HARDENER AND CURE ACCELERANT WITH FLAME RETARDANCY EFFECT FOR CURING EPOXY RESINS (II)

Abstract

The present invention relates to novel hardeners for curing epoxy resins and to cure accelerants for the accelerated curing of epoxy resins comprising, in each case, at least one compound from the group of esters of phosphorus-containing acids according to Formula (I), wherein there applies to Formula (I):

##STR00001##

wherein there applies to the radicals R.sup.1, R.sup.2, R.sup.3, R.sup.6, X and indices m, n, p, simultaneously or independently of one another: R.sup.1, R.sup.2=simultaneously or independently of one another, hydrogen or alkyl, R.sup.3=alkyl, aryl, O-alkyl, O-aryl, O-alkylaryl or O-arylalkyl, R.sup.6=hydrogen, alkyl or NHC(O)NR.sup.1R.sup.2, X=oxygen or sulphur, m=1, 2 or 3, n=0, 1 or 2, wherein there applies: m+n=3 p=0, 1 or 2.

Claims

1.-12. (canceled)

13. A composition comprising at least one compound from the group of esters of phosphorus-containing acids according to Formula (I) ##STR00016## wherein radicals R.sup.1, R.sup.2, R.sup.3, R.sup.6, X and indices m, n, p, simultaneously or independently are: R.sup.1, R.sup.2=simultaneously or independently of one another, alkyl, R.sup.3=alkyl, aryl, O-alkyl, O-aryl, O-alkylaryl or O-arylalkyl, R.sup.6=hydrogen, alkyl or NHC(O)NR.sup.1R.sup.2, X=oxygen or sulphur, m=1, 2 or 3, n=0, 1 or 2, wherein m+n=3, and p=0, 1 or 2.

14. The composition of claim 13, wherein the compound is selected from the group of phosphoric acid esters or thiophosphoric acid esters according to Formula (I), wherein R.sup.1, R.sup.2, R.sup.3, R.sup.6, X and indices m, n, p, simultaneously or independently of one another are: R.sup.1, R.sup.2=simultaneously or independently of one another, alkyl, R.sup.3=O-alkyl, O-aryl, O-alkylaryl or O-arylalkyl, R.sup.6=hydrogen, alkyl or NHC(O)NR.sup.1R.sup.2, X=sulphur or oxygen, m=1, 2 or 3, n=0, 1 or 2, wherein m+n=3, and p=0, 1 or 2.

15. The composition of claim 13, wherein the compound is selected from the group of phosphonates or thiophosphonates according to Formula (I), wherein the radicals R.sup.1, R.sup.2, R.sup.3, R.sup.6, X and the indices m, n, p, simultaneously or independently of one another are: R.sup.1, R.sup.2=simultaneously or independently of one another, alkyl, R.sup.3=alkyl or aryl, R.sup.6=hydrogen, alkyl or NHC(O)NR.sup.1R.sup.2, X=sulphur or oxygen, m=2, n=1, and p=0, 1 or 2.

16. The composition of claim 13, wherein the compound is selected from the group of phosphinates or thiophosphinates according to Formula (I), wherein the radicals R.sup.1, R.sup.2, R.sup.3, R.sup.6, X and the indices m, n, p, simultaneously or independently of one another are: R.sup.1, R.sup.2=simultaneously or independently of one another, alkyl, R.sup.3=alkyl or aryl, R.sup.6=hydrogen, alkyl or NHC(O)NR.sup.1R.sup.2, X=sulphur or oxygen, m=1, n=2, and p=0, 1 or 2.

17. The composition of claim 13, wherein the radicals R.sup.1, R.sup.2, R.sup.3, R.sup.6, X and the index p in Formula (I), simultaneously or independently of one another are: R.sup.1, R.sup.2=simultaneously or independently of one another, methyl or ethyl, R.sup.3=O-Aryl, R.sup.6=hydrogen or alkyl, X=sulphur or oxygen, and p=0.

18. The composition of claim 13, wherein the radicals R.sup.1, R.sup.2, R.sup.3, R.sup.6, X and the index p in Formula (I), simultaneously or independently of one another are: R.sup.1, R.sup.2=simultaneously or independently of one another, methyl or ethyl, R.sup.3=aryl, R.sup.6=hydrogen or alkyl, X=sulphur or oxygen, and p=0.

19. A composition comprising at least two different compounds of claim 13.

20. A composition comprising: a) at least one compound for curing epoxy resins, which is different from a compound recited in claim 13; and, b) a compound recited in claim 13.

21. An epoxy resin composition comprising: a) at least one epoxy resin; and, b) at least one compound of claim 13.

22. A composite material comprising: a) a carrier material; b) at least one epoxy resin; and, c) at least one compound of claim 13.

23. A method for curing prepregs, laminates, coatings, polymer resin mixtures, powder paints, sealing compounds or adhesives, in each case comprising use of a compound of claim 13.

24. A method for accelerated curing of prepregs, laminates, coatings, polymer resin mixtures, powder paints, sealing compounds or adhesives, in each case comprising use of a compound of claim 13.

25. A flame retardant in epoxy resins, powder paints, sealing compounds, adhesives or cured moulding compounds comprising in each case a compound of claim 13.

26. A hardener comprising the composition of claim 13.

27. A cure accelerator comprising the composition of claim 13.

Description

EXAMPLES

1) Substances Used and Associated Abbreviations

Epoxy Resin:

[0281] ER epoxy resin with EEW 182-187 (Epikote Resin 828 LVEL, Hexion)

Hardeners/Cure Accelerants:

HA TDI-Uron (DYHARD UR500, AlzChem AG)

[0282] H dicyandiamide (DYHARD 100S, AlzChem AG)
HA-I tri[p-(dimethylcarbamoylamino)phenyl]thiophosphate
HA-II tri[p-(diethylcarbamoylamino)phenyl]thiophosphate
HA-III tri[p-(dimethylcarbamoylamino)phenyl]phosphate
HA-IV di[p-(dimethylcarbamoylamino)phenyl]phenyl phosphate
HA-V [p-dimethylcarbamoylamino)phenyl]diphenyl phosphate
HA-VI di[p-(dimethylcarbamoylamino)phenyl]phenyl phosphonate
HA-VII [p-dimethylcarbamoylamino)phenyl]diphenylphosphinate
HA-VI II tri[m-(dimethylcarbamoylamino)phenyl]phosphate
HA-IX tri[o-(dimethylcarbamoylamino)phenyl]phosphate
HA-X tri[4-(dimethylcarbamoylamino)-3-methylphenyl]phosphate

2) Production of the Hardeners/Cure Accelerants According to the Invention

Example 1: tri[p-(dimethylcarbamoylamino)phenyl]thiophosphate (HA-I)

[0283] HA-I corresponds to a compound according to Formula (I) with m=3; p=0; X=S; R.sup.1=R.sup.2=methyl; R.sup.6=H, wherein the NHC(O)NR.sup.1R.sup.2 group is in the p-position.

[0284] A solution of 12.17 g (0.27 mol) dimethylamine (99%, Linde) in 400 ml toluene is prepared (for analysis, Merck) in an N.sub.2-washed three-necked flask with a return condenser, dropping funnel, thermometer and magnetic stirrer. A solution of 27.92 g (60 mmol) tri(p-isocyanatophenyl)thiophosphate (27% in ethyl acetate, Bayer MaterialScience) in 285 ml toluene is slowly added drop-wise by means of the dropping funnel, so the temperature does not rise above 25 C. (optionally cooling by water bath). During the addition, white solid precipitates. Once the addition has ended, the suspension produced is still stirred for 1.5 h at room temperature. The solid is separated off, washed with a little toluene and dried at 60 C. in a vacuum.

[0285] Yield: 36.00 g (100%)

[0286] Elementary analysis: prov.: 53.99% C; 5.54% H; 13.99% N; 5.16% P found: 54.14% C; 5.68% H; 13.70% N; 5.22% P.

[0287] IR: {tilde over ()} (cm.sup.1)=3356 (w); 1647 (s); 1605 (m); 1533 (m); 1501 (vs); 1407 (s); 1370 (s); 1303 (m); 1246 (m); 1179 (vs); 1159 (vs); 928 (vs); 832 (s); 779 (s); 754 (s); 580 (w); 558 (w); 521 (s)

[0288] .sup.1H-NMR (500.13 MHz, DMSO-d.sub.3): (ppm)=2.91 (s, 18H, CH.sub.3); 7.12 (d, 6H, ArH, .sup.3J.sub.HH=8.0 Hz); 7.50 (d, 6H, ArH, .sup.3J.sub.HH=9.0 Hz); 8.37 (s, 3H, NH)

[0289] .sup.13C-NMR (125.77 MHz, DMSO-d.sub.6): (ppm)=36.20 (CH.sub.3); 120.63 (d, ArC, .sup.3J.sub.PC=4.6 Hz); 120.88 (ArC); 138.51 (ArC); 144.46 (d, ArC, .sup.2J.sub.PC=8.3 Hz); 155.68 (CO)

[0290] .sup.31P-NMR (202.46 MHz, DMSO-d.sub.6): (ppm)=55.08 (SP(OAr).sub.3)

Example 2: tri[p-(diethylcarbamoylamino)phenyl]thiophosphate (HA-II)

[0291] HA-II corresponds to a compound according to Formula (i) with m=3; n=p=0; X=S; R.sup.1=R.sup.2=ethyl; R.sup.6=H, wherein the NHC(O)NR.sup.1R.sup.2 group is in the p-position.

[0292] The production of HA-II takes place analogously to example 1, wherein dimethylamine is replaced by 19.75 g (0.27 mol) diethylamine (99%, Fluka).

[0293] Yield: 40.20 g (98%)

[0294] Elementary analysis: prov.: 57.88% C; 6.62% H; 12.27% N; 4.52% P found: 57.75% C; 6.48% H; 12.15% N; 4.42% P.

[0295] IR: {tilde over ()} (cm.sup.1)=3291 (w); 2973 (w); 2931 (w); 1632 (s); 1603 (m); 1502 (vs); 1450 (m); 1418 (s); 1379 (m); 1303 (m); 1267 (m); 1249 (m); 1223 (vs); 1159 (vs); 1100 (m); 1080 (m); 941 (vs); 920 (vs); 830 (s); 779 (m); 752 (m)

[0296] .sup.1H-NMR (500.13 MHz, DMSO-d.sub.6): (ppm)=1.08 (t, 18H, CH.sub.3, .sup.3J.sub.HH=7.0 Hz); 3.33 (q, 12H, CH.sub.2, .sup.3J.sub.HH=7.1 Hz); 7.12 (d, 6H, ArH, .sup.3J.sub.HH=8.0 Hz); 7.52 (d, 6H, ArH, .sup.3J.sub.HH=9.1 Hz); 8.24 (s, 3H, NH)

[0297] .sup.13C-NMR (125.77 MHz, DMSO-d.sub.6): (ppm)=13.86 (CH.sub.3); 40.52 (CH.sub.2); 120.54 (d, ArC, .sup.3J.sub.PC=3.7 Hz); 121.13 (ArC); 138.51 (ArC); 144.46 (d, ArC, .sup.2J.sub.PC=8.2 Hz); 154.35 (CO)

[0298] .sup.31P-NMR (202.46 MHz, DMSO-d.sub.6): (ppm)=55.14 (SP(OAr).sub.3)

Example 3: tri[p-(dimethylcarbamoylamino)phenyl]phosphate (HA-III)

[0299] HA-III corresponds to a compound according to Formula (I) with m=3; p=0; X=O; R.sup.1=R.sup.2=methyl; R.sup.6=H, wherein the NHC(O)NR.sup.1R.sup.2 group is in the p-position.

a) Production of N-(p-hydroxyphenyl)-N,N-dimethylurea

[0300] The production of N-(p-hydroxyphenyl)-N,N-dimethylurea takes place as described in the patent EP 0 108 712 A1, using 90.00 g (0.825 mol) p-aminophenol (98%, TCI), 90.00 g (0.837 mol) N, N-dimethylcarbamoylchloride (98%, Aldrich), 84.00 g (1,000 mol) sodium bicarbonate (for the analysis, Merck) and 1,800 ml acetone (99.8%, VWR, dried by molecular sieve).

[0301] Yield: 82.48 g (55%)

[0302] Elementary analysis: prov.: 59.99% C; 6.71% H; 15.55% N found: 59.90% C; 6.71% H; 15.50% N.

[0303] Melting point: 204 C. (DSC-Onset), 210 C. (DSC-Peak)

[0304] IR: {tilde over ()} (cm.sup.1)=3341 (w); 3181 (w); 2929 (w); 1615 (m); 1594 (m); 1505 (vs); 1485 (s); 1372 (vs); 1300 (m); 1271 (vs); 1189 (s); 1163 (s); 1103 (m); 1066 (m); 844 (m); 820 (s); 748 (s); 562 (s); 514 (s)

b) Production of HA-III

[0305] 3.78 g (21 mmol) N-(p-hydroxyphenyl)-N,N-dimethylurea in 20 ml acetonitrile (100%, VWR) are prepared in an N.sub.2-washed three-necked flask with a return condenser, dropping funnel, thermometer and magnetic stirrer, 2.13 g (21 mmol) triethylamine (99.5%, Sigma-Aldrich) are added and the reaction mixture being produced is cooled by means of an ice bath to a temperature of 0 C. A solution of 1.07 g (7 mmol) phosphoryl chloride (for synthesis, Merck) in 10 ml acetonitrile is added drop-wise by means of a dropping funnel in such a way that the temperature does not rise above 5 C. Thereafter, the ice bath is removed and the reaction mixture is stirred overnight at room temperature. The reaction mixture is diluted with 250 ml water. The solid precipitating thereafter is separated off, rewashed with a little water and dried at 60 C.

[0306] Yield: 3.49 g (85%)

[0307] Elementary analysis: prov.: 55.48% C; 5.69% H; 14.38% N; 5.300% P found: 55.19% C; 567% H; 14.26% N; 524% P.

[0308] Melting point: 174.5 C. (DSC-Onset), 180.5 C. (DSC-Peak)

[0309] IR: {tilde over ()} (cm.sup.1)=3352 (w); 2924 (w); 1650 (m); 1605 (w); 1532 (m); 1500 (vs); 1409 (s); 1366 (s); 1301 (w); 1280 (m); 1244 (w); 1218 (w); 1160 (vs); 1108 (w); 1067 (w); 1015 (w); 989 (s); 964 (vs); 930 (s); 884 (w); 832 (s); 752 (m); 583 (m)

[0310] .sup.1H-NMR (500.13 MHz, DMSO-d.sub.6): (ppm)=2.91 (s, 18H, CH.sub.3); 7.11 (d, 6H, ArH, .sup.3J.sub.HH=8.7 Hz); 7.49 (d, 6H, ArH, .sup.3J.sub.HH=9.0 Hz); 8.37 (s, 3H, NH)

[0311] .sup.13C-NMR (125.77 MHz, DMSO-d.sub.6): (ppm)=36.20 (CH.sub.3); 119.70 (d, ArC, .sup.3J.sub.PC=4.6 Hz); 120.98 (ArC); 138.41 (ArC); 144.29 (d, ArC, .sup.2J.sub.PC=7.3 Hz); 155.70 (CO)

[0312] .sup.31P-NMR (202.46 MHz, DMSO-d.sub.6): (ppm)=15.94 (OP(OAr).sub.3)

Example 4: di[p-(dimethylcarbamoylamino)phenyl]phenyl phosphate (HA-IV)

[0313] HA-IV corresponds to a compound according to Formula (I) with m=2; n=1; p=0; X=O; R.sup.1=R.sup.2=methyl; R.sup.3=O-phenyl; R.sup.6=H, wherein the NHC(O)NR.sup.1R.sup.2 group is in the p-position.

[0314] 28.83 g (160 mmol) N-(p-hydroxyphenyl)-N,N-dimethylurea are suspended in 160 ml acetonitrile (100%, VWR) in an N.sub.2-washed three-necked flask with a return condenser, dropping funnel, thermometer and magnetic stirrer, 16.19 g (160 mmol) triethylamine (99.5%, Sigma-Aldrich) are added and the mixture being produced is cooled by means of an ice bath to a temperature of 0 C. A solution of 16.88 g (80 mmol) phosphoric acid phenyl ester dichloride (97%, ABCR) in 80 ml acetonitrile is added drop-wise by means of a dropping funnel in such a way that the temperature does not rise above 5 C. Thereafter, the ice bath is removed and the reaction mixture is stirred overnight at room temperature. The solid produced is separated off, rewashed with a little acetonitrile and dried in air. The solid is then suspended in 200 ml water, stirred at 50 C. for 30 min, separated off again and rewashed again with water. Drying then takes place at 60 C. in a vacuum.

[0315] Yield: 34.95 g (88%)

[0316] Elementary analysis: prov.: 57.83% C; 5.46% H; 11.24% N; 6.21% P found: 57.79% C; 5.49% H; 11.39% N; 6.11% P.

[0317] Melting point: 204 C. (DSC-Onset), 208.5 C. (DSC-Peak)

[0318] IR: {tilde over ()} (cm.sup.1)=3310 (w); 1656 (s); 1601 (w); 1531 (s); 1505 (s); 1488 (s); 1410 (m); 1374 (m); 1299 (s); 1246 (w); 1221 (w); 1181 (vs); 1161 (s); 1106 (w); 1075 (w); 1027 (w); 1011 (w); 975 (s); 956 (vs); 936 (m); 892 (w); 830 (s); 756 (s); 523 (s)

[0319] .sup.1H-NMR (500.13 MHz, DMSO-d.sub.6): (ppm)=2.91 (s, 12H, CH.sub.3); 7.12 (m, 4H, ArH); 7.23-7.30 (m, 3H, ArH); 7.44 (t, 2H, ArH, .sup.3J.sub.HH=8.0 Hz); 7.49 (d, 4H, ArH, .sup.3J.sub.HH=9.0 Hz); 8.37 (s, 2H, NH)

[0320] .sup.13C-NMR (125.77 MHz, DMSO-d.sub.6): (ppm)=36.20 (CH.sub.3); 119.67 (d, ArC, .sup.3J.sub.PC=4.6 Hz); 119.92 (d, ArC, .sup.3J.sub.PC=4.6 Hz); 120.95 (ArC); 125.78 (ArC); 130.19 (ArC); 138.46 (ArC); 144.17 (d, ArC, .sup.2J.sub.PC=8.3 Hz); 149.99 (d, ArC, .sup.2J.sub.PC=7.3 Hz); 155.66 (CO)

[0321] .sup.31P-NMR (202.46 MHz, DMSO-d.sub.6): (ppm)=16.35 (OP(OAr).sub.3)

Example 5: [p-(dimethylcarbamoylamino)phenyl]diphenyl phosphate (HA-V)

[0322] HA-V corresponds to a compound according to Formula (I) with m=1; n=2; p=0; X=O; R.sup.1=R.sup.2=methyl; R.sup.3=O-phenyl; R.sup.6=H, wherein the NHC(O)NR.sup.1R.sup.2 group is in the p-position.

[0323] 28.83 g (160 mmol) N-(p-hydroxyphenyl)-N,N-dimethylurea are suspended in 160 ml acetonitrile (100%, VWR) in an N.sub.2-washed three-necked flask with a return condenser, dropping funnel, thermometer and magnetic stirrer, 16.19 g (160 mmol) triethylamine (99.5%, Sigma-Aldrich) are added and the mixture being produced is cooled by means of an ice bath to a temperature of 0 C. A solution of 42.98 g (160 mmol) phosphoric acid diphenyl ester chloride (97%, ABCR) in 80 ml acetonitrile is added drop-wise by means of a dropping funnel in such a way that the temperature does not rise above 5 C. After the removal of the ice bath, the mixture is stirred for 90 min at room temperature and thereafter stirred again for 90 min at a temperature of 50 C. After cooling to room temperature, 400 ml water are added, a two-phase mixture being produced. The upper, aqueous phase is separated off and 240 ml water added to the organic phase. The solid being produced here is separated off, washed with water and dried at 60 C. in a vacuum.

[0324] Yield: 56.93 g (86%)

[0325] Elementary analysis: prov.: 61.16% C; 5.13% H; 6.79% N; 7.51% P found: 61.12% C; 5.09% H; 6.93% N; 7.38% P.

[0326] Melting point: 91 C. (DSC-Onset), 94 C. (DSC-Peak)

[0327] IR: {tilde over ()} (cm.sup.1)=3258 (w); 2930 (w); 1639 (s); 1588 (w); 1543 (m); 1507 (s); 1485 (s); 1455 (m); 1415 (m); 1377 (m); 1311 (s); 1302 (s); 1223 (w); 1183 (vs); 1157 (vs); 1068 (w); 1024 (m); 1017 (m); 1008 (m); 976 (s); 949 (vs); 927 (vs); 902 (s); 828 (s); 768 (s); 750 (s); 684 (s); 513 (vs)

[0328] .sup.1H-NMR (500.13 MHz, DMSO-d.sub.6): (ppm)=2.91 (s, 6H, CH.sub.3); 7.14 (m, 2H, ArH); 7.23-7.31 (m, 6H, ArH); 7.44 (t, 4H, ArH, .sup.3J.sub.HH=7.7 Hz); 7.50 (d, 2H, ArH, .sup.3J.sub.HH=9.0 Hz); 8.38 (s, 1H, NH)

[0329] .sup.13C-NMR (125.77 MHz, DMSO-d.sub.6): (ppm)=36.17 (CH.sub.3); 119.69 (d, ArC, .sup.3J.sub.PC=4.6 Hz); 119.91 (d, ArC, .sup.3J.sub.PC=4.6 Hz); 120.97 (ArC); 125.84 (ArC); 130.20 (ArC); 138.56 (ArC); 144.12 (d, ArC, .sup.2J.sub.PC=7.3 Hz); 149.93 (d, ArC, .sup.2J.sub.PC=7.3 Hz); 155.67 (CO)

[0330] .sup.31P-NMR (202.46 MHz, DMSO-d.sub.6): (ppm)=16.74 (OP(OAr).sub.3)

Example 6: di[p-(dimethylcarbamoylamino)phenyl]phenyl phosphonate (HA-VI)

[0331] HA-VI corresponds to a compound according to Formula (I) with m=2; n=1; p=0; X=O; R.sup.1=R.sup.2=methyl; R.sup.3=phenyl; R.sup.6=H, wherein the NHC(O)NR.sup.1R.sup.2 group is in the p-position.

[0332] 3.60 g (20 mmol) N-(p-hydroxyphenyl)-NN-dimethylurea in 20 ml acetonitrile (100%, VWR) are prepared in an N.sub.2-washed three-necked flask with a return condenser, dropping funnel, thermometer and magnetic stirrer, 2.02 g (20 mmol) triethylamine (99.5%, Sigma-Aldrich) are added and the reaction mixture being produced is cooled by means of an ice bath to a temperature of 0 C. A solution of 1.95 g (10 mmol) phenylphosphonic acid dichloride (for synthesis, Merck) in 10 ml acetonitrile is added drop-wise by means of a dropping funnel in such a way that the temperature does not rise above 5 C. Thereafter, the ice bath is removed and the reaction mixture is stirred overnight at room temperature. The reaction mixture is diluted with 150 ml water. The solid being precipitated is separated off, rewashed with a little water and dried at 60 C. in a vacuum.

[0333] Yield: 3.91 g (81%)

[0334] Elementary analysis: prov.: 59.75% C; 5.64% H; 11.61% N; 6.42% P found: 59.31% C; 5.70% H; 11.49% N; 6.36% P.

[0335] Melting point: 195 C. (DSC-Onset), 200 C. (DSC-Peak)

[0336] IR: {tilde over ()} (cm.sup.1)=3266 (w); 2923 (w); 1652 (s); 1603 (w); 1532 (s); 1504 (s); 1440 (m); 1410 (m); 1372 (s); 1305 (m); 1266 (m), 1184 (vs); 1162 (s); 1069 (w); 1015 (w); 939 (s); 918 (vs); 891 (m); 854 (m); 828 (vs); 756 (s); 559 (s); 519 (vs)

[0337] .sup.1H-NMR (500.13 MHz, DMSO-d.sub.6): (ppm)=2.89 (s, 12H, CH.sub.3); 7.03 (m, 4H, ArH); 7.36-7.44 (m, 4H, ArH); 7.53-7.61 (m, 2H, ArH); 7.65-7.71 (m, 1H, ArH); 7.83-7.93 (m, 2H, ArH); 8.29 (s, 2H, NH)

[0338] .sup.13C-NMR (125.77 MHz, DMSO-d.sub.6): (ppm)=36.17 (CH.sub.3); 120.12 (d, OArC, .sup.3J.sub.PC=3.7 Hz); 120.92 (OArC); 126.32 (d, PArC, .sup.3J.sub.PC=188.8 Hz); 128.96 (d, PArC, .sup.3J.sub.PC=15.6 Hz); 132.07 (d, PArC, .sup.2J.sub.PC=10.1 Hz): 133.50 (d, PArC, .sup.4J.sub.PC=2.8 Hz); 137.93 (OArC); 144.16 (d, OArC, .sup.2J.sub.PC=7.3 Hz); 155.67 (CO)

[0339] .sup.31P-NMR (202.46 MHz, DMSO-d.sub.6): (ppm)=12.31 (t, OP(Ar)(OAr).sub.2, .sup.3J.sub.PH=13.2 Hz)

Example 7: [(p-(dimethylcarbamoylamino)phenyl]diphenyl phosphinate (HA-VII)

[0340] HA-VII corresponds to a compound according to Formula (I) with m=1; n=2; p=0; X=O; R.sup.1=R.sup.2=methyl; R.sup.3=phenyl; R.sup.6=H, wherein the NHC(O)NR.sup.1R.sup.2 group is in the p-position.

[0341] 3.60 g (20 mmol) N-(p-hydroxyphenyl)-N,N-dimethylurea in 20 ml acetonitrile (100%, VWR) are prepared in an N.sub.2-washed three-necked flask with a return condenser, dropping funnel, thermometer and magnetic stirrer, 2.02 g (20 mmol) triethylamine (99.5%, Sigma-Aldrich) are added and the reaction mixture being produced is cooled by means of an ice bath to a temperature of 0 C. A solution of 4.72 g (20 mmol) diphenylphosphinic acid chloride (98%, Acros Organics) in 10 ml acetonitrile is added drop-wise by means of a dropping funnel in such a way that the temperature does not rise above 5 C. Thereafter, the ice bath is removed and the reaction mixture is stirred overnight at room temperature. The reaction mixture is diluted with 50 ml water. The solid being precipitated is separated off, rewashed with a little water and dried at 60 C. in a vacuum.

[0342] Yield: 6.35 g (83%)

[0343] Elementary analysis: prov.: 66.31% C; 5.56% H; 7.36% N; 8.14% P found: 66.30% C; 5.50% H; 7.43% N; 8.26% P.

[0344] Melting point: 222 C. (DSC-Onset), 223.5 C. (DSC-Peak)

[0345] IR: {tilde over ()} (cm.sup.1)=3312 (w); 3061 (w); 2921 (w); 1658 (s); 1601 (w); 1532 (m); 1505 (s); 1484 (m); 1439 (m); 1410 (m); 1370 (m); 1305 (w); 1293 (w); 1229 (s); 1190 (s); 1166 (s); 1128 (s); 1112 (s); 1072 (w); 1017 (w); 996 (w); 955 (w); 922 (vs); 839 (s); 817 (w); 725 (vs); 687 (s); 585 (vs); 538 (s); 527 (vs)

[0346] .sup.1H-NMR (500.13 MHz, DMSO-d.sub.6): (ppm)=2.87 (s, 6H, CH.sub.3); 7.09-7.13 (m, 2H, ArH); 7.30-7.38 (m, 2H, ArH); 7.49-7.56 (m, 4H, ArH); 7.56-7.64 (m, 2H, ArH); 7.82-7.93 (m, 4H, ArH); 8.22 (s, 1H, NH)

[0347] .sup.13C-NMR (125.77 MHz, DMSO-d.sub.6): (ppm)=36.14 (CH.sub.3); 120.30 (d, OArC, .sup.3J.sub.PC=4.6 Hz); 120.89 (OArC); 128.83 (d, PArC, .sup.3J.sub.PC=12.8 Hz); 130.89 (d, PArC, .sup.1J.sub.PC=136.6 Hz); 131.52 (d, PArC, .sup.2J.sub.PC=10.1 Hz); 132.61 (d, PArC, .sup.4J.sub.PC=2.8 Hz); 137.38 (OArC); 144.95 (d, OArC, .sup.2J.sub.PC=8.3 Hz); 155.67 (CO)

[0348] .sup.31P-NMR (202.46 MHz, DMSO-d.sub.6): (ppm)=29.01 (t, OP(Ar).sub.2(OAr), .sup.3J.sub.PH=11.7 Hz)

Example 8: tri[m-(dimethylcarbamoylamino)phenyl]phosphate (HA-VIII)

[0349] HA-VIII corresponds to a compound according to Formula (I) with m=3; n=p=0; X=O; R.sup.1=R.sup.2=methyl; R.sup.6=H, wherein the NHC(O)NR.sup.1R.sup.2 group is in the m-position.

a) Production of N-(m-hydroxyphenyl)-N,N-dimethylurea

[0350] The production of N-(m-hydroxyphenyl)-N,N-dimethylurea takes place as described in patent EP 0 108 712 A1, using 50.00 g (0.458 mol) m-aminophenol (99%, Merck), 37.10 g (0.345 mol) N, N-dimethylcarbamoylchloride (98%, Aldrich) and 325 ml tetrahydrofuran (99.8%, Merck).

[0351] Yield: 34.67 g (56%)

[0352] Elementary analysis: prov.: 59.99% C; 6.71% H; 15.55% N found: 59.92% C; 6.67% H; 15.37% N.

[0353] Melting point: 193 C. (DSC-Onset), 196.5 C. (DSC-Peak)

[0354] IR: {tilde over ()} (cm)=3369 (w); 3088 (w); 1633 (m); 1602 (m); 1537 (s); 1484 (s); 1437 (vs); 1376 (s); 1270 (s); 1231 (m); 1203 (vs); 1168 (s): 1157 (s); 1065 (m); 1031 (w); 972 (m); 871 (m); 853 (m); 777 (s); 765 (s); 740 (s); 692 (s); 610 (s)

b) Production of HA-VIII

[0355] 8.11 g (45 mmol) N-(m-hydroxyphenyl)-N,N-dimethylurea in 50 ml acetonitrile (100%, VWR) are prepared in an N.sub.2-washed three-necked flask with a return condenser, dropping funnel, thermometer and magnetic stirrer, 4.55 g (45 mmol) triethylamine (99.5%, Sigma-Aldrich) are added and the reaction mixture being produced is cooled by means of an ice bath to a temperature of 0 C. A solution of 2.30 g (15 mmol) phosphoryl chloride (for synthesis, Merck) in 25 ml acetonitrile is added drop-wise by means of a dropping funnel in such a way that the temperature does not rise above 5 C. Thereafter, the ice bath is removed and the reaction mixture is stirred further for 30 min at room temperature. The reaction mixture is then stirred for 2 h at 60 C. After cooling to room temperature, the solid present is separated off. The filtrate is reduced until dry on the rotary evaporator and then absorbed in 100 ml acetone. Insoluble components are separated off and the filtrate is then reduced again under a vacuum until it is dry. The solid thus obtained is dried in a vacuum at 60 C.

[0356] Yield: 8.48 g (97%)

[0357] Elementary analysis: prov.: 55.48% C; 5.69% H; 14.38% N; 5.30 % P found: 55.57% C; 5.74% H; 14.11% N; 5.00% P.

[0358] Melting point: >250 C.

[0359] IR: {tilde over ()} (cm.sup.1)=3312 (w); 2928 (w); 1644 (m); 1595 (m); 1530 (m); 1480 (s); 1427 (m); 1367 (m); 1274 (m); 1252 (m); 1182 (s); 1132 (s); 1007 (s); 976 (vs); 914 (s); 860 (m); 777 (m); 755 (m); 683 (m); 606 (m); 553 (m)

[0360] .sup.1H-NMR (500.13 MHz, DMSO-d.sub.6): (ppm)=2.91 (s, 18H, CH.sub.3); 7.11 (d, 6H, ArH, J.sub.HH=8.7 Hz); 7.49 (d, 6H, ArH, .sup.3J.sub.HH=9.0 Hz); 8.37 (s, 3H, NH)

[0361] .sup.13C-NMR (125.77 MHz, DMSO-d.sub.6): (ppm)=36.20 (CH.sub.3); 119.70 (d, ArC, .sup.3J.sub.PC=4.6 Hz); 120.98 (ArC); 138.41 (ArC); 144.29 (d, ArC, .sup.2J.sub.PC=7.3 Hz); 155.70 (CO)

[0362] .sup.31P-NMR (202.46 MHz, DMSO-d.sub.6): (ppm)=15.94 (OP(OAr).sub.3)

Example 9: tri[o-(dimethylcarbamoylamino)phenyl]phosphate (HA-IX)

[0363] HA-IX corresponds to a compound according to Formula (I) with m=3; n=p=0; X=O; R.sup.1=R.sup.2=methyl; R.sup.6=H, wherein the NHC(O)NR.sup.1R.sup.2 group is in the o-position.

a) Production of N-(o-hydroxyphenyl)-N,N-dimethylurea

[0364] The production of N-(o-hydroxyphenyl)-N,N-dimethylurea takes place analogously to the production of N-(m-hydroxyphenyl)-N,N-dimethylurea [see example 8 a)], wherein m-aminophenol is replaced by o-aminophenol (99%, Aldrich).

[0365] Yield: 34.70 g (56%)

[0366] Elementary analysis: prov.: 59.99% C; 6.71% H; 15.55% N found: 59.95% C; 6.62% H; 15.59% N.

[0367] Melting point: 137 C. (DSC-Onset), 139.5 C. (DSC-Peak)

[0368] IR: {tilde over ()} (cm.sup.1)=3430 (w); 3058 (w); 1644 (m); 1594 (m); 1538 (s); 1486 (s); 1451 (s); 1416 (s); 1366 (s); 1324 (s); 1280 (s); 1237 (s); 1201 (s); 1154 (m); 1103 (m); 1069 (m); 1030 (m); 923 (w); 889 (w); 807 (w); 748 (vs); 647 (w); 609 (m); 550 (s)

b) Production of HA-IX

[0369] 8.11 g (45 mmol) N-(o-hydroxyphenyl)-N,N-dimethylurea in 50 ml acetonitrile (100%, VWR) are prepared in an N.sub.2-washed three-necked flask with a return condenser, dropping funnel, thermometer and magnetic stirrer, 4.55 g (45 mmol) triethylamine (99.5%, Sigma-Aldrich) are added and the reaction mixture being produced is cooled by means of an ice bath to a temperature of 0 C. A solution of 2.30 g (15 mmol) phosphoryl chloride (for synthesis, Merck) in 25 ml acetonitrile is added drop-wise by means of a dropping funnel in such a way that the temperature does not rise above 5 C. Thereafter, the ice bath is removed and the reaction mixture is stirred further for 30 min at room temperature. The reaction mixture is then stirred for 2 h at 60 C. After cooling to room temperature, the solid present is separated off and suspended in 50 ml water. The suspension is stirred for 1 h at room temperature, the solid is then separated off again, washed with water and dried at 60 C. in a vacuum.

[0370] Yield: 6.08 g (69%)

[0371] Elementary analysis: prov.: 55.48% C; 5.69% H; 14.38% N; 5.30% P found: 55.50% C; 5.57% H; 14.30% N; 5.07% P.

[0372] Melting point: 159 C. (DSC-Onset), 160 C. (DSC-Peak)

[0373] IR: {tilde over ()} (cm.sup.1)=3318 (w); 2924 (w); 1677 (m); 1637 (s); 1596 (m); 1525 (s); 1489 (s); 1439 (s); 1375 (s); 1296 (s); 1273 (s); 1251 (s); 1172 (vs); 1099 (s); 1067 (w); 1041 (m); 989 (s); 969 (vs); 936 (s); 887 (w); 847 (s); 750 (vs); 642 (m)

[0374] .sup.1H-NMR (500.13 MHz, DMSO-d.sub.6): (ppm)=2.74 (s, 18H, CH.sub.3); 7.09 (m, 3H. ArH); 7.20 (t, 3H, ArH, .sup.3J.sub.HH=7.5 Hz); 7.28 (d, 3H, ArH, .sup.3J.sub.HH=8.0 Hz); 7.60 (d, 3H, ArH, J.sub.HH=8.0 Hz); 7.81 (s, 3H, NH)

[0375] .sup.13C-NMR (125.77 MHz, DMSO-d.sub.6): (ppm)=35.85 (CH.sub.3); 119.98 (d, ArC, .sup.3J.sub.PC=1.8 Hz); 124.35 (ArC); 125.70 (ArC); 131.22 (d, ArC, .sup.3J.sub.PC=6.4 Hz); 142.43 (d, ArC, .sup.2J.sub.PC=7.3 Hz); 155.47 (CO)

[0376] .sup.31P-NMR (202.46 MHz, DMSO-d.sub.6): (ppm)=16.72 (OP(OAr).sub.3)

Example 10: tri[4-(dimethylcarbamoylamino)-3-methylphenyl]phosphate (HA-X)

[0377] HA-IX corresponds to a compound according to Formula (I) with m=3; n=p=0; X=O; R.sup.1=R.sup.2=R.sup.6=methyl, wherein the NHC(O)NR.sup.1R.sup.2 group is in the 4-position and R.sup.6 is in the 3-position of the aromatic ring.

a) Production of N-(4-hydroxy-2-methylphenyl)-N,N-dimethylurea

[0378] The production of N-(4-hydroxy-2-methylphenyl)-N,N-dimethylurea takes place analogously to the production of N-(m-hydroxyphenyl)-N,N-dimethylurea [see example 8 a)], wherein m-aminophenol is replaced by 4-amino-3-methylphenol (98%, Alfa-Aesar).

[0379] Yield: 16.17 g (59%)

[0380] Elementary analysis: prov.: 61.84% C; 7.27% H; 14.42% N found: 61.75% C; 7.12% H; 14.29% N.

[0381] Melting point: 221 C. (DSC-Onset), 227 C. (DSC-Peak)

[0382] IR: {tilde over ()} (cm.sup.1)=3354 (w); 3161 (w); 2923 (w); 1591 (m); 1531 (s); 1461 (s); 1372 (m); 1294 (m); 1225 (vs): 1191 (m); 1158 (m); 1101 (m); 1064 (m); 1041 (w); 1002 (w); 951 (w); 880 (m); 815 (m); 752 (s); 630 (w); 556 (m)

b) Production of HA-X

[0383] 6.41 g (33 mmol) N-(4-hydroxy-2-methylphenyl)-N,N-dimethylurea in 40 ml acetonitrile (100%, VWR) are prepared in an N.sub.2-washed three-necked flask with a return condenser, dropping funnel, thermometer and magnetic stirrer, 3.34 g (33 mmol) triethylamine (99.5%, Sigma-Aldrich) are added and the reaction mixture being produced is cooled by means of an ice bath to a temperature of 0 C. A solution of 1.69 g (11 mmol) phosphoryl chloride (for synthesis, Merck) in 15 ml acetonitrile is added drop-wise by means of a dropping funnel in such a way that the temperature does not rise above 5 C. Thereafter, the ice bath is removed and the reaction mixture is stirred further for 30 min at room temperature. The reaction mixture is then stirred for 2 h at 60 C. After cooling to room temperature, the solid present is separated off. The filtrate is reduced on the rotary evaporator until it is dry and then absorbed in 30 ml acetone. Insoluble components are separated off and the filtrate is then reduced again under a vacuum until it is dry. The solid thus obtained is dried in a vacuum at 60 C.

[0384] Yield: 5.58 g (81%)

[0385] Elementary analysis: prov.: 57.50% C; 6.27% H; 13.41% N; 4.94% P found: 57.34% C; 6.23% H; 12.78% N; 4.52% P.

[0386] Melting point: >250 C.

[0387] IR: {tilde over ()} (cm.sup.1)=3287 (w); 2927 (w); 1639 (m); 1494 (s); 1412 (m); 1366 (m); 1291 (m); 1267 (m); 1199 (s); 1143 (vs); 1111 (m); 1067 (w); 1007 (s); 968 (vs); 914 (m); 893 (m); 869 (m); 812 (m); 758 (m); 708 (w); 600 (m); 558 (m)

[0388] .sup.1H-NMR (500.13 MHz, DMSO-d.sub.6): (ppm)=2.91 (s, 18H, CH.sub.3); 7.11 (d, 6H, ArH, .sup.3J.sub.HH=8.7 Hz); 7.49 (d, 6H, ArH, .sup.3J.sub.HH=9.0 Hz); 8.37 (s, 3H, NH)

[0389] .sup.13C-NMR (125.77 MHz, DMSO-d.sub.6): (ppm)=36.20 (CH.sub.3); 119.70 (d, ArC, .sup.3J.sub.PC=4.6 Hz); 120.98 (ArC); 138.41 (ArC); 144.29 (d, ArC, .sup.2J.sub.PC=7.3 Hz); 155.70 (CO)

[0390] .sup.31P-NMR (202.46 MHz, DMSO-d.sub.6): (ppm)=15.94 (OP(OAr).sub.3)

3) Epoxy Resin Compositions with Hardeners/Cure Accelerants According to the Invention and Preparation of the Formulations

[0391] The invention will be shown using the example of the formulations of epoxy resin compositions listed in Table 1.

TABLE-US-00001 TABLE 1 Epoxy resin compositions used Example (according Components of the formulation to the invention) (parts by weight) A (no) ER (100) HA (8) B (yes) ER (100) HA-I (8) C (no) ER (100) H (6.5) HA (3) D (yes) ER (100) H (6.5) HA-I (3) E (yes) ER (100) H (6.5) HA-III (5) F (yes) ER (100) H (6.5) HA-IV (5) G (yes) ER (100) H (6.5) HA-V (5) H (yes) ER (100) H (6.5) HA-VI (5) I (yes) ER (100) H (6.5) HA-VII (5) J (yes) ER (100) HA-III (8) K (yes) ER (100) HA-IV (8) L (yes) ER (100) HA-VI (8)

[0392] The components mentioned under the respective example are thoroughly mixed with one another in a mortar for DSC investigations and determinations of latencies.

[0393] For investigations on the flame retardancy effect, the individual components of a formulation are mixed in a dissolver. For this purpose, the components are weighed into a 1-L dissolver vessel and the mixture is dispersed in the dissolver for 2 min at 900 rpm, thereafter for 2 min at 3,000 rpm and finally for 3 min at 3,500 rpm. Thereafter, the mixture is degassed for 60 min at 60 rpm under vacuum. The formulation is ready for use when no further discernible bubbles are located on the surface.

[0394] Produced from the formulations thus produced are cured plates with the dimensions 4 mm180 mm350 mm, from which the test specimens required for the investigations on combustion behaviour are milled using a CNC milling machine. The conditions used for the production of the plates (1st step: curing, 2nd step: annealing) for the individual formulations are given in Table 2.

TABLE-US-00002 TABLE 2 Conditions for producing cured plates of the exemplary formulations Curing Annealing Example (according Temperature Temperature Time to the invention) [ C.] Time [h] [ C.] [h] A (no) 95 3 100 2 B (yes) 100 4 115 2 C (no) 100 2 140 2 D (yes) 100 2.5 140 2 E (yes) 95 2.5 130 2 F (yes) 105 3 140 2 G (yes) 115 3 125 2

4) DSC Investigations

[0395] The effectiveness of the compounds according to the invention as hardeners/cure accelerants is shown using the example of HA-I compared to HA, a common hardener/cure accelerant.

[0396] For this purpose, characteristic data from DSC measurements are used. The DSC measurements described below are carried out on a dynamic thermal flow difference calorimeter DSC 1 or DSC 822e (Mettler Toledo)

a) Dynamic DSC:

[0397] A sample of the formulation is heated at a heating rate of 10 K/min from 30-250 C. The exothermic reaction peak is evaluated by determining the onset temperature (T.sub.onset), the temperature at the peak maximum (T.sub.max) and the peak area as a measure of the released reaction heat (.sub.RH).

b) T.SUB.G .Determination:

[0398] To determine the maximum glass transition temperature (End-T.sub.G), a sample of the cured formulation is subjected to the following DSC temperature program: heating from 30-200 C. at 20 K/min, 10 min holding at 200 C., cooling from 200-50 C. at 20 K/min, 5 min holding at 50 C., heating from 50-200 C. at 20 K/min, 10 min holding at 200 C., cooling from 200-50 C. at 20 K/min, 5 min holding at 50 C., heating from 50-220 C. at 20 K/min. From the two last heating cycles, the glass transition temperature is determined and the average given as End-T.sub.G, in each case, by placing a tangent at the turning point of the greatest change in the thermal capacity (C.sub.p).

c) Isothermal DSC:

[0399] A sample of the formulation is kept constant at the given temperature for the given time (isothermal curing of the formulation). The evaluation takes place by determining the time of the peak maximum (as a measure for the start of the curing process) and the 90% conversion (as a measure of the end of the curing process) of the exothermal reaction peak.

[0400] The results of the DSC investigations are summarised in Table 3 and Table 4.

TABLE-US-00003 TABLE 3 Results of the dynamic DSC und T.sub.G determination Example (according End-T.sub.G to the invention) T.sub.onset [ C.] T.sub.max [ C.] .sub.RH [J/g] [ C.] A (no) 153 175 544 98 B (yes) 156 181 543 111 C (no) 137 144 477 137 D (yes) 145 153 509 147 E (yes) 143 152 475 137 F (yes) 151 159 457 142 G (yes) 150 170 575 136 H (yes) 148 157 483 136 I (yes) 150 159 451 136 J (yes) 154 177 355 112 K (yes) 152 176 223 98 L (yes) 162 185 256 100

TABLE-US-00004 TABLE 4 Results of the isothermal DSC Example (according Peak maximum 90% conversion to the invention) Conditions [min] [min] A (no) 140 C., 7.5 26.5 120 min B (yes) 140 C., 9.4 47.8 120 min C (no) 140 C., 60 min 1.4 12.5 D (yes) 140 C., 60 min 2.7 11.9 E (yes) 140 C., 60 min 2.5 13.2 F (yes) 140 C., 60 min 3.9 17.2 G (yes) 140 C., 4.4 73.3 180 min H (yes) 140 C., 60 min 3.2 18.9 I (yes) 140 C., 60 min 4.0 23.0 J (yes) 140 C., 60 min 8.3 35.9 K (yes) 140 C., 90 min 7.2 51.6 L (yes) 140 C., 9.3 65.9 120 min

[0401] The comparison of the examples according to the invention with a technically conventional hardener/cure accelerant such as HA (examples A and C) shows that when using the hardeners or cure accelerants according to the invention, comparable characteristic values for the curing process can be determined by means of DSC. The values for T.sub.onset and T.sub.max from the dynamic DSC measurements for formulations with the hardeners/cure accelerants according to the invention are slightly higher than when using HA (examples A or C), i.e. the curing is slightly slower when using the hardeners/cure accelerants according to the invention. The energy .sub.RH being released during the curing is in the same order of magnitude in all formulations, which shows that in all the formulations tested, a curing actually takes place. When using the hardeners/cure accelerants according to the invention, the achievable glass transition temperature compared to the respective formulation with the technically conventional hardener/cure accelerant is at least comparable and in some examples significantly higher (examples B, D, F, J and L).

[0402] In the isothermal DSC measurements, the results are also comparable. The peak maximum in isothermal curing in the formulations according to the invention is reached slightly later but these differences are not significant. The time up to a reaction conversion of 90% when using the hardeners/cure accelerants according to the invention compared to the technically conventional hardener/cure accelerant HA is sometimes slightly longer, but technically still feasible.

[0403] To summarise, the DSC investigations show that the compounds according to the invention can be used analogously to already known hardeners/cure accelerants and show a similar curing characteristic here.

5) Flame Retardancy Effect

[0404] The flame retardancy effect of the compounds according to the invention is shown using the example of HA-I compared to HA, a common hardener/cure accelerant. Test specimens of cured formulations are used for the investigations mentioned below. The following fire tests are carried out:

a) Oxygen Index:

[0405] The oxygen index (also limiting oxygen index, LOI) is determined according to DIN EN ISO 4589-2 (Plastics materialsDetermination of the combustion behaviour by the oxygen indexPart 2: Testing at ambient temperature). The tests are carried out using test specimens with the dimension 100 mm10 mm4 mm (test specimen type III) by ignition method A.

b) Small Burner Test:

[0406] The small burner test takes place according to UL 94 V (Tests for Flammability of Plastic Materials for Parts in Devices and Applications). The tests are carried out each with 5 test specimens with the dimension 127 mm13 mm4 mm.

[0407] The results of the individual fire tests are summarised in Table 5 and Table 6.

TABLE-US-00005 TABLE 5 Results of the oxygen index determinations Example (according to the Oxygen index [% by invention) volume] A (no) 21.1 B (yes) 26.7 C (no) 20.7 D (yes) 22.3 E (yes) 23.2 F (yes) 23.0 G (yes) 22.3

[0408] The oxygen index states what oxygen content (in % by volume) is at least required in an oxygen-nitrogen gas mixture so that an ignited test specimen continues to burn after removal of the ignition source. If the oxygen index is greater than the oxygen content present in the normal atmosphere of about 21% by volume, a self-extinguishing of the tested materials is observed and therefore a flame-retarding effect is shown. For the materials corresponding to examples A and C (not according to the invention) oxygen index values of 21.1 vol. % or 20.7 vol. % were determined. In the normal atmosphere (oxygen content about 21 vol. %) a continuing further burning after the ignition by means of a burner flame is established here. A higher value is determined for examples D, E, F and G (according to the invention, containing HA-I, HA-Ill, HA-IV or HA-V as cure accelerants). The best result is determined for example B (according to the invention, containing HA-I as the hardener) with 26.7 vol. %. In the materials mentioned last, a rapid self-extinguishing is to be expected in the normal atmosphere (air).

TABLE-US-00006 TABLE 6 Results of the small burner tests (5 test specimens each) Example Afterburn duration Afterburn duration (according to 1.sup.st flame 2nd. flame the invention) treatment [s]* treatment [s]* Observation.sup.# A (no) >180/>180/>180/ //// burning dripping off with ignition >180/>180 of the wadding and complete combustion B (yes) 16/5/5/15/5 207/32/2/28/ self-extinguishing without falling 109 away C (no) 2/>180/>180/3/ >180///>180/ burning dripping off with ignition >180 of the wadding and complete combustion D (yes) 74/166/>180/2/5 >180///77/ partial burning falling away with 184 ignition of the wadding and complete combustion, partly self-extinguishing without falling away *Given in each case are the results of the 5 individual test specimens. A second flame treatment only takes place when self-extinguishing is observed during the first flame treatment. In the case of complete combustion without self-extinguishing, >180 s is noted as the value for the afterburn duration. .sup.#The observations relate to the state after two flame treatments. If only one flame treatment was carried out, the state present thereafter is described.

[0409] The flame treatment tests of the small burner test according to UL 94 V show an improvement in the flame retardancy effect when using the hardener/cure accelerant HA-I according to the invention instead of the technically conventional hardener/cure accelerant HA. Both for example A and example C (neither according to the invention), the afterburn duration in the individual tests is predominantly more than 180 s and a burning dripping off (with ignition of the wadding located therebelow) and a complete combustion of the test specimens is to be observed. For examples B and D (both according to the invention, containing HA-I as the hardener or cure accelerant), the afterburn duration in the individual tests is predominantly less than 180 s and in some cases even significantly less (formulation B). The test specimens of formulation B, in contrast to formulation A, show self-extinguishing without dripping off or the falling away of test specimen parts. For the test specimens of formulation D, a burning falling away (with ignition of the wadding located therebelow) and complete combustion was partly observed, but some of the test specimens also exhibited self-extinguishing without dripping off or the falling away of test specimen parts. Compared to the analogous formulation C (containing HA as the cure accelerant), an improved flame retardancy effect is thus also to be seen for formulation D (containing HA-I as the cure accelerant).

[0410] To summarise, the investigations show that the compound HA-I according to the invention when used as the sole hardener or as the cure accelerant, in comparison with the technically conventional hardener/cure accelerant HA, leads to an improvement in the flame retardancy effect within an otherwise comparable epoxy resin composition. The use of the hardener/cure accelerant HA-I according to the invention in examples B and D instead of a technically conventional hardener such as HA (examples A and C) within an epoxy resin composition leads both to improvement of the oxygen index and to an improved combustion behaviour in the small burner test. For the compounds HA-III (example E), HA-IV (example F) and HA-V (example G) during use as the sole hardener, a higher oxygen index was also determined compared to the technically conventional hardener HA (example). Therefore an improved flame retardancy effect is demonstrated analogously to the compound HA-I (example D).

6) Latencies (Storage Stability)

[0411] To determine the latency (storage stability) about 20 g of the respective formulation according to Table 1 are freshly prepared and then stored at a temperature of 23 C. and a relative humidity of 50% (climatic chamber). By regularly measuring the dynamic viscosity, the progressing cross-linking (curing) of the formulation under these storage conditions is recorded. The dynamic viscosity is determined using a Haake viscosimeter [cone(1)-plate method, measurement at 25 C., shear rate 5.0 s.sup.1]. A formulation is classified as stable when stored (still suitable for processing) until the viscosity doubles.

TABLE-US-00007 TABLE 7 Results of the test for storage stability Example (according Time until the dynamic to the invention) viscosity [d] doubles A (no) 32 B (yes) 70 C (no) 30 D (yes) 70 E (yes) 150 F (yes) >80 G (yes) >120 H (yes) >60 I (yes) >120 J (yes) 130 K (yes) >80 L (yes) >60

[0412] The formulations according to the invention, at at least 60 days, have a significantly higher storage stability than the comparable formulations not according to the invention at a storage stability of 32 days (formulation A) or 30 days (formulation C).

[0413] To summarise, the tests for storage stability show that using the compounds according to the invention, formulations can be obtained which, compared to formulations that are obtained using conventional hardeners or cure accelerants, have a significantly better storage stability.