COPOLYCARBONATE COMPOSITIONS WITH IMPROVED RHEOLOGICAL AND OPTICAL PROPERTIES CONTAINING DIGLYCEROLESTERS

Abstract

The invention relates to copolycarbonate compositions containing diglycerolesters, which have improved rheological as well as optical properties, to their use for producing blends, mouldings and to moldings obtained therewith.

Claims

1.-15. (canceled)

16. A composition comprising A) 67.0 to 99.95 wt % of one or more copolycarbonates comprising monomer units selected from the group consisting of the structural units of general formulae (1a), (1b), (1c) and (1d) ##STR00017## in which R.sup.1 represents hydrogen or C.sub.1-C.sub.4-alkyl, R.sup.2 represents C.sub.1-C.sub.4-alkyl, n represents 0, 1, 2 or 3 and R.sup.3 represents C.sub.1-C.sub.4-alkyl, aralkyl or aryl, Or 67.0 to 99.95 wt % of a blend of the one or more copolycarbonates and at least one further homo- or copolycarbonate comprising one or more monomer units of general formula (2): ##STR00018## in which R.sup.4 represents H, linear or branched C.sub.1-C.sub.10 alkyl and R.sup.5 represents linear or branched C.sub.1-C.sub.10 alkyl; wherein the optionally present further homo- or copolycarbonate has no monomer units of formulae (1a), (1b), (1c) and (1d); B) 0.05 to 3.0 wt % of at least one diglycerol ester; and C) optionally one or more added substances in a total amount of up to 30.0 wt %.

17. The composition as claimed in claim 16, wherein the diglycerol ester is derived from a saturated or unsaturated monocarboxylic acid having a chain length of 6 to 30 carbon atoms.

18. The composition as claimed in claim 16, wherein the composition comprises as component B) a diglycerol ester of formula (I) or a mixture of different diglycerol esters of formula (I) ##STR00019## in which R represents COC.sub.nH.sub.2n+1 or COR′, R′ is a branched alkyl radical or a branched or unbranched alkenyl radical, C.sub.nH.sub.2n+1 is an aliphatic, saturated linear alkyl radical and n represents an integer from 6 to 24.

19. The composition as claimed in claim 16, wherein the diglycerol ester is derived from a carboxylic acid selected from the group consisting of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, palmitoleic acid, petroselic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, arachidonic acid, timnodonic acid and cervonic acid.

20. The composition as claimed in claim 16, wherein the diglycerol ester has an HLB value of 6 to 12.

21. The composition as claimed in claim 16, wherein the amount of diglycerol ester is 0.10 to 2.0 wt %.

22. The composition as claimed in claim 16, wherein the total proportion of the monomer units of formulae (1a), (1 b), (1c) and (1d) in the copolycarbonate is 0.1-88 mol % (based on the sum of the diphenol monomer units present therein).

23. The composition as claimed in claim 16, wherein the composition comprises the one or more copolycarbonates comprising the monomer units of formulae (1a), (1 b), (1c) and/or (1d) in an amount of at least 60 wt %.

24. The composition as claimed in claim 16, wherein the copolycarbonate comprising the monomer units of formulae (1a), (1b), (1c) and/or (1d) further comprises monomer units of formula (3) ##STR00020## in which R.sup.6 and R.sup.7 independently of one another represent H, C.sub.1-C.sub.18-alkyl-, C.sub.1-C.sub.18-alkoxy, halogen such as Cl or Br or respectively optionally substituted aryl or aralkyl and Y represents a single bond, —SO.sub.2—, —CO—, —O—, —S—, C.sub.1-C.sub.6-alkylene or C.sub.2-C.sub.5-alkylidene, furthermore C.sub.6-C.sub.12-arylene, which may optionally be fused with further heteroatom—comprising aromatic rings.

25. The composition as claimed in claim 16, wherein the copolycarbonate comprises monomer units derived from compounds of general formulae (1a″), (1b′), (1 c′) and/or (1 d′) in combination with monomer units derived from compounds of general formula (3c). ##STR00021## wherein R.sup.3 is methyl or phenyl.

26. The composition as claimed in claim 16, wherein the composition comprises as component A) a blend of the copolycarbonate and the further homo- or copolycarbonate comprising one or more monomer units of general formula (2), wherein R.sup.4 represents H and R.sup.5 represents linear or branched C.sub.1-C.sub.6 alkyl.

27. The composition as claimed in claim 16, wherein the composition comprises one or more additives selected from the group consisting of thermal stabilizers, demolding agents and UV stabilizers.

28. The composition as claimed in claim 16, wherein the composition comprises 0.002 to 0.2 wt % of thermal stabilizer, 0.01 wt % to 1.00 wt % of UV stabilizer and 0.05 wt % to 2.00 wt % of demolding agent.

29. A blend, molding, extrudate, film or film laminate obtainable from copolycarbonate compositions as claimed in claim 16 or else a molding, extrudate or film comprising coextrusion layers obtainable from copolycarbonate compositions as claimed in claim 16.

30. A method comprising utilizing at least one diglycerol ester for improving the breaking elongation and/or for reducing the yellowness index of compositions comprising a copolycarbonate as claimed in claim 16 or a blend of the copolycarbonate and a further homo- or copolycarbonate as claimed in claim 16.

Description

EXAMPLES

[0170] Raw materials used: [0171] Component A is a blend of PC1 and PC2 (examples 1-3), copolycarbonate PC3 or PC4 (examples 4 to 9) or one of copolycarbonates PCS to PC11 (see table 7, examples 10-30). [0172] PC 1 is a commercially available copolycarbonate based on bisphenol A and bisphenol TMC having an MVR of 18 cm.sup.3/10 min (330° C./2.16 kg) and a softening temperature (VST/B 120) of 183° C. (Apec 1895 from Bayer MaterialScience AG). [0173] PC 2 is a polycarbonate powder based on bisphenol A having an MVR of 6 cm.sup.3/10 min (300° C./1.2 kg).). It is used to improve incorporation (metering) of component B. [0174] PC 3 Lexan XHT2141; high heat copolycarbonate based on bisphenol A and the bisphenol of formula (Ib′) where R.sup.3=phenyl from Sabic Innovative Plastics having an MVR of 43 cm.sup.3/10 min (330° C., 2.16 kg) [0175] PC 4 Lexan XHT4143; UV stabilized high heat copolycarbonate based on bisphenol A and the bisphenol of formula (Ib′) where R.sup.3=phenyl from Sabic Innovative Plastics [0176] component B Poem. DL-100 (diglycerol monol.aurate, HLB=9) from Riken Vitamin. [0177] component C triisooctyl phosphate (TOF) from Lanxess AG.

[0178] Syntheis of the Bisphenol of Formula (1b′) where R.sup.3=methyl:

##STR00016##

[0179] A flange reactor is initially charged with a solution of 2 kg (20.2 mol) of N-methylpyrrolidone (NMP) and 1273.3 g (4 mol) of phenolphtalein. 2 liters of water and then 18 mol of a 40% aqueous methylamine solution are added with stirring. The reaction solution turns violet upon addition of the methylamine. The mixture is then stirred for a further 8 hours at 82° C. utilizing a. dry ice cooler. This causes the coloring of the reaction batch to change to dark yellowish. Once the reaction has ended the reaction batch is precipitated by means of a dropping funnel with stirring into a reservoir of water acidified with hydrochloric acid,

[0180] The precipitated white reaction product is slurried with 2 liters of water and then suctioned off using a G3 frit. The crude product obtained is redissolved in 3.5 liters of a dilute sodium hydroxide solution (16 mol) and in turn precipitated in a reservoir of water acidified with hydrochloric acid. The reprecipitated crude product is repeatedly slurried with 2 liters of water and then suctioned off each time. This washing procedure is repeated until the conductivity of the washing water is less than 15 μS.

[0181] The thus obtained product is dried to constant mass in a vacuum drying cabinet at 90° C.

[0182] After 4-fold performance of the experiment the following yields were obtained in each case:

[0183] 1a) 950 g of a white solid

[0184] 1b) 890 g of a white solid.

[0185] 1c) 1120 g of a white solid

[0186] 1d) 1050 g of a white solid

[0187] (melting point 264° C.)

[0188] Characterization of the obtained bisphenols was effected by .sup.1H-NMR spectroscopy.

[0189] Synthesis of Copolycarbonate Based on a Bisphenol of Formula (1b′) where R.sup.3=methyl and Bisphenol A:

[0190] To a nitrogen-inertized solution of 532.01 g (1.6055 mol) of bisphenol. A (BPA), 2601.36 g (11.39 mol) of bisphenol from example 1, 93.74 g (0.624 mol, 4.8 mol % based on diphenols) of p-tert.-butylphenol (BUP) as chain terminator and 1196 g (29.9 mol) of sodium hydroxide in 25.9 liters of water are added 11.79 liters of methylene chloride and 14.1 liters of chlorobenzene. At a pH of 12.5 13.5 and 20° C., 2.057 kg (20.8 mol) of phosgene are introduced. In order to prevent the pH from falling below 12.5, 30% sodium hydroxide solution was added during the phosgenation. Once phosgenation is complete and after purging with nitrogen the mixture is stirred for a further 30 minutes, 14.7 g (0.13 mol, 1 mol % based on diphenols) of N-ethylpiperidine are then added as catalyst and the mixture is stirred for a further 1 hour. After removal of the aqueous phase and acidification with phosphoric acid the organic phase is washed several times with water using a separator until salt-free. The organic phase is separated off and subjected to a solvent exchange in which methylene chloride is replaced with chlorobenzene. The concentrated copolycarbonate solution in chlorobenzene is then freed of solvent using a vented extruder. The obtained polycarbonate melt extrudates are cooled in a water bath, drawn off and finally pelletized. Transparent polycarbonate pellets are obtained.

[0191] Synthesis of Copolycarbonates PC5 to PC11

[0192] Copolycarbonates PC5 to PC11 were produced as per the preceding procedure for producing copolycarbonate based on a bisphenol of formula (1b′) where R.sup.3=methyl and bisphenol A (see table 7 for stoichiometry).

[0193] Synthesis of the Copolycarbonate Compositions of Examples 1-3

[0194] The copolycarbonate compositions of examples 1-3 based on raw materials PC1 and PC2 and also component B and component C are mixed according to the formulations reported in table 1 in a twin-screw extruder at 300° C. The thus-obtained polymer compositions are pelletized and are ready for polymer physical characterizations.

[0195] Synthesis of the Copolycarbonate Compositions of Examples 4-30

[0196] The polycarbonate compositions of examples 4 to 30 are produced in a DSM Miniextruder based on the raw materials stated. The melt temperature was 330° C. The thus-obtained polymer compositions are pelletized and are ready for polymer physical characterizations.

[0197] Characterization of the Molding Materials According to the Invention (Test Methods):

[0198] Characterization of the molding materials according to the invention (test methods): Melt volume flow rate (MVR) was determined in accordance with ISO 1133 (at a test temperature of 330° C., mass 2.16 kg) using a Zwick 4106 instrument from Roell.

[0199] Vicat softening temperature VST/B120 was determined as a measure of heat distortion resistance in accordance with ISO 306 on test specimens measuring 80 mm×10 mm×4 mm with a 50 N ram loading and a heating rate of 50° C./h or of 120° C./h with a Coesfeld Eco 2920 instrument from Coesfeld Materialtest.

[0200] The yellowness index (Y.I.) was determined as per ASTM E 313 (observer: 10°/light type: D65) on sample plates having a sheet thickness of 4 mm.

[0201] Charpy impact resistance was measured at room temperature according to ISO 7391/179eU on single side gate injection molded test bars measuring 80 mm×10 mm×3 mm.

[0202] Charpy notched impact resistance was measured at room temperature according to ISO 7391/179eA on single side gate injection molded test bars measuring 80 mm×10 mm×3 mm.

[0203] The rheological tests were performed with an MCR 301 cone-and-plate rheometer with a CP 25 measuring cone and the conditions below:

[0204] Test method: Oscillation—cone and plate

[0205] Frequency: 75 to 0.08 Hz =angular frequency of 471 to 0.5 [l/s]

[0206] Deformation: 10%-20 measurement points

[0207] Temperatures: 300° C., 280° C. and 260° C.,+−0.3° C.

[0208] Modulus of elasticity was measured according to ISO 527 on single side gate injection molded shoulder bars having a core measuring 80×10×4 mm

TABLE-US-00001 TABLE 1 Copolycarbonate compositions Example 1 (comparative) 2 3 PC-1 % 93.00 93.00 93.00 PC-2 % 7.00 6.79 6.59 Component B % — 0.20 0.40 Component C % — 0.01 0.01 The % values are wt % values in each case.

TABLE-US-00002 TABLE 2 Rheological and thermal properties of the compositions Example 1 (comparative) 2 3 MVR 330° C./2.16 kg cm.sup.3/10 min 16.0 19.7 25.6 Melt visc. at 300° C. eta 50 Pa .Math. s 1682 1511 1341 eta 100 Pa .Math. s 1553 1416 1249 eta 200 Pa .Math. s 1346 1244 1118 eta 500 Pa .Math. s 928 873 791 eta 1000 Pa .Math. s 628 594 542 eta 1500 Pa .Math. s 492 462 421 eta 5000 Pa .Math. s 218 205 189 Melt visc. at 320° C. eta 50 Pa .Math. s 802 719 684 eta 100 Pa .Math. s 764 682 639 eta 200 Pa .Math. s 698 628 588 eta 500 Pa .Math. s 555 506 478 eta 1000 Pa .Math. s 410 379 361 eta 1500 Pa .Math. s 328 306 292 eta 5000 Pa .Math. s 149 142 137 Melt visc. at 330° C. eta 50 Pa .Math. s 556 521 439 eta 100 Pa .Math. s 541 505 423 eta 200 Pa .Math. s 508 472 403 eta 500 Pa .Math. s 425 397 344 eta 1000 Pa .Math. s 330 311 276 eta 1500 Pa .Math. s 271 257 236 eta 5000 Pa .Math. s 129 123 117 Melt visc. at 340° C. eta 50 Pa .Math. s 398 353 310 eta 100 Pa .Math. s 383 342 305 eta 200 Pa .Math. s 367 331 288 eta 500 Pa .Math. s 321 293 255 eta 1000 Pa .Math. s 263 241 215 eta 1500 Pa .Math. s 224 206 186 eta 5000 Pa .Math. s 113 106 99 Melt visc. at 360° C. eta 50 Pa .Math. s 216 175 151 eta 100 Pa .Math. s 214 174 149 eta 200 Pa .Math. s 211 171 144 eta 500 Pa .Math. s 194 159 135 eta 1000 Pa .Math. s 171 142 123 eta 1500 Pa .Math. s 151 129 110 eta 5000 Pa .Math. s 85 77 74 Vicat VSTB 120 ° C. 179.3 178.2 176.0

[0209] For virtually identical Vicat temperatures the inventive examples 2 and 3 exhibit significantly higher MVR values which indicate an improved flowability of the melts.

[0210] The improved flowabilities are likewise demonstrable for all shear rates over the entire industrial processing range from 300° C. to 360° C.

TABLE-US-00003 TABLE 3 Optical properties of the copolycarbonate compositions Examples 1 optical data (comparative) 2 3 330° C. Transmission % 86.97 87.21 87.26 Haze % 0.49 0.64 0.53 Y.I. 1.82 1.41 1.42 360° C. Transmission % 86.97 87.2 87.2 Haze % 0.34 0.58 0.57 Y.I. 2.05 1.45 1.57

[0211] In all cases the inventive examples 2 and 3 show a higher transmission coupled with a lower yellowness index (Y.I.) than the comparative example 1.

TABLE-US-00004 TABLE 4 Mechanical properties of the copolycarbonate compositions Examples 1 mechanical properties (comparative) 2 3 Impact resistance (Charpy, kJ/m.sup.2 n.b. n.b. 9xn.b. ISO 7391/179eU 1x113 s Notched impact resistance kJ/m.sup.2 9 s 7 s 7 s (Charpy, ISO7391/179eA Tensile tests (ISO 527) Yield stress N/mm.sup.2 73 74 75 Elongation % 6.6 6.5 6.3 Tear strength N/mm.sup.2 69 70 74 Breaking elongation % 111 118 130 Modulus of elasticity N/mm.sup.2 2415 2438 2484 n.b.: test rod not broken

[0212] For virtually identical behavior for the impact resistances the inventive examples 2 and 3 exhibit mechanical properties that are consistently improved over those of comparative example 1.

TABLE-US-00005 TABLE 5 (Composition of the compounds of examples 4-9 4 7 (compar- (compar- ative) 5 6 ative) 8 9 PC-3 % 100 99.8 99.6 — — — PC-4 % — — — 100 99.8 99.6 POEM % — 0.2 0 — 0.2 0.4 DL-100 Tg [° C.] 164.2 162.4 160.7 181.7 182.1 179.3 The % values are wt % values in each case.

TABLE-US-00006 TABLE 6 (Melt viscosity at angular frequency of 471 to 0.503 [Hz]: 4 7 (compar- (compar- Example: ative) 5 6 ative) 8 9 Cone/plate rheology Cone/plate Melt visc. at 260° C. [Hz] 471 Pa .Math. s 1000 796 705 1240 1150 975 329 Pa .Math. s 1200 980 823 1680 1550 1220 229 Pa .Math. s 1420 1150 933 2140 1980 1450 160 Pa .Math. s 1640 1330 1040 2710 2530 1690 112 Pa .Math. s 1860 1490 1130 3350 3100 1910 77.8 Pa .Math. s 2080 1640 1200 4040 3700 2120 54.3 Pa .Math. s 2280 1770 1270 4790 4320 2310 37.9 Pa .Math. s 2460 1880 1320 5530 4920 2460 26.4 Pa .Math. s 2620 1960 1360 6250 5460 2590 18.4 Pa .Math. s 2750 2030 1400 6910 5950 2700 12.9 Pa .Math. s 2860 2080 1410 7520 6380 2780 8.97 Pa .Math. s 2930 2120 1430 8050 6740 2840 6.25 Pa .Math. s 2990 2150 1440 8490 7030 2880 4.36 Pa .Math. s 3030 2170 1450 8850 7250 2910 3.04 Pa .Math. s 3060 2180 1450 9130 7410 2930 2.12 Pa .Math. s 3080 2190 1450 9340 7530 2940 1.48 Pa .Math. s 3100 2190 1450 9500 7610 2940 1.03 Pa .Math. s 3110 2190 1450 9610 7670 2940 0.721 Pa .Math. s 3110 2200 1450 9670 7680 2930 0.503 Pa .Math. s 3110 2190 1450 9700 7670 2900 Melt visc. at 280° C. [Hz] 471 Pa .Math. s 577 494 353 932 814 486 329 Pa .Math. s 678 557 383 1130 960 540 229 Pa .Math. s 770 613 409 1330 1110 590 160 Pa .Math. s 854 662 431 1540 1250 636 112 Pa .Math. s 928 705 449 1750 1400 675 77.8 Pa .Math. s 990 743 463 1950 1530 707 54.3 Pa .Math. s 1040 772 472 2140 1650 731 37.9 Pa .Math. s 1080 794 479 2310 1750 749 26.4 Pa .Math. s 1110 810 483 2450 1830 762 18.4 Pa .Math. s 1140 821 486 2570 1890 771 12.9 Pa .Math. s 1150 829 487 2670 1940 776 8.97 Pa .Math. s 1170 834 487 2730 1970 779 6.25 Pa .Math. s 1170 837 487 2790 2000 780 4.36 Pa .Math. s 1180 838 486 2820 2010 780 3.04 Pa .Math. s 1180 840 486 2850 2020 779 2.12 Pa .Math. s 1180 840 484 2860 2020 777 1.48 Pa .Math. s 1190 841 483 2870 2030 775 1.03 Pa .Math. s 1190 842 482 2870 2020 772 0.721 Pa .Math. s 1190 842 481 2870 2020 769 0.503 Pa .Math. s 1190 840 479 2870 2010 764 Melt visc. at 300° C. [Hz] 471 Pa .Math. s 347 258 171 598 481 224 329 Pa .Math. s 378 275 179 689 537 240 229 Pa .Math. s 406 291 186 773 590 255 160 Pa .Math. s 430 304 192 848 637 266 112 Pa .Math. s 450 314 196 915 679 275 77.8 Pa .Math. s 465 321 199 972 713 282 54.3 Pa .Math. s 477 327 201 1020 740 287 37.9 Pa .Math. s 486 331 202 1050 760 291 26.4 Pa .Math. s 492 333 202 1080 775 293 18.4 Pa .Math. s 497 334 202 1100 784 294 12.9 Pa .Math. s 499 335 202 1110 789 295 8.97 Pa .Math. s 501 335 202 1120 792 295 6.25 Pa .Math. s 503 336 202 1120 793 295 4.36 Pa .Math. s 504 336 202 1130 794 295 3.04 Pa .Math. s 505 336 202 1130 794 295 2.12 Pa .Math. s 505 336 202 1130 793 295 1.48 Pa .Math. s 506 337 202 1130 792 296 1.03 Pa .Math. s 508 338 203 1130 792 296 0.721 Pa .Math. s 509 340 204 1120 791 297 0.503 Pa .Math. s 510 341 205 1120 789 299

[0213] Table 6 shows that compared to the inventive examples 5, 6 and 9 the comparative examples 4 and 7 which do not comprise the flow assistant exhibit higher melt viscosities at the three measurement temperatures and thus have poorer flowability.

TABLE-US-00007 TABLE 7 Composition of the copolycarbonates PC-5 to PC-11 Co- poly- carbonate no. based on: PC-5 PC-6 PC-7 PC-8 PC-9 PC-10 PC-11 Bisphenol 77.93 78.5 77.5 76.5 80 80 80 according 70.9 71.6 70.4 69.2 73.4 73.4 73.4 to formula (lb’) where R.sup.3 = methyl [mol %] [wt %] Bisphenol 22.07 21.5 22.5 23.5 20 20 20 A (BPA) 29.1 28.4 29.6 30.8 26.6 26.6 26.6 [mol %] [wt %] Glass 179.4 179.6 179.6 182.3 175.3 176.1 173.9 transition temper- ature Tg [° C.] η.sub.rel — 1.234 1.225 1.237 1.216 1.228 1.218

TABLE-US-00008 TABLE 8 (Composition of the compounds of examples 10-30): POEM DL- Tg Example PC-5% PC-6% PC-7% PC-8% PC-9% PC-10% PC-11% 100% ° C. 10 100 179.4 (comparative) 11 99.8 0.2 178.7 12 99.6 0.4 172.4 13 100 179.6 (comparative) 14 99.8 0.2 175.1 15 99.6 0.4 168.6 16 100 179.6 (comparative) 17 99.8 0.2 177.3 18 99.6 0.4 169.5 19 100 182.3 (comparative) 20 99.8 0.2 179.3 21 99.6 0.4 171.9 22 100 175.3 (comparative) 23 99.8 0.2 175.2 24 99.6 0.4 171.3 25 100 176.1 (comparative) 26 99.8 0.2 171.5 27 99.6 0.4 168.6 28 100 173.9 (comparative) 29 99.8 0.2 171.9 30 99.6 0.4 167.3 The % values are wt % values in each case.

TABLE-US-00009 TABLE 9 (Melt viscosity at angular frequency of 471 to 0.503 [Hz] 10 13 (compar- (compar- Example ative) 11 12 ative) 14 15 Cone/plate rheology Melt visc. at 260° C. [Hz] 471 Pa .Math. s 835 938 441 441 938 356 329 Pa .Math. s 1120 1210 494 494 1100 390 229 Pa .Math. s 1400 1490 548 548 1280 423 160 Pa .Math. s 1720 1820 597 597 1480 453 112 Pa .Math. s 2050 2160 641 641 1680 479 77.8 Pa .Math. s 2360 2460 679 679 1870 501 54.3 Pa .Math. s 2640 2720 712 712 2050 520 37.9 Pa .Math. s 2910 2970 739 739 2210 537 26.4 Pa .Math. s 3140 3190 763 763 2350 555 18.4 Pa .Math. s 3350 3390 783 783 2470 565 12.9 Pa .Math. s 3520 3550 802 802 2570 578 8.97 Pa .Math. s 3660 3690 820 820 2650 592 6.25 Pa .Math. s 3780 3800 839 839 2720 607 4.36 Pa .Math. s 3870 3890 858 858 2770 624 3.04 Pa .Math. s 3940 3960 879 879 2810 642 2.12 Pa .Math. s 3980 4000 898 898 2840 660 1.48 Pa .Math. s 4020 4040 918 918 2870 680 1.03 Pa .Math. s 4050 4080 936 936 2900 700 0.721 Pa .Math. s 4060 4100 955 955 2920 720 0.503 Pa .Math. s 4070 4110 975 975 2950 740 Melt visc. at 280° C. [Hz] 471 Pa .Math. s 545 612 197 679 493 155 329 Pa .Math. s 660 701 210 772 553 163 229 Pa .Math. s 752 788 221 865 611 170 160 Pa .Math. s 832 869 231 952 665 176 112 Pa .Math. s 906 943 238 1030 713 181 77.8 Pa .Math. s 973 1010 245 1100 756 185 54.3 Pa .Math. s 1030 1060 250 1160 791 189 37.9 Pa .Math. s 1080 1110 255 1210 820 193 26.4 Pa .Math. s 1120 1150 259 1250 843 197 18.4 Pa .Math. s 1150 1180 263 1290 861 200 12.9 Pa .Math. s 1170 1200 267 1310 874 204 8.97 Pa .Math. s 1190 1220 271 1320 884 208 6.25 Pa .Math. s 1200 1230 275 1330 892 212 4.36 Pa .Math. s 1210 1240 279 1340 899 217 3.04 Pa .Math. s 1210 1240 284 1350 906 222 2.12 Pa .Math. s 1220 1250 289 1350 912 227 1.48 Pa .Math. s 1220 1250 296 1350 919 233 1.03 Pa .Math. s 1220 1250 305 1350 929 240 0.721 Pa .Math. s 1230 1260 316 1350 940 248 0.503 Pa .Math. s 1230 1260 330 1350 954 258 Melt visc. at 300° C. [Hz] 471 Pa .Math. s 332 341 102 376 267 74.6 329 Pa .Math. s 363 370 104 409 287 76.4 229 Pa .Math. s 392 396 105 439 305 77.8 160 Pa .Math. s 418 419 106 465 320 79 112 Pa .Math. s 439 438 107 486 332 80 77.8 Pa .Math. s 457 453 107 503 342 80.8 54.3 Pa .Math. s 471 465 107 516 349 81.7 37.9 Pa .Math. s 481 474 107 526 354 82.5 26.4 Pa .Math. s 488 480 108 533 358 83.7 18.4 Pa .Math. s 492 485 108 538 361 84.2 12.9 Pa .Math. s 496 488 108 541 363 85.2 8.97 Pa .Math. s 497 490 109 542 365 86.3 6.25 Pa .Math. s 497 492 110 543 367 87.8 4.36 Pa .Math. s 497 494 112 544 369 89.4 3.04 Pa .Math. s 497 495 115 546 372 91.6 2.12 Pa .Math. s 496 496 119 545 375 94.2 1.48 Pa .Math. s 496 497 124 546 380 97.6 1.03 Pa .Math. s 496 499 131 545 388 102 0.721 Pa .Math. s 496 502 138 545 398 107 0.503 Pa .Math. s 497 504 147 544 412 113 16 19 (compar- (compar- Example ative) 17 18 ative) 20 21 Cone/plate rheology Melt visc. at 260° C. [Hz] 471 Pa .Math. s 1240 946 253 1310 969 329 329 Pa .Math. s 1490 1110 269 1610 1150 352 229 Pa .Math. s 1760 1290 282 1950 1340 371 160 Pa .Math. s 2050 1500 292 2310 1570 387 112 Pa .Math. s 2360 1710 300 2710 1830 399 77.8 Pa .Math. s 2680 1910 305 3130 2110 408 54.3 Pa .Math. s 2990 2110 309 3550 2360 414 37.9 Pa .Math. s 3280 2280 311 3960 2600 418 26.4 Pa .Math. s 3540 2430 314 4340 2810 422 18.4 Pa .Math. s 3770 2570 315 4680 3000 424 12.9 Pa .Math. s 3960 2680 315 4980 3160 425 8.97 Pa .Math. s 4130 2770 316 5240 3290 427 6.25 Pa .Math. s 4260 2850 317 5460 3410 429 4.36 Pa .Math. s 4360 2910 317 5630 3500 430 3.04 Pa .Math. s 4450 2970 319 5760 3580 431 2.12 Pa .Math. s 4500 3010 320 5870 3650 431 1.48 Pa .Math. s 4550 3060 323 5960 3710 433 1.03 Pa .Math. s 4580 3100 328 6020 3760 434 0.721 Pa .Math. s 4610 3140 335 6060 3800 435 0.503 Pa .Math. s 4620 3160 343 6090 3830 436 Melt visc. at 280° C. [Hz] 471 Pa .Math. s 666 545 98.7 730 514 105 329 Pa .Math. s 758 614 102 845 583 108 229 Pa .Math. s 850 681 104 968 656 110 160 Pa .Math. s 940 743 106 1090 725 112 112 Pa .Math. s 1020 799 107 1200 789 113 77.8 Pa .Math. s 1100 848 108 1300 845 113 54.3 Pa .Math. s 1160 888 109 1390 894 114 37.9 Pa .Math. s 1220 921 109 1470 936 114 26.4 Pa .Math. s 1260 946 110 1540 970 115 18.4 Pa .Math. s 1300 965 111 1590 997 115 12.9 Pa .Math. s 1320 979 111 1630 1020 115 8.97 Pa .Math. s 1340 989 112 1660 1040 116 6.25 Pa .Math. s 1360 995 114 1680 1050 117 4.36 Pa .Math. s 1370 1000 116 1700 1060 118 3.04 Pa .Math. s 1370 1010 119 1710 1070 119 2.12 Pa .Math. s 1380 1010 123 1720 1080 121 1.48 Pa .Math. s 1380 1010 128 1730 1090 125 1.03 Pa .Math. s 1390 1020 135 1740 1100 129 0.721 Pa .Math. s 1390 1020 144 1740 1110 134 0.503 Pa .Math. s 1390 1030 154 1740 1120 140 Melt visc. at 300° C. [Hz] 471 Pa .Math. s 369 265 59.1 59.1 279 41.3 329 Pa .Math. s 402 285 60.3 60.3 303 41.3 229 Pa .Math. s 433 303 61.2 61.2 325 41.2 160 Pa .Math. s 460 318 62.1 62.1 343 41.1 112 Pa .Math. s 482 330 62.9 62.9 359 41.1 77.8 Pa .Math. s 501 340 63.7 63.7 371 41.1 54.3 Pa .Math. s 515 347 64.6 64.6 381 41.1 37.9 Pa .Math. s 526 353 65.6 65.6 389 41.3 26.4 Pa .Math. s 535 358 66.7 66.7 394 41.6 18.4 Pa .Math. s 540 361 67.8 67.8 398 42.1 12.9 Pa .Math. s 544 364 68.9 68.9 401 42.9 8.97 Pa .Math. s 546 366 70.3 70.3 403 44 6.25 Pa .Math. s 547 368 71.8 71.8 405 45.7 4.36 Pa .Math. s 548 370 73.8 73.8 408 48 3.04 Pa .Math. s 549 373 76.3 76.3 411 50.8 2.12 Pa .Math. s 549 375 79.3 79.3 414 54.1 1.48 Pa .Math. s 550 378 83 83 419 58.1 1.03 Pa .Math. s 551 383 87.6 87.6 426 62.7 0.721 Pa .Math. s 551 388 93.5 93.5 437 68 0.503 Pa .Math. s 552 395 101 101 451 74.1 22 25 (compar- (compar- Example ative) 23 24 ative) 26 27 Cone/plate rheology Melt visc. at 260° C. [Hz] 471 Pa .Math. s 1320 1030 731 946 380 268 329 Pa .Math. s 1620 1220 834 1120 413 286 229 Pa .Math. s 1940 1420 935 1300 444 302 160 Pa .Math. s 2290 1630 1030 1480 471 315 112 Pa .Math. s 2670 1830 1120 1670 493 325 77.8 Pa .Math. s 3050 2030 1190 1840 511 332 54.3 Pa .Math. s 3430 2210 1260 2010 525 338 37.9 Pa .Math. s 3790 2370 1310 2160 535 342 26.4 Pa .Math. s 4120 2510 1350 2290 542 344 18.4 Pa .Math. s 4430 2630 1390 2400 547 346 12.9 Pa .Math. s 4700 2730 1410 2500 551 348 8.97 Pa .Math. s 4920 2810 1430 2570 555 350 6.25 Pa .Math. s 5110 2860 1450 2630 557 351 4.36 Pa .Math. s 5250 2900 1460 2680 559 353 3.04 Pa .Math. s 5360 2930 1470 2710 561 356 2.12 Pa .Math. s 5440 2940 1470 2730 563 359 1.48 Pa .Math. s 5500 2960 1470 2750 567 365 1.03 Pa .Math. s 5540 2960 1470 2760 571 374 0.721 Pa .Math. s 5550 2960 1470 2770 577 387 0.503 Pa .Math. s 5550 2950 1460 2770 584 407 Melt visc. at 280° C. [Hz] 471 Pa .Math. s 736 525 394 379 146 95.1 329 Pa .Math. s 846 585 431 100 152 97.6 229 Pa .Math. s 958 644 464 458 157 99.4 160 Pa .Math. s 1070 697 493 494 161 101 112 Pa .Math. s 1170 746 518 525 164 102 77.8 Pa .Math. s 1270 787 538 553 166 102 54.3 Pa .Math. s 1360 822 553 576 168 103 37.9 Pa .Math. s 1430 850 565 596 169 103 26.4 Pa .Math. s 1490 871 574 613 171 104 18.4 Pa .Math. s 1540 887 579 623 172 104 12.9 Pa .Math. s 1580 899 583 632 173 104 8.97 Pa .Math. s 1610 906 584 639 174 104 6.25 Pa .Math. s 1630 911 585 645 175 105 4.36 Pa .Math. s 1650 915 586 650 177 106 3.04 Pa .Math. s 1660 917 586 656 179 107 2.12 Pa .Math. s 1660 917 585 660 181 109 1.48 Pa .Math. s 1660 917 584 665 185 112 1.01 Pa .Math. s 1660 917 583 670 190 115 0.721 Pa .Math. s 1660 917 581 675 195 119 0.503 Pa .Math. s 1650 915 578 679 202 125 Melt visc. at 300° C. [Hz] 471 Pa .Math. s 391 231 161 243 58.4 42.2 329 Pa .Math. s 428 247 168 260 59.8 42.7 229 Pa .Math. s 463 261 174 276 60.9 43.1 160 Pa .Math. s 495 272 179 291 61.9 43.4 112 Pa .Math. s 522 282 183 303 62.8 43.8 77.8 Pa .Math. s 544 289 185 312 63.6 44.2 54.3 Pa .Math. s 563 294 187 320 64.5 44.6 37.9 Pa .Math. s 577 298 188 326 65.5 45.2 26.4 Pa .Math. s 588 301 188 331 66.7 45.9 18.4 Pa .Math. s 595 302 188 335 68.1 46.9 12.9 Pa .Math. s 599 304 188 338 69.7 48.3 8.97 Pa .Math. s 603 304 188 342 71.9 50.1 6.25 Pa .Math. s 604 304 188 344 74.3 52.5 4.36 Pa .Math. s 605 304 187 346 77.2 55.5 3.04 Pa .Math. s 604 304 188 349 80.8 59.2 2.12 Pa .Math. s 603 304 188 352 84.9 63.4 1.48 Pa .Math. s 602 305 188 356 89.8 68.4 1.03 Pa .Math. s 600 306 190 361 95.5 74 0.721 Pa .Math. s 598 307 191 368 102 80.6 0.503 Pa .Math. s 594 308 194 375 110 88.1 28 30 (compar- (compar- Example ative) 29 ative) Cone/plate rheology Melt visc. at 260° C. [Hz] 471 Pa .Math. s 831 789 315 329 Pa .Math. s 972 918 342 229 Pa .Math. s 1120 1050 367 160 Pa .Math. s 1260 1170 388 112 Pa .Math. s 1390 1300 405 77.8 Pa .Math. s 1520 1410 418 54.3 Pa .Math. s 1640 1510 428 37.9 Pa .Math. s 1740 1590 436 26.4 Pa .Math. s 1820 1660 441 18.4 Pa .Math. s 1890 1720 444 12.9 Pa .Math. s 1950 1760 446 8.97 Pa .Math. s 1990 1800 449 6.25 Pa .Math. s 2030 1820 450 4.36 Pa .Math. s 2050 1840 451 3.04 Pa .Math. s 2060 1850 454 2.12 Pa .Math. s 2070 1850 456 1.48 Pa .Math. s 2080 1860 460 1.03 Pa .Math. s 2090 1860 467 0.721 Pa .Math. s 2100 1860 476 0.503 Pa .Math. s 2100 1860 489 Melt visc. at 280° C. [Hz] 471 Pa .Math. s 379 377 145 329 Pa .Math. s 414 415 152 229 Pa .Math. s 446 450 158 160 Pa .Math. s 475 482 163 112 Pa .Math. s 500 509 166 77.8 Pa .Math. s 520 532 169 54.3 Pa .Math. s 537 550 171 37.9 Pa .Math. s 550 564 173 26.4 Pa .Math. s 560 574 175 18.4 Pa .Math. s 567 582 177 12.9 Pa .Math. s 572 586 178 8.97 Pa .Math. s 575 589 180 6.25 Pa .Math. s 577 591 182 4.36 Pa .Math. s 578 592 185 3.04 Pa .Math. s 580 594 189 2.12 Pa .Math. s 581 594 193 1.48 Pa .Math. s 583 596 200 1.03 Pa .Math. s 586 597 208 0.721 Pa .Math. s 589 600 217 0.503 Pa .Math. s 592 602 228 Melt visc. at 300° C. [Hz] 471 Pa .Math. s 279 189 63.5 329 Pa .Math. s 301 201 65 229 Pa .Math. s 321 211 66.1 160 Pa .Math. s 338 219 67.1 112 Pa .Math. s 353 226 67.9 77.8 Pa .Math. s 365 231 68.6 54.3 Pa .Math. s 375 235 69.3 37.9 Pa .Math. s 382 237 70.1 26.4 Pa .Math. s 388 239 70.9 18.4 Pa .Math. s 393 241 72 12.9 Pa .Math. s 397 242 73.4 8.97 Pa .Math. s 399 243 75.3 6.25 Pa .Math. s 402 244 77.8 4.36 Pa .Math. s 403 245 81.1 3.04 Pa .Math. s 405 247 85.4 2.12 Pa .Math. s 407 249 90.5 1.48 Pa .Math. s 410 254 96.6 1.03 Pa .Math. s 412 260 104 0.721 Pa .Math. s 417 268 111 0.503 Pa .Math. s 420 277 120

[0214] Table 9 shows that compared to the inventive examples 11-12, 14-15, 17-18, 20-21, 23-24, 26-27 and 29-30 the comparative examples 10, 13, 16, 19, 22, 25 and 28 which do not comprise the diglycerol ester in each case exhibit higher melt viscosities in the table at the three measurement temperatures and thus have poorer flowability.