FLOOR PROTECTION SYSTEM WITH HIGH DYNAMIC CRACK BRIDGING

Abstract

A floor protection system including (i) optionally at least one epoxy resin primer, (ii) at least one polyurethane coating, (iii) optionally quartz sand, which has been scattered into and/or onto the polyurethane coating, and (iv) an epoxy resin sealant, obtained from a resin component containing at least one epoxy liquid resin and a hardener component containing at least one amine of formula (I). The floor protection system has an aesthetically pleasing, hard and robust surface and a good dynamic crack bridging with surprisingly high elasticity of the sealant. The system is particularly suitable as a surface protection system for parking levels and drivable ramps.

Claims

1. A floor protection system comprising (i) optionally at least one epoxy resin primer, (ii) at least one polyurethane coating, (iii) optionally quartz sand, scattered into and/or onto the polyurethane coating, and (iv) an epoxy resin seal obtained from a resin component containing at least one liquid epoxy resin and a curing agent component containing at least one amine of the formula (I)
Z-NH-A-NH—CH.sub.2—Y  (I) where A is a divalent C.sub.2 to C.sub.15 alkylene, cycloalkylene or arylalkylene radical optionally containing one or more nitrogen atoms or ether groups, Z is H or —CH.sub.2—Y and Y is H or a C.sub.1 to C.sub.11 alkyl, cycloalkyl, arylalkyl or aryl radical, wherein the two nitrogen atoms to which the A radical is bonded are separated from one another by at least two carbon atoms, and the amine of the formula (I) contains a total of at least 8 carbon atoms.

2. The floor protection system as claimed in claim 1, wherein the polyurethane coating has a layer thickness in the range from 2 to 6 mm.

3. The floor protection system as claimed in claim 1, wherein the polyurethane coating consists of one or more layers, and at least one of these layers has an elongation at break of at least 200%, determined at 23° C. to DIN EN 53504 at a strain rate of 200 mm/min.

4. The floor protection system as claimed in claim 1, wherein the polyurethane coating consists of two layers, wherein the lower layer has a thickness in the range from 1.2 to 3 mm and an elongation at break of at least 200%, and the upper layer has a thickness in the range from 1.2 to 3 mm and a tensile strength of at least 9 MPa and has optionally been filled and/or scattered with quartz sand, wherein tensile strength and elongation at break are determined at 23° C. to DIN EN 53504 at a strain rate of 200 mm/min.

5. The floor protection system as claimed in claim 1, comprising quartz sand scattered onto the polyurethane coating.

6. The floor protection system as claimed in claim 1, wherein A is selected from the group consisting of 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene, 1,3-butylene, 2-methyl-1,2-propylene, 1,3-pentylene, 1,5-pentylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene, 2-methyl-1,5-pentylene, 1,7-heptylene, 1,8-octylene, 2,5-dimethyl-1,6-hexylene, 1,9-nonylene, 2,2(4),4-trimethyl-1,6-hexylene, 1,10-decylene, 1,11-undecylene, 2-butyl-2-ethyl-1,5-pentylene, 1,12-dodecylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, (1,5,5-trimethylcyclohexan-1-yl)methane-1,3,4(2)-methyl-1,3-cyclohexylene, 1,3-cyclohexylenebis(methylene), 1,4-cyclohexylenebis(methylene), 1,3-phenylenebis(methylene), 1,4-phenylenebis(methylene), 3-oxa-1,5-pentylene, 3,6-dioxa-1,8-octylene, 4,7-dioxa-1,10-decylene, 3-aza-1,5-pentylene, 3,6-diaza-1,8-octylene, 4,7-diaza-1,11-decylene and 3-aza-1,6-hexylene.

7. The floor protection system as claimed in claim 1, wherein Y is selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, butyl, pentyl, heptyl, hept-2-yl, phenyl, 4-methylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 4-dimethylaminophenyl, 1-naphthyl, benzyl and cyclohexyl.

8. The floor protection system as claimed in claim 1, wherein A is 1,2-ethylene and Y is phenyl.

9. The floor protection system as claimed in claim 1, wherein 5% to 80% of all amine hydrogens present in the curing agent component come from amines of the formula (I) and at least one further amine having at least four aliphatic amine hydrogens is present.

10. The floor protection system as claimed in claim 9, wherein the further amine having at least four aliphatic amine hydrogens present is 1,3-bis(aminomethyl)cyclohexane.

11. The floor protection system as claimed in claim 1, wherein the epoxy resin seal has a layer thickness in the range from 0.1 to 1 mm.

12. The floor protection system as claimed in claim 1, wherein it passes a test for dynamic crack bridging at −20° C. to EN 1062-7 method B 3.2 without cracks in the epoxy resin seal.

13. A method of protecting floors, wherein an epoxy resin seal comprising at least one amine of the formula (I)
Z-NH-A-NH—CH.sub.2—Y  (I) where A is a divalent C.sub.2 to C.sub.15 alkylene, cycloalkylene or arylalkylene radical optionally containing one or more nitrogen atoms or ether groups, Z is H or —CH.sub.2—Y and Y is H or a C.sub.1 to C.sub.11 alkyl, cycloalkyl, arylalkyl or aryl radical, wherein the two nitrogen atoms to which the A radical is bonded are separated from one another by at least two carbon atoms, and the amine of the formula (I) contains a total of at least 8 carbon atoms, in a layer thickness in the range from 0.1 to 1 mm is applied to a polyurethane coating that has optionally been scattered with quartz sand.

14. The method as claimed in claim 13, wherein 5% to 80% of all amine hydrogens present in the epoxy resin seal come from amines of the formula (I) and at least one further amine having at least four aliphatic amine hydrogens is present.

15. The method as claimed in claim 13, wherein the polyurethane coating has a layer thickness in the range from 2 to 6 mm and consists of one or more layers, wherein at least one of these layers has an elongation at break of at least 200%, determined at 23° C. to DIN EN 53504 at a strain rate of 200 mm/min.

Description

EXAMPLES

[0161] Working examples are adduced hereinafter, which are intended to further elucidate the invention described. The invention is of course not limited to these described working examples.

[0162] “AHEW” stands for amine hydrogen equivalent weight.

[0163] “EEW” stands for epoxy equivalent weight.

[0164] “Standard climatic conditions” (“SCC”) refers to a temperature of 23±1° C. and a relative air humidity of 50±5%.

[0165] The chemicals used were unless otherwise stated from Sigma-Aldrich Chemie GmbH.

Substances and Abbreviations Used:

[0166] Araldite® GY 250: Bisphenol A diglycidyl ether, EEW 187 g/mol (from Huntsman)

[0167] Araldite® DY-E: Monoglycidyl ethers of C.sub.12 to C.sub.14 alcohols, EEW approx. 290 g/equiv. (from Huntsman)

[0168] Ancamine® K54 2,4,6-Tris(dimethylaminomethyl)phenol (from Air Products) [0169] B-EDA N-Benzylethane-1,2-diamine, AHEW 50.1 g/equiv., prepared as described below [0170] DB-EDA N,N′-Dibenzylethane-1,2-diamine, AHEW 120.2 g/equiv. [0171] 1,3-BAC 1,3-Bis(aminomethyl)cyclohexane, AHEW 35.5 g/equiv. (from Mitsubishi Gas Chemical) [0172] IPDA 1-Amino-3-aminomethyl-3,5,5-trimethylcyclohexane, AHEW 42.6 g/equiv. (Vestamin® IPD from Evonik) [0173] MXDA 1,3-Bis(aminomethyl)benzene, AHEW 34 g/equiv. (from Mitsubishi Gas Chemical) [0174] D-230 Polyoxypropylenediamine, average molecular weight 230 g/mol, AHEW 60 g/mol (Jeffamine® D-230, from Huntsman) [0175] Sikafloor®-151: 2-component epoxy resin primer (from Sika) [0176] Sikafloor®-376: 2-component polyurethane coating based on TDI-based polymer containing isocyanate groups and 3,5-dimethylthiotoluene-2,4(6)-diamine, having a tensile strength of ≥5 MPa, an elongation at break of ≥500% and a Shore A hardness of ≥60 (from Sika) [0177] Sikafloor®-377: 2-component polyurethane coating based on polymeric MDI, castor oil and castor oil-based polyol, having a tensile strength of ≥11 MPa and an elongation at break of ≥50% (from Sika) [0178] Sikafloor®-378: 2-component epoxy resin seal with a curing agent component based on IPDA, MXDA and D-230 (from Sika)
N-Benzylethane-1,2-diamine (B-EDA):

[0179] An initial charge of 180.3 g (3 mol) of ethane-1,2-diamine at room temperature was mixed with a solution of 106.0 g (1 mol) of benzaldehyde in 1200 ml of isopropanol and stirred for 2 hours, then hydrogenated at 80° C., hydrogen pressure 80 bar, and a flow rate of 5 ml/min in a continuous hydrogenation apparatus with a fixed bed Pd/C catalyst, and the hydrogenated solution was concentrated on a rotary evaporator at 65° C., removing unreacted ethane-1,2-diamine, water and isopropanol. The resultant reaction mixture was purified by distillation at 80° C. under reduced pressure. This gave a colorless liquid having an N-benzylethane-1,2-diamine content determined by GC of >97%.

Production of Epoxy Resin Seals:

Examples 1 to 8

[0180] For these examples, a resin component was produced by mixing the following ingredients by means of a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.) and storing it with exclusion of moisture: [0181] 166.8 parts by weight of Araldite® GY 250, [0182] 26.7 parts by weight of Araldite® DY-E, [0183] 153.8 parts by weight of quartz flour, [0184] 4.4 parts by weight of defoamer, [0185] 61.3 parts by weight of silica gray pigment paste.

[0186] For each example, the ingredients of the curing agent component that are specified in tables 1 and 2 were mixed in the stated amounts (in parts by weight) by means of the centrifugal mixer and stored with exclusion of moisture.

[0187] The two components were then processed using the centrifugal mixer to give a homogeneous liquid, and this was tested immediately as follows: [0188] Viscosity was measured 5 min after the resin component and the curing agent component had been mixed by means of a cone-plate viscometer at a shear rate of 10 s.sup.−1 and a temperature of 20° C. [0189] Gel time was determined by moving a freshly mixed amount of about 3 g under standard climatic conditions with a spatula at regular intervals until the mass gelated. [0190] Shore D hardness was determined to DIN 53505 on two cylindrical test specimens (diameter 20 mm, thickness 5 mm), with storage of one under standard climatic conditions and one at 8° C. and 80% relative humidity. Hardness was measured here after 1 day, 2 days and 7 days in each case.

[0191] As a measure of the extensibility of the seal, each composition was applied to a cured polyurethane film in a layer thickness of 500 μm and left to cure under standard climatic conditions for 14 days. The cured polyurethane film was produced with Sikafloor®-376, which was mixed as specified and stored under standard climatic conditions in a layer thickness of 2 mm for 14 days. 3 specimens of 70×40×2.5 mm in each case were cut out of the layer composite thus produced, and these were used to conduct a 3-point bending test with a braced width of 48 mm at a testing speed of 10 mm/min with the seal on the pulling side (outside of the bend), in accordance with DIN EN ISO 178, with determination of the maximum bend or deflection of the sample perpendicularly at the maximum force.

[0192] The results are reported in Tables 1 and 2.

[0193] The examples designated “(Ref.)” are comparative examples.

TABLE-US-00001 TABLE 1 Composition and properties of examples 1 to 4. Example 1 (Ref.) 2 3 4 Resin component: 413.0 413.0 413.0 413.0 Curing agent component: 1,3-BAC 35.5 30.2 24.9 30.5 B-EDA — 7.5 15.0 — DB-EDA — — — 16.8 Benzyl alcohol 10.0 10.0 10.0 10.0 Ancamine ® K54 2.0 2.0 2.0 2.0 Viscosity (5′) [Pa .Math. s] 1.84 1.58 1.42 1.45 Gel time [h:min] 2:15 2:35 3:00 2:50 Shore D (1d SCC) 81 84 76 78 (2 d SCC) 82 85 85 80 (7 d SCC) 85 86 85 80 Shore D (1d 8°/80%) 73 73 69 68 (2 d 8°/80%) 82 81 81 83 (7 d 8°/80%) 85 81 82 85 Maximum bend [mm] 7.9 8.8 9.6 9.0

TABLE-US-00002 TABLE 2 Composition and properties of examples 5 to 8. Example 5 8 (Ref.) 6 7 (Ref.) Resin component: 413.0 413.0 413.0 413.0 Curing agent component: IPDA 21.3 14.9 17.0 14.9 MXDA 17.0 11.9 13.6 11.9 B-EDA — 15.0 — — DB-EDA — — 18.0 — D-230 — — — 18.0 Benzyl alcohol 10.0 10.0 10.0 10.0 Ancamine ® K54 2.0 2.0 2.0 2.0 Viscosity (5′) [Pa .Math. s] 1.88 1.59 1.57 1.48 Gel time [h:min] 3:00 3:10 3:30 4:10 Shore D (1d SCC) 80 80 72 72 (2 d SCC) 81 81 78 77 (7 d SCC) 83 85 83 83 Shore D (1d 8°/80%) 49 n.d. n.d. n.d. (2 d 8°/80%) 82 72 60 60 (7 d 8°/80%) 84 82 72 72 Maximum bend [mm] 6.3 8.0 9.4 7.0 “n.d.” stands for “not determined” (too soft)

Production of Floor Protection Systems:

Example 9

[0194] Three concrete prisms of dimensions (length x width x height) 225×160×50 mm were primed with 0.5 kg/m.sup.2 Sikafloor®-151, and the still-wet primer was sparingly sanded with 0.8 kg/m.sup.2 of 0.3 to 0.8 mm quartz sand.

[0195] After a curing time of 24 h, 1.9 kg/m.sup.2 of the polyurethane coating Sikafloor®-376 as sealing layer was applied and left to cure for 24 h.

[0196] Subsequently, 1.7 kg/m2 of the polyurethane coating Sikafloor®-377 was applied as wear layer, into which 0.85 kg/m.sup.2 of 0.1 to 0.3 mm quartz sand had been scattered, and then the surface of the still-wet coating was scattered with an excess of 0.3 to 0.8 mm quartz sand. After a curing time of 24 h, the excess quartz sand was removed by means of a brush and vacuum cleaner.

[0197] Finally, the epoxy resin seal from example 2 was applied in an amount of 0.7 kg/m.sup.2 by means of a roller to the polyurethane coating scattered with quartz sand, and left to cure.

[0198] The epoxy resin seal showed excellent workability with barely any odor, good leveling and good deaeration. The resultant gray-pigmented surface was even, hard, shiny, nontacky and free of streaks or cloudiness.

[0199] The structure corresponds to an OS 11 a surface protection system according to DIN EN 1504-2.

[0200] After storage under standard climatic conditions for 14 days, followed by 7 days in an air circulation oven at 70° C., the concrete prisms coated with the floor protection system were tested for dynamic crack bridging at −20° C. to EN 1062-7 method B. For this purpose, a crack was made in the concrete prism without damaging the floor protection system. The test was conducted according to method B 3.2 with a lower crack width of 0.1 mm, an upper crack width of 0.3 mm and a change in crack width of 0.2 mm with 1000 crack cycles at a frequency of 0.03 Hz. After the test, the floor protection system on the three prisms was checked visually for cracks in the region of the polyurethane coating and in the epoxy resin seal. The results are reported in table 3.

Example 10

[0201] A further three concrete prisms were coated with a floor protection system as described for example 9. The structure of the floor protection system and the result of the testing for dynamic crack bridging are reported in table 3.

[0202] This structure corresponds to an OS 10 surface protection system according to DIN EN 1504-2.

[0203] The test was conducted according to method B 4.2 with a lower crack width of 0.2 mm, an upper crack width of 0.5 mm and a change in crack width of 0.3 mm with 1000 crack cycles at a frequency of 0.03 Hz.

Examples 11 (Ref.) and 12 (Ref.)

[0204] As a comparison, 3 concrete prisms in each case, as specified for examples 9 and 10, were coated with a floor protection system, using a noninventive epoxy resin seal: Sikafloor®-378 (2-component epoxy resin seal with a curing agent based on IPDA, MXDA and D-230, from Sika). The structure of the floor protection systems and the results of the testing for dynamic crack bridging are reported in table 3.

TABLE-US-00003 TABLE 3 Structure and results of examples 9 to 12 Example 11 12 9 10 (Ref.) (Ref.) Substrate: polished concrete polished concrete Primer: Sikafloor ®-151 Sikafloor ®-151 0.5 kg/m.sup.2 0.5 kg/m.sup.2 Seal layer Sikafloor ® 376 Sikafloor ® 376 Sikafloo r® 376 Sikafloo r® 376 (polyurethane): 1.9 kg/m.sup.2 2.5 kg/m.sup.2 1.9 kg/m.sup.2 2.5 kg/m.sup.2 Wear layer Sikafloor ® 377 Sikafloor ® 377 Sikafloor ® 377 Sikafloor ® 377 (polyurethane): 1.7 kg/m.sup.2, 2.2 kg/m.sup.2, 1.7 kg/m.sup.2, 2.2 kg/m.sup.2, filled with 0.85 filled with 1.1 filled with 0.85 filled with 1.1 kg/m2 of 0.1 to kg/m2 of 0.1 to kg/m2 of 0.1 to kg/m2 of 0.1 to 0.3 mm quartz 0.3 mm quartz 0.3 mm quartz 0.3 mm quartz sand sand sand sand scattered with an 0.3 to 0.8 mm quartz sand 0.3 to 0.8 mm quartz sand excess of: Epoxy resin seal: from example 2 Sikafloor®-378 0.7 kg/m.sup.2 0.7 kg/m.sup.2 Structure OS 11 a OS 10 OS 11 a OS 10 corresponding to Dynamic crack Method B 3.2: Method B 4.2: Method B 3.2: Method B 4.2: bridging at no cracks, either in no cracks, either in cracks in the seal cracks in the seal −20° C.: the polyurethane the polyurethane coating or in the coating or in the seal seal Passed? yes yes no no