TWO-COMPONENT POLYURETHANE COMPOSITION

Abstract

A two-component polyurethane composition made of a polyol component and a polyisocyanate component, wherein the polyol component includes at least one reaction product of castor oil with ketone resins A1, at least one aliphatic triol A2, an aliphatic diol A3, and a polybutadiene polyol A4. The polyurethane composition has high strength and only a minor dependence of mechanical properties, especially of strength, on temperature, especially in the range from 60 C. to +60 C. Moreover, the composition is capable of curing without blistering under ambient conditions, even in the presence of substrates that typically promote foaming reactions owing to the presence of residual moisture, for example glass fiber weave.

Claims

1. A two-component polyurethane composition consisting of a polyol component K1 and a polyisocyanate component K2; wherein the polyol component K1 comprises at least one reaction product of castor oil with ketone resins having an OH number of 110 to 200 mg KOH/g A1, and at least one aliphatic triol having an average molecular weight of 170-500 g/mol and an OH number of 400-1100 mg KOH/g, comprising polyether polyols based on 1,1,1-trimethylolpropane A2, and at least one aliphatic diol having a molecular weight of 90-146 g/mol A3, and at least one polybutadiene polyol having an average OH functionality of 2.1 to 2.9, and having an average molecular weight in the range from 2000 to 4000 g/mol, and an OH number of 40-100 A4, and wherein the polyisocyanate component K2 comprises at least one aromatic polyisocyanate B1, where the ratio of the percentages by weight of ((A1+A2)/(A3+A4)) is 0.5-5; and where the ratio of all NCO groups of the aromatic polyisocyanates B1:all OH groups of the sum total of (A1+A2+A3+A4)=0.95:1-1.25:1; and where the ratio of the percentages by weight of (A4/A3) is 1-15.

2. The two-component polyurethane composition as claimed in claim 1, wherein the at least one aliphatic diol A3 is selected from the list consisting of butane-1,4-diol, 2-ethylhexane-1,3-diol, 3-methylpentane-1,5-diol and pentane-1,5-diol.

3. The two-component polyurethane composition as claimed in claim 1, wherein the ratio of the percentages by weight of ((A1+A2)/(A3+A4)) is 1.6-3.2.

4. The two-component polyurethane composition as claimed in claim 1, wherein the ratio of the percentages by weight of (A4/A3) is 0.8-7.5.

5. The two-component polyurethane composition as claimed in claim 1, wherein the sum total of all OH groups of (A1+A2+A3+A4) is 95% of the sum total of all OH groups of the two-component polyurethane composition.

6. The two-component polyurethane composition as claimed in claim 1, wherein the aromatic polyisocyanate B1 comprises oligomers, polymers and derivatives derived from MDI.

7. The two-component polyurethane composition as claimed in claim 1, wherein the sum total of the NCO groups that do not originate from B1 is 5%, based on the sum total of all NCO groups of the two-component polyurethane composition.

8. A method of bonding a first substrate to a second substrate, comprising the steps of: mixing the polyol component (K1) and the polyisocyanate component (K2) of a two-component polyurethane composition as claimed in claim 1, applying the mixed polyurethane composition to at least one of the substrate surfaces to be bonded, joining the substrates to be bonded within the open time, curing the polyurethane composition.

9. A method of filling joins and gaps between two substrates, comprising the steps of: mixing the polyol component (K1) and the polyisocyanate component (K2) of a two-component polyurethane composition as claimed in claim 1, applying the mixed polyurethane composition to the join or gap, curing the polyurethane composition.

10. A method of filling joins and gaps in a substrate, comprising the steps of: a) mixing the polyol component (K1) and the polyisocyanate component (K2) of a two-component polyurethane composition as claimed in claim 1, b) applying the mixed polyurethane composition to the gap or join to be filled in the substrate, c) curing the polyurethane composition in the join or gap.

11. A method of producing fiber-reinforced composite parts and a two-component polyurethane composition as claimed in claim 1, wherein the polyol component K1 and the polyisocyanate component K2 are mixed and then are introduced into a mold containing the fibers under reduced pressure and/or elevated pressure.

12. The method as claimed in claim 11, wherein no reduced pressure is applied to the polyol component K1 for more than 10 min, within less than 1 day prior to the mixing.

13. The method as claimed in claim 11, wherein the fibers are selected from the group consisting of natural fibers, glass fibers, carbon fibers, polymer fibers, ceramic fibers and metal fibers.

14. The method as claimed in claim 11, wherein the fibers are not dried for more than 60 min, and/or heating to a temperature above 50 C. for more than 60 min, within less than 24 h prior to the introduction of the mixture of the polyol component K1 and the polyisocyanate component K2 into the mold containing the fibers.

15. A fiber composite consisting of fibers and a cured two-component polyurethane composition as claimed in claim 1.

16. A method comprising applying a two-component polyurethane composition as claimed in claim 1 as infusion resin.

Description

EXAMPLES

Substances Used:

[0157]

TABLE-US-00002 Setathane 1150 Reaction product of castor oil with ketone resin, Setathane 1150, OH number of 155 mg KOH/g, OH equivalent weight of about 360 g/eq, Nuplex Resins GmbH, Germany Desmophen T 4011 Propoxylated 1,1,1-trimethylolpropane, Desmophen 4011 T, OH number of 550 25 mg KOH/g, molecular weight of about 300 20 g/mol, Covestro AG, Germany Polyvest HT Polybutadiene polyol having primary OH groups, Polyvest HT, OH functionality 2.4-2.6, average molecular weight about 2800 g/mol, OH number 48-50 mg KOH/g (Evonik AG, Germany) Zr catalyst Zirconium chelate complex, Zr content 3.5% by weight (K-Kat A-209 from King Industries Inc., USA) Sylosiv Zeolite (Sylosiv A3 from W. R. Grace & Co., USA) Desmodur VL Polymeric MDI, average NCO functionality of 2.5, Desmodur VL, Covestro AG, Germany

[0158] Production of Polyurethane Compositions

[0159] For each composition, the ingredients specified in tables 1 to 7 were processed in the specified amounts (in parts by weight) of the polyol component K1 by means of a vacuum dissolver with exclusion of moisture to give a homogeneous paste, and stored. The ingredients of the polyisocyanate component K2 specified in tables 1 to 7 were likewise processed and stored. Subsequently, the two components were processed by means of a SpeedMixer (DAC 150 FV, Hauschild) for 30 seconds to give a homogeneous paste and immediately tested as follows:

[0160] To determine the mechanical properties, the adhesive was converted to dumbbell form according to ISO 527, Part 2, 1B, and stored for 7 days under standard climatic conditions (23 C., 50% relative humidity) or stored under standard climatic conditions for 12-24 h and then cured for 3 h at 80 C. Thereafter, at room temperature, modulus of elasticity in the range from 0.05% to 0.25% elongation (Modulus of elasticity, Em 0.05-0.25%), modulus of elasticity in the range from 0.5% to 5% elongation (Modulus of elasticity, Em 0.5-5%), tensile strength (TS) and elongation at break (EB) of the test specimens thus produced were measured to ISO 527 on a Zwick Z020 tensile tester at a testing rate of 10 mm/min.

[0161] Glass transition temperature, abbreviated in the tables to T.sub.g, was determined from DMTA measurements on strip samples (height 2-3 mm, width 2-3 mm, length 8.5 mm) which were stored/cured at 23 C. for 24 h and then at 80 C. for 3 h, with a Mettler DMA/SDTA 861e instrument. The measurement conditions were: measurement in tensile mode, excitation frequency 10 Hz and heating rate 5 K/min. The samples were cooled down to 70 C. and heated to 200 C. with determination of the complex modulus of elasticity E* [MPa], and a maximum in the curve for the loss angle tan was read off as T.sub.g.

[0162] The results are reported in tables 1 to 7.

TABLE-US-00003 TABLE 1 R1 R2 R3 E1 E1a E2 E3 E4 E5 E6 E7 E8 E9 E10 Polyol comp. K1 A1 Setathane 1150 64 64 64 64 64 64 64 64 64 64 64 64 64 64 A2 Desmophen T 4011 4 4 4 4 4 4 4 4 4 4 4 4 4 4 A3 Butane-1,4-diol 2 4 2 2 4 4 6 6 8 8 10 10 A4 Polyvest HT 20 32 32 32 20 20 20 20 20 20 20 20 20 20 Catalyst 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Sylosiv 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Polyisocyanate comp. K2 Desmodur VL 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Mixing ratio 37.4 34.4 43.5 49.4 47.3 43.5 53.8 49.4 60 55.1 66 60.5 71.6 65.7 NCO/OH ratio 1.1 1.1 1.2 1.2 1.2 1.1 1.2 1.1 1.2 1.1 1.2 1.1 1.2 1.1 (A1 + A2)/(A3 + A4) 3.4 2.1 2.0 1.9 3.1 3.1 2.8 2.8 2.6 2.6 2.4 2.4 2.3 2.3 (A4/A3) 16.0 8.0 10.0 10.0 5.0 5.0 3.3 3.3 2.5 2.5 2.0 2.0 Gelation time [min] 25 30 25 15 25 28 20 16 10 15 10 11 10 4 3 h at 80 C. TS [MPa] 13.5 9.5 13.5 15.9 17.7 15.7 18.6 19.1 23.6 22.1 26.3 24 25.5 29.3 EB [%] 125.1 122.3 105.7 96.9 108.1 78 88 62 75.2 40 34.1 48 30.8 41 Em0.05-0.25% [MPa] 81 31 264 335 383 362 540 446 907 684 1050 1060 1510 634 Em 0.5-5% [MPa] 22 7 107 218 157 206 293 331 451 413 506 430 472 555 1st Tg ( C.) 62 60 62 62 64 65 64 64 63 66 63 64 64 65 2nd Tg ( C.) 55 52 66 71 67 69 73 76 81 81 88 88 87 96 7 d RT TS [MPa] 11.5 7.76 13.1 15.6 16.3 19.6 27.2 29.1 27.4 EB [%] 113.4 101.1 89.2 88.4 89.8 79.5 75.6 13.2 20.1 Em0.05-0.25% [MPa] 73 15.4 211 494 509 410 842 738 1170 Em 0.5-5% [MPa] 22 5 135 266 214 384 566 627 530

TABLE-US-00004 TABLE 2 E11 E12 E13 E14 E15 E16 Polyol comp. K1 A1 Setathane 1150 64 64 64 64 64 64 A2 Desmophen 4 4 4 4 4 4 T 4011 A3 Butane-1,4-diol 12 12 14 14 16 16 A4 Polyvest HT 20 20 20 20 20 20 Catalyst 0.3 0.3 0.3 0.3 0.3 0.3 Sylosiv 2 2 2 2 2 2 Polyisocyanate comp. K2 Desmodur VL 100 100 100 100 100 100 Mixing ratio 77 70.7 82.2 75.5 87.1 80.1 NCO/OH ratio 1.2 1.1 1.2 1.1 1.2 1.1 (A1 + A2)/ 2.1 2.1 2.0 2.0 1.9 1.9 (A3 + A4) (A4/A3) 1.7 1.7 1.4 1.4 1.3 1.3 Gelation time [min] 10 3 7 7 6 3 3 h at 80 C. TS [MPa] 26.2 32.1 29.1 29.1 26.7 31.6 EB [%] 23.9 53 18.7 18.7 13 27.2 Em0.05-0.25% [MPa] 737 441 1730 1730 923 1350 Em 0.5-5% [MPa] 515 611 550 550 517 594 1st Tg ( C.) 65 65 64 64 64 63 2nd Tg ( C.) 94 100 93 96 94 100 7 d RT TS [MPa] 27.5 28.3 25.6 28.3 EB [%] 13.9 15.1 7.6 15.1 Em0.05-0.25% [MPa] 923 846 779 846 Em 0.5-5% [MPa] 531 548 554 548

TABLE-US-00005 TABLE 3 R1 R2 R4 E17 E18 E19 E20 E21 E22 Polyol comp. K1 A1 Setathane 1150 64 64 64 64 64 64 64 64 64 A2 Desmophen T 4011 4 4 4 4 4 4 4 4 4 A3 2-Ethylhexane-1,3-diol 2 2 4 8 12 16 20 A4 Polyvest HT 20 32 32 20 20 20 20 20 20 Catalyst 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Sylosiv 2 2 2 2 2 2 2 2 2 Polyisocyanate comp. K2 Desmodur VL 100 100 100 100 100 100 100 100 100 Mixing ratio 37.4 34.4 37.6 40.9 44.2 50.5 56.3 61.6 66.6 NCO/OH ratio 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 (A1 + A2)/(A3 + A4) 3.4 2.1 2.0 3.1 2.8 2.4 2.1 1.9 1.7 (A4/A3) 16.0 10.0 5.0 2.5 1.7 1.3 1.0 Gelation time [min] 25 30 40 20 20 17 24 22 18 3 h at 80 C. TS [MPa] 13.5 9.5 11.3 16.8 18.1 20.8 25.3 28.5 30.7 EB [%] 125.1 122.3 130.2 114.4 127.4 102.8 66.1 53 17.9 Em0.05-0.25% [MPa] 81 31 58.8 326 244 744 605 852 2040 Em 0.5-5% [MPa] 22 7 17 115 119 331 524 575 589 1st Tg ( C.) 62 60 61 62 63 64 64 64 65 2nd Tg ( C.) 55 52 57 62 66 76 82 89 92 7 d RT TS [MPa] 11.5 7.76 9.36 15.2 17.4 24.1 29.2 33.1 33.1 EB [%] 113.4 101.1 118.4 104 101 76 17 20 18 Em0.05-0.25% [MPa] 73 15.4 47.8 224 608 1470 598 1820 815 Em 0.5-5% [MPa] 22 5 14 115 186 434 624 636 706

TABLE-US-00006 TABLE 4 R1 E23 E24 E25 E26 E27 E28 E29 E30 E31 E32 Polyol comp. K1 A1 Setathane 1150 64 64 64 64 64 64 64 64 64 64 64 A2 Desmophen T 4011 4 4 4 4 4 4 4 4 4 4 4 A3 3-Methylpentane-1,5-diol 2 2 4 4 6 6 8 8 10 10 A4 Polyvest HT 20 20 20 20 20 20 20 20 20 20 20 Catalyst 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Sylosiv 2 2 2 2 2 2 2 2 2 2 2 Polyisocyanate comp. K2 Desmodur VL 100 100 100 100 100 100 100 100 100 100 100 Mixing ratio 37.4 45.5 41.9 50.2 46.2 54.7 50.3 59.1 54.3 63.2 58.1 NCO/OH ratio 1.1 1.2 1.1 1.2 1.1 1.2 1.1 1.2 1.1 1.2 1.1 (A1 + A2)/(A3 + A4) 3.4 3.1 3.1 2.8 2.8 2.6 2.6 2.4 2.4 2.3 2.3 (A4/A3) 10.0 10.0 5.0 5.0 3.3 3.3 2.5 2.5 2.0 2.0 Gelation time [min] 25 20 26 15 17 15 14 10 12 15 5 3 h at 80 C. TS [MPa] 13.5 18.5 17.8 20.5 19.6 19.6 19.1 22.2 20.7 23.8 24.2 EB [%] 125.1 121.9 97 112.9 101 100.2 76 98.7 64 28.5 33 Em0.05-0.25% [MPa] 81 302 445 555 457 517 522 624 686 1130 740 Em 0.5-5% [MPa] 22 117 153 241 280 330 355 421 373 476 454 1st Tg ( C.) 62 63 64 63 65 64 65 64 2nd Tg ( C.) 55 64 69 72 74 76 78 90 7 d RT TS [MPa] 11.5 17.1 19.7 26.8 23.8 25.4 EB [%] 113.4 107.1 105.2 14.6 68 26.2 Em0.05-0.25% [MPa] 73 380 771 1030 944 952 Em 0.5-5% [MPa] 22 138 296 547 470 538

TABLE-US-00007 TABLE 5 E33 E34 E35 E36 E37 E38 Polyol comp. K1 A1 Setathane 1150 64 64 64 64 64 64 A2 Desmophen T 4011 4 4 4 4 4 4 A3 3- Methylpentane-1,5-diol 12 12 14 14 16 16 A4 Polyvest HT 20 20 20 20 20 20 Catalyst 0.3 0.3 0.3 0.3 0.3 0.3 Sylosiv 2 2 2 2 2 2 Polyisocyanate comp. K2 Desmodur VL 100 100 100 100 100 100 Mixing ratio 67.1 67.1 70.9 65.3 74.5 68.6 NCO/OH ratio 1.2 1.1 1.2 1.1 1.2 1.2 (A1 + A2)/(A3 + A4) 2.1 2.1 2.0 2.0 1.9 1.9 (A4/A3) 1.7 1.7 1.4 1.4 1.3 1.3 Gelation time [min] 10 3 17 8 18 7 3 h at 80 C. TS [MPa] 25.8 27.9 24.2 24.3 23.7 24.4 EB [%] 24.2 15 33.1 69.6 32.7 46.9 Em0.05-0.25% [MPa] 942 914 1360 1110 1130 1570 Em 0.5-5% [MPa] 500 534 458 444 447 513 1st Tg ( C.) 66 65 65 66 66 2nd Tg ( C.) 85 82 80 82 83 7 d RT TS [MPa] 20.3 27.5 25.7 20.3 EB [%] 86.1 9.1 17 86.1 Em0.05-0.25% [MPa] 671 1250 981 671 Em 0.5-5% [MPa] 387 512 468 387

TABLE-US-00008 TABLE 6 R1 E39 E40 E41 E42 E43 E44 E45 E46 E47 Polyol comp. K1 A1 Setathane 1150 64 64 64 64 64 64 64 64 64 64 A2 Desmophen T 4011 4 4 4 4 4 4 4 4 4 4 A3 Pentane-1,5-diol 2 4 4 6 6 8 8 10 10 A4 Polyvest HT 20 20 20 20 20 20 20 20 20 20 Catalyst 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Sylosiv 2 2 2 2 2 2 2 2 2 2 Polyisocyanate comp. K2 Desmodur VL 100 100 100 100 100 100 100 100 100 100 Mixing ratio 37.4 42.6 51.8 47.6 57 52.4 62 57 66.8 61.4 NCO/OH ratio 1.1 1.1 1.2 1.1 1.2 1.1 1.2 1.1 1.2 1.1 (A1 + A2)/(A3 + A4) 3.4 3.1 2.8 2.8 2.6 2.6 2.4 2.4 2.3 2.3 (A4/A3) 10.0 5.0 5.0 3.3 3.3 2.5 2.5 2.0 2.0 Gelation time [min] 25 23 20 25 10 15 <10 9 13 5 3 h at 80 C. TS [MPa] 13.5 16.5 19.1 17.4 22.7 19.6 24.3 22.7 23 25.3 EB [%] 125.1 107 87.3 84 79 49 68.3 30 23.9 41 Em0.05-0.25% [MPa] 81 370 480 542 954 866 800 646 521 908 Em 0.5-5% [MPa] 22 188 320 271 426 353 479 414 468 465 1st Tg ( C.) 62 65 63 65 63 64 64 62 64 2nd Tg ( C.) 55 71 73 80 76 84 81 81 77 7 d RT TS [MPa] 11.5 20.5 25.3 27.3 26.5 EB [%] 113.4 89.3 59.2 52.4 19.2 Em0.05-0.25% [MPa] 73 649 795 727 843 Em 0.5-5% [MPa] 22 376 507 559 520

TABLE-US-00009 TABLE 7 E48 E49 E50 E51 E52 E53 Polyol comp. K1 A1 Setathane 1150 64 64 64 64 64 64 A2 Desmophen T 4011 4 4 4 4 4 4 A3 Pentane-1,5-diol 12 12 14 14 16 16 A4 Polyvest HT 20 20 20 20 20 20 Catalyst 0.3 0.3 0.3 0.3 0.3 0.3 Sylosiv 2 2 2 2 2 2 Polyisocyanate comp. K2 Desmodur VL 100 100 100 100 100 100 Mixing ratio 71.4 65.6 75.7 69.7 79.9 73.6 NCO/OH ratio 1.2 1.1 1.2 1.1 1.2 1.1 (A1 + A2)/(A3 + A4) 2.1 2.1 2.0 2.0 1.9 1.9 (A4/A3) 1.7 1.7 1.4 1.4 1.3 1.3 Gelation time [min] 10 4 10 6 10 10 3 h at 80 C. TS [MPa] 26.1 29.5 24.7 23 23.3 22.4 EB [%] 23.4 44.7 24.1 58.4 10.4 26.6 Em0.05-0.25% [MPa] 1080 802 746 1240 1160 778 Em 0.5-5% [MPa] 525 556 468 428 429 423 1st Tg ( C.) 66 66 65 66 65 71 2nd Tg ( C.) 85 93 94 84 94 86 7 d RT TS [MPa] 29.3 24.8 23.4 EB [%] 13.3 14.8 11 Em0.05-0.25% [MPa] 990 624 916 Em 0.5-5% [MPa] 588 495 450

[0163] Tables 1 to 7 specify the components of the polyol comp. K1, or of the polyisocyanate comp. K2, in parts by weight. The figures ((A1+A2)/(A3+A4)) and (A4/A3) in tables 1 to 7 relate to the weight ratios of the proportions of A1 Setathane 1150, A2 Desmophen T 4011, A3 aliphatic diol and A4 Polyvest HT present.

[0164] The term NCO/OH ratio indicates the ratio of all NCO groups of the aromatic polyisocyanates B1 to all OH groups of the sum total of (A1+A2+A3+A4).

[0165] The term Mixing ratio indicates the proportion of component K2 in parts by weight that has been added to 100 parts by weight of the appropriate component K1.

[0166] Gelation time [min] as a measure of open time was determined the tack-free time. For this purpose, a few grams of the adhesive were applied to cardboard in a layer thickness of about 2 mm and, under standard climatic conditions, the time until, when the surface of the adhesive was gently tapped by means of an LDPE pipette, there were for the first time no residues remaining any longer on the pipette was determined.

[0167] Initial viscosity was measured with a cone-plate rheometer (measured by Brookfield RTV, speed 10 rpm, cone/plate, CP 50/1 at 23 C.) 30 seconds after conclusion of the mixing time. Initial viscosity of the mixed compositions R1, E2 and E16 was measured and was 1730 mPas for R1, 1660 mPas for E2 and 1330 mPas for E16.

[0168] E1 to E53 are inventive examples. R1 to R4 are comparative examples.

[0169] The plot of the modulus of elasticity (complex modulus of elasticity E* [MPa] as a function of the temperature [ C.]) for the compositions R1 (), E2 (.square-solid.), E6 (.box-tangle-solidup.), E10 (), E12 (x) and E16 (+) is shown in FIG. 1. The plot of the modulus of elasticity (complex modulus of elasticity E* [MPa] as a function of the temperature [ C.]) for the compositions R1 (), E39 (.square-solid.), E43 (.box-tangle-solidup.), E47 () and E53 (x) is shown in FIG. 2.

[0170] It follows from this that the compositions of the invention, especially in the temperature range between 60 C. and 120 C., have a higher complex modulus of elasticity E* with increasing proportion of butane-1,4-diol or pentane-1,5-diol. Moreover, the second Tg (Tg2) is increased by up to 30 kelvin. Surprisingly, the aforementioned effects are attenuated again over and above a certain proportion by weight of A3, as apparent in examples E16 and E53.

[0171] Production of Composite Components (Glass Fiber-Reinforced (GFR) Plastic Laminates)

[0172] GFR laminates were produced with compositions E16 and R5 in a vacuum-assisted resin injection (VARI) method.

[0173] The glass fiber weaves (Tissa Glasweberei AG, Oberkulm, CH, 445 g/m.sup.2) consist of fiber bundles of thickness 0.2-0.25 mm and width 2.3-2.5 mm that are composed of continuous fibers, where the fibers are in a unidirectional arrangement and hence form the glass fiber weave. 6 of the unidirectional glass fiber weaves mentioned were laid one on top of another such that the fiber bundles were arranged in the same direction. By means of VARI methods after GFR laminates of thickness 2 mm were obtained.

[0174] Composition R5 (comparative example) is a polyurethane composite resin system consisting of Biresin CRP55 resin (polyol component comprising various polyols) and Biresin B21 (hardener component, comprising MDI-based isocyanates), both obtainable from Sika Deutschland GmbH.

[0175] When R5 was used, the polyol component had to be freed of air/dried by applying reduced pressure (20 mbar for 120 min) while stirring immediately prior to the mixing with the hardener component. Moreover, the glass fiber weave, arranged in the chamber of the VARI method, had to be dried under a reduced pressure of about 70 mbar for 6 hours at 60 C. Immediately after the cooling of the dried glass fiber weave, the mixed composition R5 was injected. If one/both of the aforementioned steps was not executed, this led to formation of finely divided bubbles in the GFR laminates obtained. This resulted in laminates that were hazy as a result of formation of microfoam with mechanical values that were reduced significantly (by more than 20%). Such bubble formation is typical in the case of use of prior art 2K PU compositions that are used for injection methods when the components and/or the substrates are not dried. The values for R5 reported in table 8 were therefore obtained by a method in which the aforementioned steps (drying of the polyol component and of the glass fiber weave) were conducted and which therefore did not have any microfoam formation.

[0176] In the processing of composition E16 to give a laminate, both of these steps were omitted. The GFR laminate obtained did not have any bubble formation and was therefore transparent. The values for E16 reported in table 8 were therefore obtained by a method in which the polyol component was not freed of air/dried prior to or during the mixing with the polyol component, nor was the glass fiber weave dried.

[0177] The compositions were mixed with a SpeedMixer, and immediately thereafter sucked into the chamber of the VARI method in which the 6 glass fiber weaves were disposed by application of reduced pressure. The curing was effected at room temperature for 8 hours under reduced pressure, followed by further curing at 80 C. for 3 hours under reduced pressure. Thereafter, the laminate sheets obtained were removed from the chamber of the VARI method and cooled down to room temperature in an unassisted manner. GFR laminates of thickness 2 mm were obtained.

[0178] 3-point bending samples (6025 mm.sup.2) were cut out of the GFR laminates with a precision disk saw (DIADISC 4200, Mutronic GmbH & Co. KG, Germany) and tested (Z250 SW, Zwick GmbH & Co, KG, Germany) with a span width of 32 mm at a crosshead speed of 1 mm/min, to ISO 178. The values of Bending strength, Elongation at F max and Modulus of elasticity were calculated by the classical beam theory. The measurements are shown in table 8.

TABLE-US-00010 TABLE 8 Properties (25 C., 1 mm/min) E16 R5 Bending strength 0 [MPa] .sup.420 (+/69) 750 (+/32) Elongation at F max 0 [%] .sup.1.9 (+/0.3) 2.6 (+/0.2) Modulus of elasticity 24000 (+/2600) 32000 (+/960).sup. 0 [MPa] Bending strength 90 [MPa] .sup.470 (+/20) 240 (+/7) Elongation at F max 90 [%] .sup.3.7 (+/0.2) 3.1 (+/1.0) Modulus of elasticity 90 25000 (+/3500) 9000 (+/4600).sup. [MPa] Bubble formation* none Bubble formation* *Production of GFR laminates without drying of the polyol component and/or of the glass fiber weave. All mechanical measurements for R5 were measured on GFR laminates that did not have any bubble formation owing to drying of the polyol component and the glass fiber weave.

[0179] Laminates with composition E16 surprisingly showed almost equal values for bending strength and modulus of elasticity both in longitudinal direction to the fiber bundles (0 direction) and in transverse direction (90 direction). This is advantageous especially in relation to resistance to material fatigue.