, which is prepared according to a method briefly outlined below.

[0039] This relates to a method for preparing vinyl ester urethane resins, particularly urethane (meth)acrylate resins (hereinafter also referred to as U(M)A-resins), characterized in that, as the reaction raw materials for preparing vinyl ester urethane resins, especially U(M)A-resins, an isocyanate with an average functionality of 2 or especially greater than 2 (which can also be achieved by mixing isocyanates with a functionality less than 2 and isocyanates with a functionality greater than 2), for example 2 or especially 2.1-5, for example 2.2-4, advantageously for example 2.3-3.5, reacts with a fatty alcohol having at least one C-C double bond (non-conjugated-olefinic bond), especially a hydroxyalkyl (meth)acrylate, preferably a hydroxy-lower alkyl (meth)acrylate, such as hydroxyethyl (meth)acrylate or especially hydroxypropyl (meth)acrylate, preferably 2-hydroxypropyl methacrylate (HPMA). Industrially available HPMA is considered here as a mixture of 2-hydroxypropyl methacrylate and hydroxyisopropyl methacrylate. Other fatty alcohols with olefinic bonds may also exist as industrial mixtures of isomers or as pure isomers.

[0040] Isocyanates with an average functionality less than 2 or more than 2, such as 2.1-5, or 2.2-4, and advantageously 2.3-3.5, are, for example, urea diketones, isocyanurates, iminooxadiazine ketones, urea ketimines, biurets, urethanes, and / or carbodiimides (advantageously having a molecular weight distribution such that no single molecule species is present in more than 50% by weight and at the same time more than 50% by weight of the chain is composed of at least 3+). 1. A covalently bonded monomer unit / reactant composition (see the precise definition of a polymer according to REACH)) polyisocyanate, or preferably (e.g., typically produced in industrial production processes or subsequently targeted (e.g., by adding and / or distilling off monomers or mixtures of monomers)) a mixture of (i) and (ii), where (i) is a mono- or especially diisocyanate of one or more monomers, such as diphenylmethane diisocyanate (MDI), especially 4,4'-diphenylmethyl diisocyanate or 2,2'-diphenylmethane diisocyanate or a mixture of diphenylmethane diisocyanate isomers (with the isocyanate group at different positions on the phenyl core), as mentioned above, and (ii) is one or more "polymerized" diphenylmethane diisocyanates (PMDI), i.e., preferably Roh-MDI having (i.e., containing) multiple isomers and higher functional homologs (crude product of industrially produced MDI, without, for example, separation of individual isomers by distillation) and the Roh-MDI having, for example, an average molecular weight on the order of 200-800 g / The product has the functionality described above, for example, an average molecular weight of 280-500, such as 310-480, and a functionality of 2.4-3.4, such as 3.2. Preferably, it is a commercially available PMDI obtained from Roh-MDI itself or also from Roh-MDI, for example by distillation away and / or addition of monomeric MDI, and has an average molecular weight of 310-450. It may also contain ureadione, isocyanurate, iminooxadiazineone, urea-ketimine, biuret, urethane, and / or carbodiimine structures. Particularly preferred are commercially available PMDIs with a molecular weight distribution in which no single molecule is present in greater than 50% by weight.

[0041] "Functionality" should be understood as the (average) number of isocyanate groups per molecule. The functionality of diphenylmethane diisocyanate (basically, excluding deviations caused by contamination) is 2. For the PMD, which refers to the average functionality (usually described by the manufacturer), it can be calculated according to the following formula:

[0042]

[0043] ( f =Functionality, n i =Sensitivity f i (number of molecules)

[0044] And preferably less than or equal to 2 or particularly preferably greater than 2, for example 2.1-5.0 or within the range described above.

[0045] The method for preparing urethane (meth)acrylate resins is preferably carried out in the presence of a catalyst, wherein the appropriate catalyst is well known to those skilled in the art and catalyzes the reaction between hydroxyl and isocyanate groups, such as tertiary amines, such as 1,2-dimethylimidazole, diazabicyclooctane, diazabicyclononane, or organometallic compounds (e.g., compounds of K, Sn, Pb, Bi, Al, and especially compounds of transition metals such as Ti, Zr, Fe, Zn, Cu); and mixtures of two or more of these. For example (based on the reaction mixture) in a proportion of 0.001-2.5% by weight; preferably in the presence of a stabilizer (inhibitor), such as, for example, phenothiazine, TEMPO, TEMPOL, hydroquinone, dimethyl hydroquinone, triphenyl phosphite, tert-butylhydroquinone, hydroquinone monoethyl ether, tert-butylcatechol and / or p-benzoquinone, and mixtures of two or more thereof; for example, in an amount of 0.0001-2.5% by weight based on the reaction mixture, the preferred temperature is, for example, in the range of 0-120°C, advantageously in the range of 50-95°C.

[0046] Examples of suitable catalysts and stabilizers are known to those skilled in the art, for example, as can be seen in "Polyurethane Kunststoff-Handbuch 7" by Becker, GW; Braun, D.; Oertel, G., 3rd edition, Carl Hanser Verlag, 1993.

[0047] The reaction can be carried out in the absence of a solvent (a fatty alcohol having at least one C-C double bond, especially a hydroxy (lower) alkyl (meth)acrylate itself, which then acts as a solvent) or in the presence of a suitable solvent, such as other reactive diluents. "Reactive" here refers to the formulation of the adhesive and its curing, and does not involve the addition of alcohol to the isocyanate.

[0048] The reaction can also be carried out in such a way that a prepolymer is formed by pre-extension, and only thereafter the remaining isocyanate groups react with an aliphatic alcohol having at least one C-C double bond, especially a hydroxy (lower) alkyl (meth)acrylate, as described in the context.

[0049] Here, in order to prepare the prepolymer, isocyanates as described above and polyols having two or more hydroxyl groups per molecule and / or polyamines having two or more amino groups per molecule, or amines having two or more amino and hydroxyl groups per molecule, are used to achieve an average isocyanate functionality of less than 2, 2, or especially greater than 2, or isocyanates with a functionality of 2 are used with polyols, polyamines, or amines with an average OH- and / or amino-functionality greater than 2.

[0050] Polyols (alcohols with di- or higher functionality), particularly alcohols with di- or higher functionality, such as subsequent products of ethylene oxide or propylene oxide, like ethylene glycol, diethylene glycol or triethylene glycol, propane-1,2- or -1,3-diol, dipropylene glycol, other diols such as 1,2-, 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 2-ethylpropane-1,3-diol or 2,2-bis(4-hydroxy-cyclohexyl)propane, triethanolamine, bisphenol A or bisphenol F or their oxyethylated, hydrogenated and / or halogenated products, higher alcohols such as glycerol, trihydroxy... Methylpropane, hexanetriol, and pentaerythritol; hydroxyl-containing polyethers, such as oligomers of aliphatic or aromatic ethylene oxides and / or higher cyclic ethers, such as ethylene oxide, propylene oxide, styrene oxide, and furans; polyethers each with terminal hydroxyl groups, which contain aromatic structural units in their main chain, such as those of bisphenol A or F; and hydroxyl-containing polyesters based on the aforementioned alcohols or polyethers and dicarboxylic acids or their anhydrides, such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydro- or hexahydrophthalic acid, methylenetetrahydrophthalic acid, maleic acid, fumaric acid, itaconic acid, sebacic acid, etc. Particularly preferred are hydroxyl compounds having aromatic structural units that cause chain hardening, hydroxyl compounds with unsaturated components for increasing crosslinking density, such as fumaric acid, or branched or star-shaped hydroxyl compounds, especially tri- or higher functional alcohols and / or polyethers or polyesters containing their structural units. A particularly preferred option is a lower alkyl diol (which produces a divalent group -O-lower alkylene-O-).

[0051] Amino alcohols are compounds that contain, in particular, one or more hydroxyl groups and one or more amino groups in one and the same molecule. Preferably, they are aliphatic amino alcohols, especially hydroxyl lower alkylamines (producing groups -NH-lower alkyl-O- or -O-lower alkyl-NH-), such as ethanolamine, diethanolamine or 3-aminopropanol, or aromatic amino alcohols, such as 2-, 3- or 4-aminophenol.

[0052] Polyamines (di- or higher functional amines) are organic amino compounds having two or more amino groups, especially hydrazine, N,N'-dimethylhydrazine, aliphatic di- or polyamines, especially lower alkane diamines (producing the -NH-lower alkyl-NH- group), such as ethylenediamine, 1,3-diaminopropane, tetra- or hexamethylenediamine or diethylenetriamine, or aromatic di- or polyamines, such as phenylenediamine, 2,4- and 2,6-toluenediamine, or 4,4'-diaminodiphenylmethane, polyether diamines (polyethylene oxide with terminal amino groups), or polyphenylene / polymethylene-polyamines obtainable by condensation of aniline with formaldehyde.

[0053] The ratio of the free isocyanate group in one or more isocyanates to the hydroxyl groups in one or more hydroxyl lower alkyl (meth)acrylates is advantageously chosen such that the isocyanate group is rapidly and completely converted, that is, the molar amount of the hydroxyl group (and therefore the associated molar amount of the hydroxyl lower alkyl (meth)acrylate) is greater than the molar amount of the isocyanate group, for example, by a factor of 1.03-5, such as a factor of 1.05-4 or 1.1-3. The excess hydroxyl lower alkyl (meth)acrylate is used as a reactive diluent.

[0054] Vinyl ester resins, especially esters of unsaturated carboxylic acids and aromatic di- or polyepoxides, particularly bisphenol-A, bisphenol-F and / or linear phenolic varnish-di- and / or poly-glycidyl ethers, react with unsaturated carboxylic acids, such as C2-C7-olefinic acids, such as (meth)acrylic acid, as reaction products.

[0055] Examples of epoxy (meth)acrylates present or used in specific embodiments of the present invention are those of the following ideal form:

[0056]

[0057] Or, generally, when considering the pre-extension reaction in the preparation of bisphenol A-diglycidyl ether, the following ideal formulations are:

[0058]

[0059] Where n represents a value greater than or equal to 1 (when different molecular mixtures with different n values ​​exist and when expressed by the formula, the average value can also be a non-integer value).

[0060] Propanthoxylated or especially ethoxylated aromatic diols or linear phenolic varnishes (especially di-)(meth)acrylates are preferably propoxylated or especially ethoxylated bisphenol-A, bisphenol-F or linear phenolic varnishes (especially di-)(meth)acrylates.

[0061] Examples of propoxylated or especially ethoxylated aromatic diols such as bisphenol-A, bisphenol-F, or linear phenolic varnishes (especially di-)(meth)acrylates present or used in specific embodiments of the invention are those of the following ideal formulations.

[0062]

[0063] Or, generally, when considering a higher degree of ethoxylation, the following ideal formula should also be taken into account:

[0064]

[0065] Where a and b each represent values ​​greater than or equal to 0 independently, provided that at least one value is greater than 0, and preferably both are 1 or greater (when different molecular mixtures with different (a and b) values ​​exist and are expressed by the formula, the average value may also be a non-integer value, while for the isolated single molecules observed, each is only an integer).

[0066] In addition to the polymerizable components mentioned above (which are polymerizable components of synthetic resins), other (especially conventional) inclusions may be contained in the synthetic resin composition.

[0067] Important examples of other inclusions are amine accelerators, inhibitors, non-reactive diluents, reactive diluents, thixotropic agents, fillers and / or other additives.

[0068] As amine accelerators, those with sufficiently high activity are considered, such as, in particular (preferably tert-, especially hydroxyalkylamino group-substituted) aromatic amines selected from the group consisting of epoxy-alkylated anilines, toluidines, or dimethylanilines, such as, for example, ethoxylated toluidines, anilines, or dimethylanilines, such as N,N-bis(hydroxypropyl- or hydroxyethyl)-toluidine or -dimethylaniline, such as N,N-bis(hydroxypropyl- or hydroxyethyl)-p-toluidine, N,N-bis(hydroxyethyl)-dimethylaniline, and very particularly corresponding higher alkoxylated industrial products. One or more of these accelerators are possible. The accelerator preferably has a proportion (concentration) of 0.005-10, especially 0.1-5% by weight, here based on the synthetic resin composition.

[0069] As inhibitors, non-phenolic (anaerobic) and / or phenolic inhibitors can be added.

[0070] As phenol inhibitors (which are typically provided as pre-mixed components of commercially available free radical curing reactive resins, but may also be absent elsewhere), considerations include (non-alkylated or alkylated) hydroquinones, such as hydroquinone, as well as mono-, di-, or trimethylhydroquinone; (non-alkylated or alkylated) phenols, such as 4,4'-methylene-bis(2,6-di-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene; (non-alkylated or alkylated) catechols, such as tert-butylcatechol, 3,5-di-tert-butyl-1,2-benzene, or especially 4-methoxyphenol, or mixtures of two or more thereof. The preferred proportions of these inhibitors are at most 1% by weight, especially 0.0001-0.5% by weight, for example 0.01-0.1% by weight, based on the synthetic resin composition.

[0071] As a non-phenolic or anaerobic (i.e., as opposed to phenolic inhibitors, effective even in the absence of oxygen) inhibitor (especially since it has little effect on curing time), phenothiazine or organic nitryl radicals are preferred considerations. Organic nitryl radicals can be added, for example, as described in DE 199 56 509, which is incorporated herein by reference in particular with respect to the compounds described therein, especially 1-oxy-2,2,6,6-tetramethyl-piperidin-4-ol (“4-OH-TEMPO” or “TEMPOL”). Based on the reactive resin formulation, the weight percentage of the non-phenolic inhibitor is preferably in the range of 1 ppm (wt) to 2 wt%, particularly, for example, 10 ppm to 1 wt%, based on the synthetic resin composition.

[0072] As a non-reactive diluent, it can be added, for example, vegetable oils such as castor oil, or in addition, bio-alcohols and fatty acids and their esters, or mixtures of two or more thereof, for example, in proportions of 3-60% by weight, such as 4-55% by weight, based on the synthetic resin content.

[0073] As thixotropic agents, rheology modifiers that typically induce thixotropy, such as pyrolytic silica, can be used. They can be added, for example, in amounts of 0.01-50% by weight, such as 0.5-20% by weight, based on the synthetic resin composition.

[0074] Common fillers are used, particularly cement (e.g., Portland cement or alumina-fused cement), chalk, sand, quartz sand, quartz powder, corundum, etc., which can be added in powder, granular, or molded form, or other fillers or mixtures thereof, wherein the filler may also be silanized. The proportion of the filler is preferably 0-90% by weight, for example 5-80% by weight, based on the entire product including the casing wall (sleeve housing, membrane housing). Hydraulic fillers such as gypsum, quicklime, or cement (e.g., alumina- or Portland cement), water glass, or activated aluminum hydroxide, or two or more of these, can be added as a supplement or alternative to one or more of the above fillers.

[0075] Other additives may also be added, such as plasticizers, non-reactive diluents, toughening agents, stabilizers, rheology modifiers, wetting agents and dispersants, coloring additives, such as dyes or especially pigments, for example, to color the components differently in order to better control their mixing, etc., in mixtures of two or more. These other additives may preferably be added in total at a weight ratio of 0-90%, for example 0-40% by weight, based on the entire product including the casing walls.

[0076] As a "reactive diluent," for example, for preferred vinyl esters, one or more (low viscosity) free radical curable unsaturated reactive diluents may also be added, wherein it should be understood first that in this case, the free radical curable (including "curable (e.g., before the addition of a hardener)") component comprises an organic compound having unsaturated (e.g., olefin) groups or is particularly composed of such compounds, for example, especially (meth)acrylates—or (meth)acrylamide monomers, such as acrylic acid and / or methacrylic acid or preferably their esters (called (meth)acrylates) or Amides, especially (meth)acrylates, such as mono-, di-, tri-, or poly(meth)acrylates (including hydroxyalkyl (meth)acrylates, such as hydroxypropyl (meth)acrylate or hydroxy-ethyl (meth)acrylate), alkyl (meth)acrylates having 1-10 (meth)acrylate groups, such as mono-, di-, tri-, tetra-, penta-, hexa-, or poly(meth)acrylates, such as alkyl di- or tri(meth)acrylates, such as 1,2-ethylene glycol di(meth)acrylate (ethylene glycol di(meth)acrylate), butanediol di(meth)acrylate. Acrylates, such as 1,3- or especially 1,4-butanediol di(meth)acrylate, hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate, polyglycerol poly(meth)acrylate, polyethylene glycol di(meth)acrylate, cycloalkyl-, bicycloalkyl-, or heterocyclic (meth)acrylates, wherein the cycloalkyl or bicycloalkyl group has 5-7 ring carbon atoms and the heterocyclic group has 5 or 6 ring atoms and 1 or 2 ring carbon atoms. A cyclic heteroatom selected from nitrogen, oxygen, and sulfur, such as tetrahydrofurfuryl (meth)acrylate or isoborneol (meth)acrylate or acetylacetoxyalkyl (meth)acrylate; or in addition, styrene, such as styrene, α-methylstyrene, vinyltoluene, tert-butylstyrene, and / or divinylbenzene; or a mixture of two or more thereof, wherein the unsaturated reactive diluent is provided as a component for parallel curing with a free radical-cured unsaturated reactive resin, for example, at a weight percentage of 0.1-90% by weight, for example, 0.5-75% by weight or 1-40% by weight, based on the synthetic resin composition.

[0077] Advantageously, the cassette used according to the invention also has, as an additive, a silane containing at least one hydrolyzable group bonded to Si, or the filler is modified with such a silane prior to its addition, wherein the silane is in particular a substance that contains reactive groups (olefin double bonds, for example in (meth)acrylate groups, for corresponding free radical-curable anchoring materials) in the polymerization of the anchoring material, and on the other hand has hydrolyzable groups bonded to Si, such as alkoxy groups (e.g., having 1-7 carbon atoms) or halogens, such as chlorine. Surface modification can be performed, for example, by a silane or during use (e.g., for fixing anchoring elements), wherein the silane contains one or more hydrolyzable groups bonded to silicon atoms, such as alkoxy groups, for example methoxy or ethoxy groups, selected from the following groups, or mixtures of two or more thereof: selected from 3-aminopropyltrialkoxysilane, such as 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrialkoxysilane (particularly preferred in epoxy systems), such as 3-glycidoxypropyltrimethoxysilane or ethoxysilane, glycidoxymethyltrimethoxysilane, 3-glycidoxypropylmethyldi-methoxysilane, bis-(3-trialkoxysilylpropyl)amine, such as bis-(3-trimethoxysilylpropyl)amine or bis-(3-triethoxysilylpropyl)amine. )amines, 3-mercaptopropyltrialkoxysilanes, such as 3-mercaptopropyltrimethoxysilane, and (as particular variants, especially in the case of systems based on unsaturated reactive-synthetic resins) 3-(meth)acryloyl-oxypropyltrialkoxysilanes, such as 3-(meth)acryloyl-oxypropyltrimethoxysilane or triethoxysilane or 3-(meth)acryloyl-oxymethyltrimethoxysilane or triethoxysilane, 3-(meth)acryloyl-oxypropylmethyldimethoxysilane and alkenylalkoxysilanes, such as vinylalkoxysilanes, such as vinyltrimethoxysilane or vinyltriethoxysilane, and / or additionally tetraalkoxysilanes in all embodiments, such as tetraethoxysilane, tetramethoxysilane or tetrapropoxysilane, or alkoxy polysilicone esters (esters of (poly)silicone), such as ethyl or propyl polysiloxane. Oligomeric silanes may also be used or formed by reaction with water (diffused into or remaining in the system).

[0078] On the other hand, in specific embodiments of the subject matter of the present invention, such silanes may preferably be 3-(meth)acryloyl-oxypropyltrialkoxysilanes, such as 3-(meth)acryloyl-oxypropyltrimethoxysilane or triethoxysilane or 3-(meth)acryloyl-oxymethyltrimethoxysilane or triethoxysilane, 3-(meth)acryloyl-oxypropylmethyldimethoxysilane and alkenylalkoxysilanes, such as vinylalkoxysilanes, for example vinyltrimethoxysilane or vinyltriethoxysilane.

[0079] The silane having a hydrolyzable group may be provided in the synthetic resin component of the anchoring material to be used according to the invention, for example, in a weight ratio of 0.01-50%, especially 0.1% or higher, such as 1-30% by weight, preferably 2% or higher, such as 2-30 or -15% by weight, 3% or higher, such as 3-20 or -10% by weight, more preferably 3.5% or higher, such as 3.5-20 or -8% by weight.

[0080] The proportion of synthetic resin component in the entire product (kit) is preferably in the range of 5-90% by weight, for example, 10-50% by weight.

[0081] A hole or gap should be understood as a hole or gap that exists in a solid (especially already completed) building substrate, particularly brick or concrete, optionally also in a fractured substrate, such as fractured concrete, and is accessible from at least one side, for example, by drilling, or in the case of mortar with inorganic mortar or lime material (such as with cement or gypsum) or in the case of concrete pouring, such as a recessed area.

[0082] Anchoring elements should be understood to be those derived particularly from metal, such as back-cut anchors, threaded rods, screws, drill anchors, or bolts.

[0083] By introducing a sleeve (especially a sleeve or film bag) based on the present invention, the introduction of the anchoring element causes the wall material to break down and thus enables the synthetic resin component and the curing agent component to come into contact with each other and react together to form a cured synthetic resin, thereby fixing the anchoring element in the hole permanently.

[0084] The application of the invention is particularly applicable in the field of construction. "Field of construction" should be understood to mean construction in the narrow sense, such as building elements, such as exterior wall panels, which are anchored in the substrate by means of anchoring elements (that is, receiving materials within the scope of the invention, especially as long as they are components of hand-built buildings, particularly concrete, brickwork (e.g., derived from natural stone, solid bricks, in addition porous bricks, tiles, expanded concrete blocks, etc.), and also plastics or wood).

[0085] This invention also relates to the inventive subject matter set forth in the claims, which are therefore to be construed as part of this specification.

[0086] The following examples are for illustrative purposes only and are not intended to limit the scope of the invention:

[0087] E2BADMA Industrially ethoxylated bisphenol-A-dimethacrylate

[0088] VE is a vinyl ester resin based on bisphenol A.

[0089] UMA is a carbamate methacrylate based on MDI and HPMA.

[0090] BDDMA Butylene Glycol Dimethacrylate

[0091] HPMA 2-hydroxypropyl methacrylate

[0092] Silane methacryloyloxypropyltrimethoxysilane

[0093] Quartz sand gradation 80-200 µm

[0094] Corundum, common corundum 1100-1700 µm

[0095] A sleeve M12 is manufactured, consisting of an inner tube (inner ampoule) and an outer tube (outer ampoule) for the curing agent. The inner tube contains 0.32 g of 50 wt% benzoyl peroxide (based on the desensitized curing agent powder) desensitized by ethylene glycol dibenzoate (melting point 70 °C), and is composed of 1.05 g of glass and is heat-sealed. The curing agent inner tube, the resin, and the solid filler are introduced into the outer tube of the sleeve, which contains 3.60 g of glass, and are similarly welded.

[0096] Wholesale materials E2BADMA VE UMA BDDMA HPMA silane quartz Corundum A1 3.55 0.29 0.15 8.6 A2 3.55 0.29 0.15 11.9 A3 3.13 0.82 11.9 A4 2.15 1.01 0.82 8.6 A5 2.15 1.01 0.82 11.9 A6 2.15 1.01 0.82 11.9 A7 3.44 0.30 0.30 8.6 A8 3.44 0.30 0.30 11.9 A9 3.23 0.82 11.9

Claims

1. A sleeve or film bag in the form of a cassette for securing anchoring elements in holes in a building substrate, the sleeve or film bag having multiple compartments, one of which contains a synthetic resin component comprising a synthetic resin that can be polymerized by free radicals, another compartment containing a desensitizing free radical initiator in a curing agent component, wherein the free radical initiator is desensitized by a phthalate-free plasticizer in at least partial coating, and wherein the plasticizer has a melting point in the range of 40-90°C, the free radical initiator is in solid form at room temperature and the desensitizing free radical initiator is in particulate form at room temperature and is implemented as a free-flowing powder, and wherein the phthalate-free plasticizer is selected from ethylene glycol dibenzoate or triethylene glycol dibenzoate. The particle size distribution d of the desensitized free radical initiator 50 In the range of 150-400μm.

2. The use according to claim 1, wherein the particle size distribution d of the desensitized free radical initiator is... 50 In the range of 180-300μm.

3. The use according to claim 1, wherein the proportion of the free radical initiator is 45-55% by weight, based on the curing agent composition.

4. The use according to any one of claims 1 to 3, wherein, in the case of the desensitizing free radical initiator, each of the following proportions is a maximum of 5% by weight of fine particles with a particle size < 100 μm and a maximum of 5% by weight of coarse particles with a particle size > 500 μm, wherein the description in weight % is based on the curing agent composition.

5. The use according to claim 4, wherein the proportion of the fine particles is a maximum of 1% by weight, and the proportion of the coarse particles is a maximum of 1% by weight.

6. The use according to any one of claims 1 to 3, wherein the plasticizer free of dicyclohexyl phthalate is ethylene glycol dibenzoate.

7. The use according to claim 4, wherein the phthalate-free plasticizer is ethylene glycol dibenzoate.

8. The use according to claim 5, wherein the phthalate-free dicyclohexyl phthalate plasticizer is ethylene glycol dibenzoate.

9. The use according to claim 4, wherein the free radical initiator is benzoyl peroxide.

10. The use according to claim 9, wherein the proportion of the free radical initiator is 45-55% by weight, based on the curing agent composition.

11. The use according to any one of claims 1 to 3, wherein the free radical polymerizable synthetic resin in the synthetic resin component is a vinyl ester urethane resin, a vinyl ester resin, a propoxylated or ethoxylated aromatic diol-(meth)acrylate or a linear phenolic varnish-(meth)acrylate or an unsaturated polyester.

12. The use according to claim 9, wherein the free radical polymerizable synthetic resin in the synthetic resin component is a vinyl ester urethane resin, a vinyl ester resin, a propoxylated or ethoxylated aromatic diol-(meth)acrylate or a linear phenolic varnish-(meth)acrylate or an unsaturated polyester.

13. The use according to claim 11, wherein the free radical polymerizable synthetic resin comprises vinyl ester carbamate, which is prepared by a method characterized in that, as the reaction raw material for preparing the vinyl ester carbamate resin, an isocyanate having an average functionality of 2 or greater, or a mixture of an isocyanate having a functionality of less than 2 and an isocyanate having a functionality of greater than 2, is used, and the reaction raw material reacts with a fatty alcohol having at least one C-C double bond.

14. The use according to claim 13, wherein the fatty alcohol having at least one C-C double bond is hydroxypropyl (meth)acrylate.

15. The use according to any one of claims 1 to 3, characterized in that, The free radical polymerizable synthetic resin has the following ideal formulas: Where a and b each represent values ​​greater than or equal to 0 independently, where at least one value of a and b is greater than 0, and where, when different molecular mixtures with different values ​​of a and b exist and are represented by the above formula, the average value is a non-integer value.

16. The use according to claim 15, wherein a and b are each 1 or greater.

17. The use according to claim 4, characterized in that, The free radical polymerizable synthetic resin has the following ideal formulas: Where a and b each represent values ​​greater than or equal to 0 independently, where at least one value of a and b is greater than 0, and where, when different molecular mixtures with different values ​​of a and b exist and are represented by the above formula, the average value is a non-integer value.

18. The use according to claim 17, wherein a and b are each 1 or greater.

19. The use according to any one of claims 1 to 3, characterized in that, The free radical polymerizable synthetic resin is a vinyl ester resin.

20. The use according to claim 4, characterized in that, The free radical polymerizable synthetic resin is a vinyl ester resin.

21. The use according to any one of claims 1 to 3, wherein the synthetic resin component and / or curing agent component further comprises other inclusions selected from amine accelerators, inhibitors, non-reactive diluents, reactive diluents, thixotropic agents, fillers and / or other additives.

22. A method for securing an anchoring element in a hole in a building substrate, wherein the use according to any one of claims 1 to 3 occurs, and the sleeve or film bag is broken by introducing the anchoring element, and the components of the sleeve are in contact with each other and with the anchoring element and the hole wall, and the anchoring element is secured in the borehole under polymerization.

23. A method for securing an anchoring element in a hole in a building substrate, wherein the use according to claim 4 occurs, and the sleeve or film bag is broken by introducing the anchoring element, and the components of the sleeve are in contact with each other and with the anchoring element and the hole wall, and the anchoring element is secured in the borehole under polymerization.

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