Storage-stable, multi-component reaction resin system and use of same

Abstract

A multi-component reaction resin system for use with thread-forming screws contains a curable compound. In particular, the multi-component reaction resin system contains at least one radically curable compound and an inorganic filler in a first component, and contains a hardener for at least one radically curable reactive resin and water in a further second component. The inorganic filler has hydrophilic properties, and the reaction resin system is characterized by a low content of radically curable compounds that carry hydroxyl groups. The multi-component reaction resin system can be used with thread-forming screws.

Claims

1. A multi-component reaction resin system for use with thread-forming screws, comprising: a first component, comprising at least one radically curable compound and an inorganic filler, and a second component, comprising a hardener for the at least one radically curable compound and water wherein the inorganic filler has hydrophilic properties, and wherein a proportion of the at least one radically curable compound that carries hydroxyl groups is at most 10 wt. % of a total amount of the at least one radically curable compound.

2. The multi-component reaction resin system according to claim 1, wherein the at least one radically curable compound comprises a reaction resin, a reactive diluent, or a mixture consisting of the reaction resin and the reactive diluent.

3. The multi-component reaction resin system according to claim 2, wherein the at least one radically curable compound or the reaction resin is a compound based on urethane (meth)acrylate, epoxy (meth)acrylate, a (meth)acrylate of an alkoxylated bisphenol, or a further ethylenically unsaturated compound.

4. The multi-component reaction resin system according to claim 2, wherein the reactive diluent is a (meth)acrylic acid ester, with the proviso that the (meth)acrylic acid ester is not a hydroxyalkyl (meth)acrylic acid ester.

5. The multi-component reaction resin system according to claim 4, wherein the (meth)acrylic acid ester is selected from the group consisting of 2-ethylhexyl (meth)acrylate, phenylethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethyl triglycol (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminomethyl (meth)acrylate, acetoacetoxyethyl (meth)acrylate, 3-(meth)acryloyl-oxymethyl-tricylo-5.2.1.0..sup.2.6-decane, 3-(meth)cyclopentadienyl (meth)acrylate, methoxy polyethylene glycol mono(meth)acrylate, trimethylcyclohexyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, bisphenol A (meth)acrylate, isobornyl (meth)acrylate, decalyl-2-(meth)acrylate, ethanediol-1,2-di(meth)acrylate, propanediol-1,3-di(meth)acrylate, butanediol- 1,2-di(meth)acrylate, butanediol-1,3-di(meth)acrylate, butanediol-1,4-di(meth)acrylate, hexanediol-1,6-di(meth)acrylate, ethylene-, diethylene glycol di(meth)acrylate, oligo- and polyalkylene glycol di(meth)acrylate, PEG200 di(meth)acrylate, alkoxylated tri-, tetra- and pentamethylacrylate, tricyclopentadienyl di(meth)acrylate, novolac epoxy di(meth)acrylate, trimethylolpropane tri(meth)acrylate, di-[(meth)acryloyl-maleoyl]-tricyclo-5.2.1.0..sup.2.6-decane and dicyclopentenyloxyethyl crotonate.

6. The multi-component reaction resin system according to claim 1, wherein the inorganic filler having hydrophilic properties comprises minerals selected from the group consisting of an alkaline earth metal and a salt thereof, bentonite, a carbonate, a silica, silica gel, a salt of alkaline earth metals with silica, and a silicate.

7. The multi-component reaction resin system according to claim 6, characterized in that wherein the inorganic filler is a silicon oxide-based filler.

8. The multi-component reaction resin system according to claim 7, wherein the silicon oxide-based filler comprises a silica.

9. The multi-component reaction resin system according to claim 8, wherein the silica is an amorphous silica selected from the group consisting of colloidal silica, precipitated silica, silica gel, fumed silica, silica smoke, silica glass (quartz glass), silica material (quartz material), and a skeleton of radiolarians and diatoms in a form of diatomaceous earth.

10. The multi-component reaction resin system according to claim 1, wherein the inorganic filler is surface-treated.

11. The multi-component reaction resin system according to claim 1, wherein the at least one radically curable compound is a compound based on urethane (meth)acrylate, epoxy (meth)acrylate, or a further ethylenically unsaturated compound.

12. The multi-component reaction resin system according to claim 1, wherein the hardener is a peroxide.

13. The multi-component reaction resin system according to claim 1, wherein the hardener and the water are in a form of an aqueous suspension.

14. The multi-component reaction resin system according to claim 1, wherein the first component and/or the second component contains, as a further additive, at least one further inorganic or organic additive.

15. The multi-component reaction resin system according to claim 1, wherein the multi-component reaction resin system is a two-component system.

16. The multi-component reaction resin system according to claim 15, it wherein the multi-component reaction resin system is a bag system, ampoule system, or capsule system.

17. A method, comprising: fastening an anchoring means in a borehole with the multi-component reaction resin system according to claim 1.

18. The method according to claim 17, wherein the anchoring means is a thread-forming screw.

19. The method according to claim 18, wherein the thread-forming screw is a concrete screw.

Description

EXAMPLES

List of the Constituents Used in the Examples and References (Explanation of Abbreviations) as Well as Their Trade Names and Sources of Supply:

Resin Components:

[0208] UMA-1 urethane methacrylate-HPMA, produced as described in Example 1a from EP 2 838 949 61, as a result of which a mixture with a ratio of urethane methacrylate:HPMA of 65:35 is obtained; [0209] UMA-2 urethane methacrylate-BDDMA, produced analogously to Example 1a from EP 2 838 949 61, wherein instead of the described 688 g HPMA, a mixture of 344 g HPMA and 344 g [0210] BDDMA was used, as a result of which a mixture with a ratio of urethane methacrylate:BDDMA of 65:35 is obtained with a remainder of approximately 1 wt. % HPMA; [0211] HPMA hydroxypropyl methacrylate, from Inchem (CAS number: 27813-02-1) [0212] BDDMA VISIOMER® BDDMA, 1,4-butanediol dimethacrylate, from Evonik Performance Materials GmbH (CAS number: 2082 7) [0213] DIPPT diisopropanol-p-toluidine; from BASF (CAS number: 38668-4-3) [0214] tBBK 4-tort-butylpyrocatechol, from RHODIA Operations (CAS number: 98-29-3) [0215] Aerosil® 200 hydrophilic fumed silica, from Evonik (CAS number: 112945-52-5; specific surface area 200 m.sup.2/g; average particle size [0216] 0.2-0.3 μm (aggregates))

Hardener Component:

[0217] BP20SAQ dibenzoyl peroxide 20%, suspension in water, unbuffered; from United Initiators (94-36-0) [0218] Optigel CK activated phyllosilicate (bentonite); from BYK-Chemie GmbH (specific density 2.6 g/cm.sup.3, bulk density 550-750 kg/m.sup.3, moisture content 10% ±2%)

Examples 1 to 4

[0219] To determine the influence of the content of compounds containing hydroxyl groups on the storage stability, the following resin components were prepared in the amounts shown in Table 1 and their viscosity was measured after preparation and after storage. For this purpose, the urethane methacrylate-HPMA mixture or the urethane methacrylate-BDDMA mixture, the HPMA or the BDDMA, DIPPT, tBBK and Aerosil® 200 were stirred in the dissolver at 2,000 rpm and a pressure of 80 mbar for 8 minutes.

[0220] The viscosity measurements were carried out on a Haake RS 600 rheometer from Thermo Fisher Scientific Inc, at a shear rate of 150/s. A cone/plate measuring system having a diameter of 20 mm (cone C20/01°, Ti) and an angle of 1° was used; measuring temperature 23° C.

[0221] The resin components were heated to the specified temperature of 23° C. in advance. The sample was removed using a disposable Pasteur pipette and applied to the plate of the rheometer. After setting the gap, the temperature is controlled again for 30 seconds and the measurement is started. The viscosity is evaluated at the shear rate of 150/s. The results of the measurements are shown in Table 1.

TABLE-US-00001 TABLE 1 Composition of example formulations 1 to 4 Example 1 (Comparison) Example 2 Example 3 Example 4 [wt. %] UMA-1 47.59 UMA-2 48.11 47.60 47.10 HPMA 14.28 1.00 1.00 1.00 BDDMA 46.68 48.20 45.71 DIPPT 1.16 1.19 1.18 1.17 tBBK 0.02 0.02 0.02 0.02 Aerosil ® 200 6.00 3.00 4.00 5.00 Viscosity Storage [mPa .Math. s] Freshly prepared 718 182 383 774 3 months at 25° C. 386 3 months at 40° C. 397 4 months at 40° C. 157 385 977

[0222] Example 1, the comparative example, showed the desired flowability at the beginning of storage and the mixture was stable immediately after mixing the two components. After storage of example formulation 1, however, a mixture consisting of this together with a hardener formulation was no longer stable.

[0223] Examples 2 to 4, each containing only 1 wt. % of HPMA, were used to determine the optimal Aerosil content. Example 2 was identified as optimal. Although example formulations 3 and 4 had lost some of their flowability, they could be mixed well with a liquid hardener formulation and the mixtures were stable.

[0224] This clearly shows that due to the strong reduction in the proportion of HPMA and thus of compounds containing hydroxyl groups, the compounds were able to maintain their storage stability.

Examples 5 to 8

[0225] To determine the influence of the content of compounds containing hydroxyl groups on the storage stability, resin components were prepared with the compositions shown in Table 2. For this purpose, the urethane methacrylate-BDDMA mixture (UMA-2), which still contains 1 wt. % of HPMA due to the production process, the HPMA, the BDDMA, the DiPpT, the tBBK and the Aerosil® 200 were stirred in the dissolver at 2,000 rpm and a pressure of 80 mbar for 8 minutes in the amounts shown in Table 2.

[0226] Samples of the formulations were each bottled and stored for 1 day, 1 week, 3 weeks, 6 weeks, 8 weeks, 10 weeks, 12 weeks, 14 weeks and 16 weeks. After storage, the condition of the resin components was determined.

[0227] The dynamic viscosity of the respective stored resin components was also determined. The viscosity measurements were carried out on a Haake RS 600 rheometer from Thermo Fisher Scientific Inc. at a shear rate of 150/s. A cone/plate measuring system having a diameter of 20 mm (cone C20/01°, Ti) and an angle of 1° was used; measuring temperature 23° C.

[0228] The resin components were heated to the specified temperature of 23° C. in advance. The sample was removed using a disposable Pasteur pipette and applied to the plate of the rheometer. After setting the gap, the temperature is controlled again for 30 seconds and the measurement is started. The viscosity is evaluated at the shear rate of 150/s. The results are reported in Table 3.

[0229] In addition, the effect of storage on a mixture with a hardener component was examined.

[0230] For this purpose, 15 g of resin component was placed in a SpeedMixer can (150 ml), 6 g of hardener component was added and the can was sealed. Then the two components were mixed within 2 seconds by shaking. The stability of the mixture was then assessed visually by means of a mouth stack, by observing how easily the compound flows from the spatula when it is held at an angle of approx. 45°.

TABLE-US-00002 TABLE 2 Composition of example formulations 5 to 8, with increasing HPMA content Example 5 Example 6 Example 7 Example 8 [wt. %] UMA-2 49.11 49.11 49.11 49.11 HPMA 1.00 2.00 3.00 BDDMA 46.68 45.68 44.68 43.68 DIPPT 1.19 1.19 1.19 1.19 tBBK 0.08 0.02 0.08 0.02 Aerosil ® 200 3.00 3.00 3.00 3.00 Proportion of 1.00 2.00 3.00 4.00 HPMA

TABLE-US-00003 TABLE 3 Results of the viscosity measurements and the observation of the consistency of the compositions of example formulations 5 to 8 Proportion of HPMA Example 5 Example 6 Example 7 Example 8 [wt. %] 1 2 3 4 Freshly prepared Dynamic viscosity 292.6 286.5 268.7 275.0 [mPa .Math. s] Resin component slightly thickened, slightly thickened, slightly thickened, slightly thickened, consistency flowable flowable flowable flowable Storage for 1 week Dynamic viscosity 156.2 143.9 133.2 129.4 at +40° C. [mPa .Math. s] Resin component thickened, flowable thickened, flowable thickened, flowable slightly thickened, consistency flowable Storage for 2 weeks Dynamic viscosity 234.7 232.5 214.4 183.2 at +40° C. [mPa .Math. s] Resin component quite heavily thickened, quite heavily thickened, thickened, flowable, slightly thickened, consistency but flowable but flowable thinner layer on top flowable, thinner layer on top Storage for 4 weeks Dynamic viscosity 245.6 241.0 233.0 203.0 at +40° C. [mPa .Math. s] Resin component very heavily thickened, heavily thickened, quite heavily thickened, thickened, consistency liquid settled on top, still flowable, flowable, good flowability no longer flowable liquid settled on top liquid settled on top Curing stable mixture with slight stable mixture with slight stable mixture with slight stable mixture with streaks, but streaks, but streaks, but slight streaks, but homogeneous curing homogeneous curing homogeneous curing homogeneous curing Storage for 6 weeks Dynamic viscosity 224.7 238.7 236.0 207.0 at +40° C. [mPa .Math. s] Resin component very heavily thickened, heavily thickened, still thickened, flowable, slightly thickened, consistency no longer flowable, flowable, sedimentation, approx. good flowability, liquid has settled on top sedimentation? Approx. 3 mm of liquid settled sedimentation, approx. 2 mm of liquid has on top 1 cm of clear liquid settled on top. on top Curing good thickening effect, good thickening effect, good thickening effect, good thickening effect, good and fast curing good and fast curing good and fast curing good and fast curing Storage for 8 weeks Dynamic viscosity 205.0 225.0 225.0 219.0 at +40° C. [mPa .Math. s] Resin component Sedimentation, gel-like, Sedimentation, gel-like, Sedimentation, gel-like, slightly thickened, consistency inner core, liquid settled inner core, liquid settled inner core, a lot of liquid good flowability, on the outside, approx. on the outside, approx. settled on the outside, sedimentation, approx. 2 mm of liquid on top 2 mm of liquid on top approx. 0.5 cm of liquid 1 cm of clear liquid on top on top Storage for 10 weeks Dynamic viscosity 174.0 223.0 197.0 171.0 at +40° C. [mPa .Math. s] Resin component sedimentation, gel-like, sedimentation, gel-like, sedimentation, gel-like, slightly thickened, consistency inner core, approx. inner core, approx. inner core, approx. good flowability, 2 mm of liquid on top 2 mm of liquid on top 0.5 cm of liquid on top sedimentation, approx. 1 cm of liquid on top Storage for 14 weeks Dynamic viscosity 129.4 pipette 126.3 pipette 128.6 pipette 92.0 pipette at +40° C. [mPa .Math. s] 92.7 spatula 83.9 spatula 89.6 spatula 91.4 spatula Resin component heavily thickened, inner heavily thickened, inner heavily thickened, inner slightly thickened resin, consistency gel-like core, approx. gel-like core, approx. gel-like core, more good flowability, 1 mm of liquid settled 2 mm of liquid settled liquid around the core, approx. 10 mm of clear on top on top smaller core than with 1 liquid on top, no gel or 2% HPMA core Storage for 16 weeks Dynamic viscosity 194.6 191.0 209.5 175.3 at +40° C. [mPa .Math. s] Resin component heavily thickened gel- heavily thickened gel- heavily thickened, inner slightly thickened resin, consistency like core, approx. 1 mm like core, approx. 2 mm gel-like core, more good flowability, of liquid settled on of liquid settled on liquid around the core, approx. 12 mm of clear top −> no change top −> no change smaller core than with 1 liquid on top, small gel or 2% HPMA, approx. core? 0.5 mm of liquid on top −> no change Curing thickening effect after thickening effect after thickening effect after thickening effect after mixing, good curing mixing, good curing mixing, good curing mixing, good curing Storage for 20 weeks Dynamic viscosity 225.0 215.7 224.6 182.1 at +40° C. [mPa .Math. s] Resin component heavily thickened gel- heavily thickened gel- heavily thickened gel- slightly thickened resin, consistency like core in liquid like core, approx. 1 cm like core, approx. 1 cm good flowability, of liquid on top of liquid on top approx. 2 cm of clear liquid on top Curing thickening effect after thickening effect after thickening effect after thickening effect after mixing; good curing mixing; good curing mixing; good curing mixing; good curing Storage for 24 weeks Dynamic viscosity 270.7 308.8 205.1 169.9 at +40° C. [mPa .Math. s] Resin component large gel-like core, large gel-like core, gel-like core in liquid approx. 2 cm of clear consistency some liquid outside slightly more liquid on liquid on top, gel-like the outside than with sediment of approx. 1% HPMA 1 cm on bottom Curing Sampling Sampling Sampling Sampling in the A comp.: in the A comp.: in the A comp.: in the A comp.: on top.sup.1): even slighter on top: no thickening on top: even smaller on top: no thickening thickening effect after effect after mixing thickening effect after effect after mixing mixing on bottom: good mixing, marginal on bottom: good on bottom.sup.2): good thickening of the on bottom: good thickening of the thickening of the mixture thickening of the mixture mixture both: good curing mixture both: good curing both: good curing both: good curing .sup.1)and .sup.2)sampling points of the sample vessel

Examples 9 and 10

[0231] In order to determine the upper limit of the content of compounds containing hydroxyl groups, resin components were prepared with the compositions shown in Table 4. For this purpose, the urethane methacrylate-BDDMA mixture, which still contains 1 wt. % of HPMA due to the production process, the BDDMA, the HPMA, the DiPpT, the tBBK and the Aerosil® 200 were stirred in the dissolver at 2,000 rpm and a pressure of 80 mbar for 8 minutes in the amounts shown in Table 4. A composition containing a total of 10 wt. % and a formulation containing a total of 20 wt. % of HPMA were obtained.

TABLE-US-00004 TABLE 4 Composition of example formulations 9 and 10 Example 9 Example 10 [wt. %] UMA-2 49.11 49.11 HPMA 9.00 19.00 BDDMA 37.68 27.68 DiPpT 1.19 1.19 tBBK 0.08 0.02 Aerosil ® 200 3 Proportion of 10 20 HPMA [wt. %]

[0232] Samples of example formulation 9 and example formulation 10 were each bottled and stored for 1 week, 3 weeks, 6 weeks, 8 weeks, 10 weeks, 12 weeks, 14 weeks and 16 weeks. After storage, the condition of the formulations was determined. For this purpose, 15 g of resin component was placed in a SpeedMixer can (150 ml), 6 g of hardener component was added and the can was sealed. Then the two components were mixed within 2 seconds by shaking. The stability of the mixture was then assessed visually by means of a mouth stack, by observing how easily the compound flows from the spatula when it is held at an angle of approx. 45°.

[0233] In addition, the stored formulations were each mixed with a hardener formulation composed of 98 wt. % of BP 20 SAQ and 2 wt. % of Optigel OK in order to determine the curing properties after storage.

[0234] The results are reported in Table 5. It can be seen from these results that the example formulation is somewhat stable in storage for 9 to 3 weeks, However, after longer storage, sedimentation and impaired curing of the formulation were observed. In the case of example formulation 10, it is already observed after storage for 2 weeks that the formulation increasingly thickened and sedimentation occurred.

TABLE-US-00005 TABLE 5 Results of the storage test of the resin components containing 10 wt. % of HPMA (example 9) and containing 20 wt. % of HPMA (example 10) Example 9 Example 10 Proportion of HPMA [%] 10 20 1 day Resin component slightly thickened, good slightly thickened, good consistency flowability flowability Mixture with hardener good thickening after good thickening after component mixing, good curing mixing, good curing 1 week Resin component slightly thickened, slightly thickened, clear, consistency clear, except on the except on the bottom, bottom, approx. 2 cm approx. 1 cm of slightly of slightly unclear unclear bottom layer bottom layer Mixture with hardener good thickening after low level of thickening component mixing, good curing immediately after mixing, the mixture only thickens with increasing curing, good curing 2 weeks Resin component slightly thickened, slightly thickened, clear, consistency clear, except approx. except approx. 1 cm of 2 cm of slightly unclear unclear layer on the layer on the bottom bottom, sharp separation between the layers Mixture with hardener even slighter thickening no thickening effect component effect after mixing immediately after mixing the two components 3 weeks Resin component slightly thickened, slightly thickened, approx. consistency approx. 3 cm of clear 5 cm of clear layer on top, layer on top, approx. approx. 1 cm of unclear 2 cm of unclear layer layer on the bottom on the bottom Mixture with hardener marginal there is no longer any component thickening effect 4 weeks Resin component slightly thickened, slightly thickened, approx. consistency approx. 2.5 cm of 1 cm of “sediment” on the “sediment” on the bottom bottom, clear on top Mixture with hardener “on top: still normal, no test: see 3 weeks component slightly smaller thickening effect, on the bottom: normal” 5 weeks Resin component see 4 weeks; on top: marginal; even consistency unchanged smaller on the bottom: still normal Mixture with hardener no test no test component