FILLED POLYCARBONATE COMPOSITIONS HAVING IMPROVED FLOWABILITY AND GREAT RIGIDITY
20170362430 · 2017-12-21
Inventors
- Helmut Werner Heuer (Leverkusen, DE)
- Rolf Wehrmann (Krefeld, DE)
- Anke Boumans (Goch, DE)
- Michael Erkelenz (Duisburg, DE)
- Hans Franssen (Krefeld, DE)
Cpc classification
C08K5/0066
CHEMISTRY; METALLURGY
C08L2205/035
CHEMISTRY; METALLURGY
C08K5/0066
CHEMISTRY; METALLURGY
C08L2205/03
CHEMISTRY; METALLURGY
C08K5/005
CHEMISTRY; METALLURGY
C08L69/00
CHEMISTRY; METALLURGY
C08L2205/025
CHEMISTRY; METALLURGY
C08K5/005
CHEMISTRY; METALLURGY
C08L69/00
CHEMISTRY; METALLURGY
International classification
Abstract
The present invention relates to glass fibre, carbon fibre and/or carbon nanotube reinforced polycarbonate compositions comprising flame retardant, diglycerol monoester and optionally antidripping agent and having high flowability, excellent stiffness and possibly improved flame retardant properties. The present invention further relates to the use of the compositions according to the invention in particular in the manufacture of housing parts in the EE and IT sector, for example for electrical housings/junction boxes or for frames of LCD/LED screens and also for component parts for the manufacture of Ultrabooks.
Claims
1.-15. (canceled)
16. A composition comprising A) 20 wt % to 99.0 wt % of an aromatic polycarbonate, B) 0.0 to 1.0 wt % of at least one flame retardant, C) 0.5 wt % to 50.0 wt % of at least one glass fibre, one carbon fibre and/or carbon nanotubes, D) 0.01 wt % to 3.0 wt % of at least one flow auxiliary selected from the group of diglycerol esters, E) 0.0 wt % to 5.0 wt % of at least one antidripping agent, F) 0.0 wt % to 1.0 wt % of at least one thermal stabilizer, G) 0.0 wt % to 10.0 wt % of further additives.
17. The composition according to claim 16, wherein the components A) to G) add up to 100 wt %.
18. The composition according to claim 16, wherein the diglycerol ester content is an ester of formula (I) ##STR00003## where R=COC.sub.nH.sub.2n+1 and/or R═COR′, where n is an integer and where R′ is a branched alkyl moiety or a branched or unbranched alkenyl moiety and C.sub.nH.sub.2n+1 is an aliphatic, saturated linear alkyl moiety.
19. The composition according to claim 18, wherein R=COC.sub.nH.sub.2n+1, where n is an integer from 6-24.
20. The composition according to claim 16, wherein the flame retardant present is an alkali and/or alkaline earth metal salt of an aliphatic/aromatic sulphonic acid or of a sulphonamide.
21. The composition according to claim 16, wherein at least 0.05 wt % of an antidripping agent is present.
22. The composition according to claim 16, comprising glass fibres and from 0.001 to 1.0 wt % of a flame retardant.
23. The composition according to claim 16, wherein glass fibres are present and the glass fibres have a precompounding length of 3 mm to 6 mm.
24. The composition according to claim 16, wherein glass fibres are present and the glass fibres are chopped glass fibres.
25. The composition according to claim 16, wherein glass fibres are present and the glass fibres have a mean fibre diameter of 5 to 25 μm.
26. The composition according to claim 16, wherein the composition has a melt volume flow rate MVR of 7-25 cm.sup.3/10 min, determined to ISO 1133 (test temperature 300° C., mass 1.2 kg) and the modulus of elasticity, determined to ISO 527, is at least 2700 kg*m.sup.−1*s.sup.−2.
27. The composition according to claim 16, wherein the composition comprises carbon fibres.
28. A method comprising utilizing the composition according to claim 16 in the manufacture of thin walled shaped articles 0.1-3 mm in thickness for the electrical/electronics sector or the IT sector with a UL94 V-0 flammability rating at 1.5 mm wall thickness.
29. A method comprising utilizing the composition according to claim 16 with a melt volume flow rate MVR of 1-30 cm.sup.3/10 min, determined to ISO 1133 (test temperature 300° C., mass 1.2 kg) and a Charpy impact strength, determined to DIN EN ISO 179/1 eU at room temperature, of above 35 kJ/m.sup.2 in the manufacture of shaped articles.
30. A method comprising utilizing a diglycerol ester to improve the flowability of polycarbonate melts.
1. Composition comprising A) 20 wt % to 99.0 wt % of an aromatic polycarbonate, B) 0.0 to 1.0 wt % of at least one flame retardant, C) 0.5 wt % to 50.0 wt % of at least one glass fibre, one carbon fibre and/or carbon nanotubes, D) 0.01 wt % to 3.0 wt % of at least one flow auxiliary selected from the group of diglycerol esters, E) 0.0 wt % to 5.0 wt % of at least one antidripping agent, F) 0.0 wt % to 1.0 wt % of at least one thermal stabilizer, G) 0.0 wt % to 10.0 wt % of further additives.
2. Composition according to claim 1, characterized in that the components A) to G) add up to 100 wt %.
3. Composition according to claim 1 or 2, characterized in that the diglycerol ester content is an ester of formula (I) ##STR00004## where R=COC.sub.nH.sub.2n+1 and/or R═COR′, where n is an integer and where R′ is a branched alkyl moiety or a branched or unbranched alkenyl moiety and C.sub.nH.sub.2n+1 is an aliphatic, saturated linear alkyl moiety.
4. Composition according to claim 3, characterized in that R=COC.sub.nH.sub.2n+1, where n is an integer from 6-24, preferably from 8 to 18, more preferably from 10 to 16 and yet more preferably 12.
5. Composition according to any preceding claim, characterized in that the flame retardant present is an alkali and/or alkaline earth metal salt of an aliphatic/aromatic sulphonic acid or of a sulphonamide.
6. Composition according to any preceding claim, characterized in that at least 0.05 wt % of an antidripping agent is present.
7. Composition according to any preceding claim, comprising glass fibres and from 0.001 to 1.0 wt % of a flame retardant.
8. Composition according to any preceding claim, characterized in that glass fibres are present and the glass fibres have a precompounding length of 3 mm to 6 mm.
9. Composition according to any preceding claim, characterized in that glass fibres are present and the glass fibres are chopped glass fibres.
10. Composition according to any of claims 1 to 9, characterized in that glass fibres are present and the glass fibres have a mean fibre diameter of 5 to 25 μm, preferably of 8 to 20 μm and more preferably of 11 to 17 μm.
11. Composition according to any preceding claim, characterized in that the composition has a melt volume flow rate MVR of 7-25 cm.sup.3/10 min, determined to ISO 1133 (test temperature 300° C., mass 1.2 kg) and the modulus of elasticity, determined to ISO 527, is at least 2700 kg*m.sup.−1*s.sup.−2.
12. Composition according to any of claims 1 to 7, characterized in that the composition comprises carbon fibres.
13. Use of a composition according to any of claims 1 to 12 in the manufacture of thin walled shaped articles 0.1-3 mm in thickness for the electrical/electronics sector or the IT sector with a UL94 V-0 flammability rating at 1.5 mm wall thickness.
14. Use of the composition according to any of claims 1 to 12 with a melt volume flow rate MVR of 1-30 cm.sup.3/10 min, determined to ISO 1133 (test temperature 300° C., mass 1.2 kg) and a Charpy impact strength, determined to DIN EN ISO 179/1 eU at room temperature, of above 35 kJ/m.sup.2 in the manufacture of shaped articles, specifically for component parts for Ultrabooks.
15. Use of diglycerol esters to improve the flowability of polycarbonate melts.
Description
EXAMPLES
1. Description of Raw Materials and Test Methods
[0124] The polycarbonate compositions of the present invention are produced on customary machines, for example multiscrew extruders, by compounding, with or without admixture of additives and other added substances, at temperatures between 280° C. and 360° C.
[0125] The compounds of the present invention which relate to the examples hereinbelow were produced on a BerstorffZE 25 extruder at a throughput of 10 kg/h. Melt temperature was 275° C.
[0126] A base polycarbonate A utilized mixtures of components A-1, A-2, A-3, A-4, A-6 and/or A-7.
[0127] Component A-1: Linear polycarbonate based on bisphenol A having a melt volume flow rate MVR of 9.5 cm.sup.3/10 min (as per ISO 1133 at a test temperature of 300° C. and 1.2 kg loading).
[0128] Component A-2: Linear polycarbonate powder based on bisphenol A having a melt volume flow rate MVR of 6 cm.sup.3/10 min (as per ISO 1133 at a test temperature of 300° C. and 1.2 kg loading).
[0129] Component A-3: Linear polycarbonate based on bisphenol A having a melt volume flow rate MVR of 12.5 cm.sup.3/10 min (as per ISO 1133 at a test temperature of 300° C. and 1.2 kg loading).
[0130] Component A-4: Linear polycarbonate based on bisphenol A having a melt volume flow rate MVR of 6 cm.sup.3/10 min (as per ISO 1133 at a test temperature of 300° C. and 1.2 kg loading).
[0131] Component A-6: Powder of a linear polycarbonate based on bisphenol A having a melt volume flow rate MVR of 19 cm.sup.3/10 min (as per ISO 1133 at a test temperature of 300° C. and 1.2 kg loading).
[0132] Component A-7: Linear polycarbonate based on bisphenol A having a melt volume flow rate MVR of 19 cm.sup.3/10 min (as per ISO 1133 at a test temperature of 300° C. and 1.2 kg loading).
[0133] Component B: Potassium perfluoro-1-butanesulphonate, commercially available as Bayowet® C4 from Lanxess, Leverkusen, Germany, CAS No. 29420-49-3.
[0134] Component C-1: CS108F-14P chopped short glass fibres (noncoupling) from 3B having an average fibre diameter of 14 m and an average fibre length of 4.0 mm prior to compounding.
[0135] Component C-2: CS 7942 chopped short glass fibres (coupling) from Lanxess AG having an average fibre diameter of 14 μm and an average fibre length of 4.5 mm prior to compounding.
[0136] Component C-3: CF Tenax A HT C493, chopped carbon fibre from Toho Tenax Europe GmbH Germany with thermoplastic sizing and with an average chopped length of 6 mm prior to compounding.
[0137] Component C-4: Baytubes C150 HP, agglomerates of multiwall carbon nanotubes with low outside diameter, narrow diameter distribution and ultrahigh length to diameter ratio. Number of walls: 3-15/outside diameter 13-16 nm/outside diameter distribution: 5-20 nm/length: 1 to >10 μm/inside diameter: 4 nm/inside diameter distribution: 2-6 nm.
[0138] Component C-5: AC 3101 chopped carbon fibre from Dow Aksa (Turkey) with an average length of 6 mm prior to compounding.
[0139] Component C-6: Tairyfil CS2516 chopped carbon fibre from Formosa Plastic Corporation Taiwan with an average length of 6 mm prior to compounding.
[0140] Component C-7: CS Special 7968 chopped glass fibre from Lanxess AG with an average fibre diameter of 11 μm and an average fibre length of 4.5 mm prior to compounding.
[0141] Component C-8: CSG 3PA-830 chopped flat glass fibre from Nittobo with a thickness/length ratio of 1:4.
[0142] Component C-9: MF7980 ground glass fibre from Lanxess. Unsized E-glass having a fibre thickness of 14 μm and an average fibre length of 190 μm.
[0143] Component D: Poem DL-100 (diglycerol monolaurate) from Riken Vitamin as flow auxiliary.
[0144] Component E: Polytetrafluoroethylene (Blendex® B449 (about 50 wt % of PTFE and about 50 wt % of SAN [from 80 wt % of styrene and 20 wt % of acrylonitrile] from Chemtura).
[0145] Component F: triisooctylphosphate (TOF) from Lanxess AG.
[0146] Component G-1: glycerol monostearate (GMS) from Emery Oleochemicals.
[0147] Component G-2: pentaerythritol tetrastearate (PETS) from Emery Oleochemicals.
[0148] Component G-3: Elvaloy 1820 AC; ethylene-methyl acrylate copolymer from Dupont.
[0149] Charpy impact strength was measured to ISO 7391/179 eU at room temperature on single side gate injection moulded test bars measuring 80×10×4 mm.
[0150] The Charpy notched impact strength was measured to ISO 7391/179A at room temperature on single side gate injection moulded test bars measuring 80×10×3 mm.
[0151] As a measure of heat resistance the Vicat softening temperature VST/B50 was determined according to ISO 306 on 80×10×4 mm test specimens with a needle load of 50 N and a heating rate of 50° C./h using a Coesfeld Eco 2920 instrument from Coesfeld Materialtest.
[0152] UL94 V flammability was measured on bars measuring 127×12.7×1.0 mm, 127×12.7×1.5 mm and 127×12.7×3 mm. Fire class was determined by performing five tests in each case, initially after storage for 48 h at 23° C. and then after storage for 7 days at 70° C.
[0153] UL94-5V flammability was measured on bars measuring 127×12.7×1.5 mm, 127×12.7×2.0 mm and 127×12.7×3.0 mm and also on sheets measuring 150×105×1.5 mm, 150×105×2.0 mm, 150×105×3.0 mm.
[0154] The modulus of elasticity was measured to ISO 527 on single side gate injection moulded shoulder bars having a core measuring 80×10×4 mm.
[0155] Melt viscosities were determined to ISO 11443 (cone-plate arrangement).
[0156] The melt volume flow rate (MVR) was determined to ISO 1133 (at a test temperature of 300° C., mass 1.2 kg) using a Zwick 4106 from Zwick Roell.
2. Compositions
[0157]
TABLE-US-00001 TABLE 1a Inventive compositions comprising glass fibres and Comparative Examples 1V and 4V Example 1V 2 3 4V 5 6 A-1 [wt %] 79.35 79.35 79.35 70 70 70 A-2 [wt %] 3.65 3.65 3.65 3 3 3 A-2 powder [wt %] 6.29 6.09 5.89 6.29 6.09 5.89 B [wt %] 0.2 0.2 0.2 0.2 0.2 0.2 C-1 [wt %] 10 10 10 — — — C-2 [wt %] — — — 20 20 20 F [wt %] 0.01 0.01 0.01 0.01 0.01 0.01 D [wt %] — 0.2 0.4 — 0.2 0.4 E [wt %] 0.5 0.5 0.5 0.5 0.5 0.5 MVR [cm.sup.3/10 min] 5.5 10.8 16.1 4.8 10.3 20.8 VST/B50 [° C.] 148 144.9 141.7 149.3 146.2 143.2 Charpy impact [kJ/m.sup.2] 193 149 111 48 59 56 strength at RT Modulus of [N/mm.sup.2] 3933 4080 4147 5869 6062 6194 elasticity UL 94 V V0 V0 V0 V0 V0 V0 1.5 mm Assessment
[0158] Table 1a reports important properties of Inventive Compositions 2, 3, 5 and 6. Comparative Examples 1V and 4V are presented in juxtaposition. The table reveals that the compositions of the comparative examples, which do not contain any diglycerol ester, have distinctly worse melt volume flow rates MVR.
[0159] The inventive compositions surprisingly not only display the appreciable improvement in melt volume flow rate and the improvement in melt viscosity but also an increase in the modulus of elasticity (stiffness).
TABLE-US-00002 TABLE 1b Inventive compositions comprising glass fibres, FR additive and Comparative Examples 7V and 10V The melt viscosity values are each reported in the table hereinbelow together with the shear rates in [1/sec]. Example 7V 8 9 10V 11 12 A-1 [wt %] 70 70 70 70 70 70 A-4 [wt %] 3.00 3.00 3.00 3.00 3.00 3.00 A-2 [wt %] 6.29 6.09 5.89 6.31 6.1 5.9 C-2 [wt %] 20 20 20 20 20 20 B [wt %] 0.2 0.2 0.2 0.2 0.2 0.2 E [wt %] 0.5 05 0.5 0.5 0.5 0.5 D [wt %] — 0.2 0.4 — 0.2 0.4 F [wt %] 0.01 0.01 0.01 — — — Tests: MVR [ml/10 min] 4.8 11.1 17.6 4.7 10.2 19.4 IMVR20′ [ml/10 min] 4.8 11.9 19.7 4.9 12.1 20.8 Melt viscosity at 300° C. eta 50 [Pas] 782 431 294 667 379 286 eta 100 [Pas] 672 375 260 627 346 254 eta 200 [Pas] 583 326 220 542 303 212 eta 500 [Pas] 454 265 175 425 252 168 eta 1000 [Pas] 350 216 147 329 210 143 eta 1500 [Pas] 291 186 129 279 181 128 eta 5000 [Pas] 152 109 79 141 102 77 Melt viscosity at 320° C. eta 50 [Pas] 413 195 141 269 166 124 eta 100 [Pas] 375 177 130 244 153 112 eta 200 [Pas] 336 157 114 214 135 98 eta 500 [Pas] 277 134 92 182 109 80 eta 1000 [Pas] 229 115 79 153 95 67 eta 1500 [Pas] 197 101 73 138 87 62 eta 5000 [Pas] 109 65 52 83 58 44 Melt viscosity at 340° C. eta 50 [Pas] 199 111 — 199 95 — eta 100 [Pas] 185 104 83 184 90 — eta 200 [Pas] 162 92 77 160 86 61 eta 500 [Pas] 137 78 65 131 74 54 eta 1000 [Pas] 120 70 54 112 65 48 eta 1500 [Pas] 109 66 49 102 59 44 eta 5000 [Pas] 70 46 36 67 42 32 Vicat VSTB 120 [° C.] 153.1 148.2 145.9 153.3 148.6 145.8 Impact test ISO7391/ [kJ/m.sup.2] 59 66 65 61 66 64 179eU 4 mm RT Tensile test Yield stress [N/mm.sup.2] 102 106 112 101 108 — Elongation [%] 3.3 3.2 3.2 3.3 3.3 — Ultimate tensile strength [N/mm.sup.2] 101 106 111 100 108 11 Elongation at break [%] 3.3 3.2 3.1 3.5 3.3 3.1 Modulus of elasticity [N/mm.sup.2] 5972 6050 6295 5834 6118 6246 UL94V on 1.5 mm (48 h 23° C.) V1 V1 V1 V0 V1 V1 Individual assessment 3/2/—/— 3/2/—/— —/5/—/— 5/—/—/— 3/2/—/— 3/2/—/— V0/V1/V2/Vn.b. Afterflame time [s] 60 88 80 49 65 77 Afterflame time [s] — — — — — — (1st application of flame) 7 d 70° C. V1 V1 V1 V1 V1 V1 Individual assessment, 4/1/—/— 3/2/—/— 3/2/—/—- 1/4/—/— 4/1/—/— 3/2/—/— V0/V1/V2/Vn.b Afterflame time [s] 48 69 72 102 62 79 Afterflame time [s] 75 — — — — — (1st application of flame) Overall assessment V1 V1 V1 V1 V1 V1 Vn.b: fail
[0160] Table 1b reports important properties regarding Inventive Compositions 8, 9, 11 and 12. Comparative Examples 7V and 10V are presented in juxtaposition. The table reveals that the compositions according to the comparative examples, which do not contain any diglycerol ester, have distinctly worse melt volume flow rates MVR. The flow curves of the inventive compositions exhibit distinctly reduced melt viscosities at each of the various measurement temperatures across the full shear range, indicating an improved flowability.
[0161] The inventive compositions surprisingly not only show the appreciable improvement in the rheological properties but also an increase in the modulus of elasticity (stiffness) while retaining the good flammability properties.
TABLE-US-00003 TABLE 1c Inventive compositions comprising glass fibres and FR additive and Comparative Examples 13V and16V The melt viscosity values are each reported in the table hereinbelow together with the shear rates in [1/sec]. Examples 13V 14 15 16V 17 18 A-7 [wt %] 30.00 30.00 30.00 30.00 30.00 30.00 A-2 [wt %] 50.42 50.42 50.42 50.42 50.42 50.42 A-6 [wt %] 5.55 5.35 5.15 5.54 5.34 5.14 C-1 [wt %] 14.00 14.00 14.00 14.00 14.00 14.00 D [wt %] — 0.20 0.40 — 0.20 0.40 B [wt %] 0.03 0.03 0.03 0.03 0.03 0.03 F [wt %] — — — 0.01 0.01 0.01 Tests: MVR [ml/10 min] 7.2 13.4 16.5 7.4 13.5 22.6 IMVR20′ [ml/10 min] 7.2 13.6 16.8 7.6 14.2 24.2 Melt viscosity at 300° C. eta 50 [Pas] 623 492 371 666 493 370 eta 100 [Pas] 577 438 313 568 416 302 eta 200 [Pas] 502 378 268 504 354 247 eta 500 [Pas] 400 313 231 408 299 207 eta 1000 [Pas] 316 258 197 328 247 176 eta 1500 [Pas] 268 222 173 274 213 157 eta 5000 [Pas] 139 119 102 142 119 94 Melt viscosity at 320° C. eta 50 [Pas] 349 286 270 391 355 243 eta 100 [Pas] 337 248 222 327 286 197 eta 200 [Pas] 297 235 183 293 233 165 eta 500 [Pas] 252 198 149 250 194 133 eta 1000 [Pas] 214 165 130 211 166 116 eta 1500 [Pas] 186 146 119 185 148 105 eta 5000 [Pas] 108 88 78 103 95 72 Melt viscosity at 340° C. eta 50 [Pas] 169 232 164 278 255 115 eta 100 [Pas] 168 186 137 204 207 109 eta 200 [Pas] 167 148 114 192 171 99 eta 500 [Pas] 147 127 99 162 142 83 eta 1000 [Pas] 125 110 86 140 124 73 eta 1500 [Pas] 112 101 79 127 113 69 eta 5000 [Pas] 78 70 54 83 71 52 Vicat VSTB 50 [Pas] 150.2 146.9 145.0 150.5 146.3 143.8 UL94V in 3.0 mm ( 48 h 23° C.) V0 V0 V0 V0 V0 V0 Individual assessment 5/—/—/— 5/—/—/— 5/—/—/— 5/—/—/— 5/—/—/— 5/—/—/— V0/V1/V2/Vn.b. Afterflame time [s] 24 28 29 32 21 41 Afterflame time [s] — — — — — — (1st application of flame) ( 7 d 70° C.) V0 V0 V0 V0 V0 V0 Individual assessment, 5/—/—/— 5/—/—/— 5/—/—/— 5/—/—/— 5/—/—/— 5/—/—/— V0/V1/V2/Vn.b. Afterflame time [s] 23 22 33 26 24 22 Afterflame time [s] — — — — — — (1st application of flame) Overall evaluation [s] V0 V0 V0 V0 V0 V0 Vn.b: fail
[0162] Table 1c reports important properties regarding Inventive Compositions 14, 15, 17 and 18. Comparative Examples 13V and 16V are presented in juxtaposition. The table reveals that the compositions according to the comparative examples, which do not contain any diglycerol ester, have distinctly worse melt volume flow rates MVR. The flow curves of the inventive compositions exhibit distinctly reduced melt viscosities at each of the various measurement temperatures across the full shear range, indicating an improved flowability.
[0163] The inventive compositions surprisingly not only show the appreciable improvement in the rheological properties but also good flammability properties.
TABLE-US-00004 TABLE 1d Inventive compositions comprising glass fibres and FR additive and Comparative Examples 19V and 22V The melt viscosity values are each reported in the table hereinbelow together with the shear rates in [1/sec]. Examples 19V 20 21 22V 23 24 A-7 [wt %] 73.00 73.00 73.00 73.00 73.00 73.00 A-6 [wt %] 4.94 4.74 4.54 4.93 4.73 4.53 C-7 [wt %] 20.00 20.00 20.00 20.00 20.00 20.00 B [wt %] 0.06 0.06 0.06 0.06 0.06 0.06 G-3 [wt %] 2.00 2.00 2.00 2.00 2.00 2.00 D [wt %] — 0.20 0.40 — 0.20 0.40 F [wt %] — — — 0.01 0.01 0.01 Tests: MVR [ml/10 min] 8.5 15.7 33.4 8.2 18.2 28.9 IMVR20′ [ml/10 min] 8.7 16.1 32.3 8.7 18.9 28.3 Vicat VSTB50 [° C.] 151.8 147.6 143.7 151.4 147.9 144 Melt viscosity at 300° C. eta 50 [Pas] 462 308 148 508 291 193 eta 100 [Pas] 415 255 135 449 260 176 eta 200 [Pas] 369 242 124 399 235 157 eta 500 [Pas] 302 203 107 320 200 133 eta 1000 [Pas] 236 167 94 250 167 117 eta 1500 [Pas] 201 143 87 213 144 104 eta 5000 [Pas] 108 83 57 117 86 65 Melt viscosity at 320° C. eta 50 [Pas] 261 182 97 287 183 130 eta 100 [Pas] 247 164 85 266 159 111 eta 200 [Pas] 238 149 77 239 39 101 eta 500 [Pas] 203 128 67 204 124 88 eta 1000 [Pas] 169 111 60 169 108 77 eta 1500 [Pas] 145 94 56 144 97 71 eta 5000 [Pas] 89 61 40 85 61 47 Melt viscosity at 340° C. eta 50 [Pas] 159 99 60 183 120 76 eta 100 [Pas] 151 97 56 168 105 71 eta 200 [Pas] 138 88 49 156 94 63 eta 500 [Pas] 122 80 42 137 83 58 eta 1000 [Pas] 108 72 39 119 74 51 eta 1500 [Pas] 98 66 35 105 68 47 eta 5000 [Pas] 65 45 28 68 46 35 UL94V in 1.0 mm (48 h 23° C.) V1 V2 V2 V2 V1 V2 Individual assessment 4/1/—/— 3/—/2/— 2/1/2/— 3/1/1/— 3/2/—/— —/—/5/— V0/V1/V2/Vn.b. Afterflame time [s] 73 61 55 81 97 72 Afterflame time [s] 118 — — <115 — — (1st application of flame) (7 d 70° C.) V2 V2 V2 V2 V2 V2 Individual assessment, 3/—/2/— 1/2/2/— 1/—/4/— —/3/2/— 1/—/4/— —/—/5/— V0/V1/V2/Vn.b Afterflame time [s] 67 92 63 118 54 75 Afterflame time [s] — — — — — — (1st application of flame) Overall evaluation evaluation V2 V2 V2 V2 V2 V2 Vn.b: fail
[0164] Table 1d reports important properties regarding Inventive Compositions 20, 21, 23 and 24. Comparative Examples 19V and 22V are presented in juxtaposition. The table reveals that the compositions according to the comparative examples, which do not contain any diglycerol ester, have distinctly worse melt volume flow rates MVR. The flow curves of the inventive compositions exhibit distinctly reduced melt viscosities at each of the various measurement temperatures across the full shear range, indicating an improved flowability.
TABLE-US-00005 TABLE 1e Inventive compositions comprising glass fibres and Comparative Examples 25V and 28V The melt viscosity values are each reported in the table hereinbelow together with the shear rates in [1/sec]. Example 25V 26 27 28V 29 30 A-3 [wt %] 63.00 63.00 63.00 63.00 63.00 63.00 A-2 [wt %] 7.00 6.80 6.60 6.99 6.79 6.59 C-8 [wt %] 30.00 30.00 30.00 30.00 30.00 30.00 D [wt %] — 0.20 0.40 — 0.20 0.40 F [wt %] — — — 0.01 0.01 0.01 Tests MVR 300° C./1.2 kg [cm.sup.3/10 min] 4.5 9.1 15.3 4.5 8.8 15.3 IMVR20′ 300° C./1.2 kg [cm.sup.3/10 min] 5.1 104 19.9 5.6 10.9 19.0 Melt viscosity at 300° C. eta 50 [Pas] 763 532 376 721 540 420 eta 100 [Pas] 669 483 340 677 455 367 eta 200 [Pas] 581 430 301 591 377 324 eta 500 [Pas] 452 346 249 460 302 266 eta 1000 [Pas] 346 274 205 348 258 218 eta 1500 [Pas] 294 235 174 303 222 189 eta 5000 [Pas] 154 129 104 158 132 113 Melt viscosity at 320° C. eta 50 [Pas] 397 278 133 372 299 220 eta 100 [Pas] 60 237 128 365 255 180 eta 200 [Pas] 321 209 114 325 228 165 eta 500 [Pas] 265 176 95 250 199 132 eta 1000 [Pas] 221 154 83 206 167 110 eta 1500 [Pas] 190 139 75 170 149 95 eta 5000 [Pas] 110 88 55 100 93 68 Melt viscosity at 340° C. eta 50 [Pas] 178 114 84 215 120 104 eta 100 [Pas] 168 106 72 187 115 92 eta 200 [Pas] 153 95 65 159 105 82 eta 500 [Pas] 131 84 57 141 92 66 eta 1000 [Pas] 118 76 51 117 89 57 eta 1500 [Pas] 112 71 48 113 83 52 eta 5000 [Pas] 75 55 35 73 65 42
[0165] Table 1e reports important properties regarding Inventive Compositions 26, 27, 29 and 30. Comparative Examples 25V and 28V are presented in juxtaposition. The table reveals that the compositions according to the comparative examples, which do not contain any diglycerol ester, have distinctly worse melt volume flow rates MVR. The flow curves of the inventive compositions exhibit distinctly reduced melt viscosities at each of the various measurement temperatures across the full shear range, indicating an improved flowability.
TABLE-US-00006 TABLE 1f Inventive compositions comprising glass fibres and Comparative Examples 31V and 34V The melt viscosity values are each reported in the table hereinbelow together with the shear rates in [1/sec]. Examples 31V 32 33 34V 35 36 A-3 [wt %] 63.00 63.00 63.00 63.00 63.00 63.00 A-2 [wt %] 7.00 6.80 6.60 6.99 6.79 6.59 C-9 [wt %] 30.00 30.00 30.00 30.00 30.00 30.00 D [wt %] — 0.20 0.40 — 0.20 0.40 F [wt %] — — — 0.01 0.01 0.01 Tests MVR 300° C./1.2 kg [cm.sup.3/10 min] 5.3 10.0 19.4 5.5 9.9 19.8 IMVR20′ 300° C./1.2 kg [cm.sup.3/10 min] 5.9 13.4 24.3 5.8 12.6 24.8 Melt viscosity at 300° C. eta 5 [Pas] 699 586 436 630 534 397 eta 100 [Pas] 633 531 390 628 523 390 eta 200 [Pas] 580 483 361 579 486 369 eta 500 [Pas] 480 408 313 479 411 307 eta 1000 [Pas] 384 334 263 381 336 264 eta 1500 [Pas] 317 282 230 318 284 227 ets 5000 [Pas] 157 145 125 15 147 122 Melt viscosity at 320° C. eta 50 [Pas] 328 250 175 260 281 200 ets 100 [Pas] 305 237 172 255 267 191 eta 200 [Pas] 282 233 161 250 254 182 eta 500 [Pas] 250 212 152 237 230 169 eta 1000 [Pas] 217 186 138 211 201 153 eta 1500 [Pas] 193 167 124 192 180 142 eta 5000 [Pas] 111 104 81 116 116 91 Melt viscosity at 340° C. eta 50 [Pas] 142 105 69 174 147 90 eta 100 [Pas] 137 102 66 173 140 87 esa 200 [Pas] 133 99 62 166 137 84 eta 500 [Pas] 128 96 60 156 120 82 eta 1000 [Pas] 119 93 56 142 105 79 eta 1500 [Pas] 112 88 56 132 95 77 eta 5000 [Pas] 77 65 46 85 69 58
[0166] Table 1f reports important properties regarding Inventive Compositions 32, 33, 35 and 36. Comparative Examples 31V and 34V are presented in juxtaposition. The table reveals that the compositions according to the comparative examples, which do not contain any diglycerol ester, have distinctly worse melt volume flow rates MVR. The flow curves of the inventive compositions exhibit distinctly reduced melt viscosities at each of the various measurement temperatures across the full shear range, indicating an improved flowability.
TABLE-US-00007 TABLE 1g Inventive compositions comprising glass fibres and Comparative Example 37V Composition 37V 38 39 40 41 42 43 A-1 [wt %] 79.35 79.35 79.35 74.35 74.35 69.35 69.35 A-4 [wt %] 3.65 3.65 3.65 3.65 3.65 3.65 3.65 A-2 [wt %] 5.85 6.1 5.9 6.1 5.9 6.1 5.9 G-2 [wt %] 0.45 — — — — — — D [wt %] — 0.2 0.4 0.2 0.4 0.2 0.4 Blendex 449 [wt %] 0.2 0.2 0.2 0.2 0.2 0.2 0.2 E [wt %] 0.5 0.5 0.5 0.5 0.5 0.5 0.5 C-1 [wt %] 10 10 10 15 15 20 20 Tests: MVR [cm.sup.3/10 min] 5.7 10.4 16.6 8.1 11.9 6.6 11.9 IMVR20′ [cm.sup.3/10 min] 5.8 1.1 17.3 8.4 12.3 7.2 11.0 Delta MVR/IMVR20′ 0.1 0.7 0.7 0.3 0.4 0.6 −0.9 KET [° C.] 137 137 133 137 132 136 133 UL 94-5V in 3.0 mm Bar testing yes yes yes yes yes yes yes Sheet testing passed passed passed passed passed passed passed Classification 94-5VA 94-5VA 94-5VA 94-5VA 94-5VA 94-5VA 945VA UL94-5V in 2.0 mm Bar testing yes yes yes yes yes yes yes Sheet testing no no no passed passed passed passed Classification 94-5VB 94-5VB 94-5VB 94-5VA 94-5VA 94-5VA 94-5VA UL94-5V in 1.5 mm Bar testing yes no no no yes yes no Sheet testing no — — — no passed — Classification 94-5VB — — — 94-5VB 94-5VA —
[0167] Table 1g reports important properties regarding Inventive Compositions 38 to 43. Comparative Example 37V is presented in juxtaposition. The table reveals that the composition according to the comparative example, which does not contain any diglycerol ester, has a distinctly worse melt volume flow rate MVR.
[0168] Example 41 shows that the UL 94-5V classification in the fire test is retained despite the improved flow rate. Example 42 shows that for an approximately unchanged MVR an even higher rating is achievable in the 94-5V test (from 5VB to 5VA at 1.5 mm)
TABLE-US-00008 TABLE 2a Inventive compositions comprising carbon fibres and Comparative Example 44 V The melt viscosity values are each reported in the table hereinbelow together with the shear rates in [1/sec]. Example 44 V 45 46 47 A-3 [wt %] 81 .00 81.00 81.00 81.00 A-2 [wt %] 7.00 6.79 6.69 6.59 C-3 [wt %] 12.00 12.00 12.00 12.00 D [wt %] — 0.20 0.30 0.40 F [wt %] — 0.01 0.01 0.01 Results MVR [cm.sup.3/10 min] 7.0 8.6 11.7 20.5 IMVR20′ [cm.sup.3/10 min] 7.6 9.9 16.9 24.1 Melt viscosity at 300° C. eta 50 [Pas] 535 492 468 401 eta 100 [Pas] 497 466 441 379 eta 200 [Pas] 452 423 401 343 eta 500 [Pas] 365 346 327 287 eta 1000 [Pas] 292 278 264 233 eta 1500 [Pas] 253 241 226 203 eta 5000 [Pas] 138 130 124 116 Melt viscosity at 320° C. eta 50 [Pas] 254 236 240 216 eta 100 [Pas] 250 227 235 200 eta 200 [Pas] 249 225 221 199 eta 500 [Pas] 217 198 192 176 eta 1000 [Pas] 184 167 163 154 eta 1500 [Pas] 162 147 143 134 eta 5000 [Pas] 100 93 91 87 Melt viscosity at 340° C. eta 50 [Pas] 149 118 109 101 eta 100 [Pas] 146 115 107 99 eta 200 [Pas] 139 114 105 96 eta 500 [Pas] 126 113 103 88 eta 1000 [Pas] 107 102 99 77 eta 1500 [Pas] 102 93 90 72 eta 5000 [Pas] 70 64 64 50
[0169] Table 2a reports important properties regarding Inventive Compositions 45 to 47. Comparative Example 44V is presented in juxtaposition. The table reveals that the compositions according to the comparative example, which does not contain any diglycerol ester, has distinctly worse melt volume flow rates MVR. The flow curves of the inventive compositions exhibit distinctly reduced melt viscosities at each of the various measurement temperatures across the full shear range, indicating an improved flowability.
TABLE-US-00009 TABLE 2b Inventive compositions comprising carbon fibres and Comparative Examples 48V and 52V The melt viscosity values are each reported in the table hereinbelow together with the shear rates in [1/sec]. Recipe 48V 49 50 51 52V 53 54 55 A-3 [wt %] 81.00 81.00 81.00 81.00 81.00 81.00 81.00 81.00 A-2 [wt %] 7.00 6.79 6.69 6.59 7.00 6.79 6.69 6.59 C-5 [wt %] 12.00 12.00 12.00 12.00 — — — — C-6 [wt %] — — — — 12.00 12.00 12.00 12.00 D [wt %] — 0.20 0.30 0.40 — 0.20 0.30 0.40 F [wt %] — 0.01 0.01 0.01 — 0.01 0.01 0.01 Tests: MVR [cm.sup.3/10 min] 6.8 10.6 12.6 18.3 6.3 7.9 9.1 10.4 IMVR20′ [cm.sup.3/10 min] 7.5 13.2 17.4 25.8 7.0 10.4 11.1 13.6 Melt viscosity at 300° C. eta 50 [Pas] 456 366 349 302 513 456 453 452 eta 100 [Pas] 424 350 329 284 512 446 427 423 eta 200 [Pas] 388 322 303 270 458 411 391 386 eta 500 [Pas] 330 275 263 236 376 339 324 320 eta 1000 [Pas] 269 226 222 197 299 275 263 257 eta 1500 [Pas] 233 197 196 173 257 239 228 223 eta 5000 [Pas] 126 111 111 103 135 126 123 121 Melt viscosity at 320° C. eta 50 [Pas] 236 164 146 90 350 252 243 225 eta 100 [Pas] 217 158 150 88 326 240 229 218 eta 200 [Pas] 193 151 141 86 322 241 225 198 eta 500 [Pas] 165 135 134 85 270 211 198 175 eta 1000 [Pas] 145 122 121 78 224 180 171 157 eta 1500 [Pas] 126 110 109 76 192 161 154 135 eta 5000 [Pas] 85 74 74 54 110 97 93 85 Melt viscosity at 340° C. eta 50 [Pas] 102 56 67 38 163 145 122 134 eta 100 [Pas] 101 55 66 37 162 143 117 126 eta 200 [Pas] 99 53 61 35 161 138 113 121 eta 500 [Pas] 92 52 55 34 136 127 112 110 eta 1000 [Pas] 85 49 50 33 124 115 104 97 eta 1500 [Pas] 81 48 48 32 111 106 95 85 eta 5000 [Pas] 58 38 37 25 75 70 63 62
[0170] Table 2b reports important properties regarding Inventive Compositions 49 to 51 and 53 to 55. Comparative Examples 48V and 52V are presented in juxtaposition. The table reveals that the compositions according to the comparative examples, which do not contain any diglycerol ester, have distinctly worse melt volume flow rates MVR. The flow curves of the inventive compositions exhibit distinctly reduced melt viscosities at each of the various measurement temperatures across the full shear range, indicating an improved flowability.
TABLE-US-00010 TABLE 3a Inventive compositions comprising carbon nanotubes and Comparative Examples 56V to 63V Example 56V 57V 58V 59V 60V 61V 62V 63V 64 65 66 A-3 [wt %] 90.00 90.00 90.00 90.00 90.00 90.00 90.00 90.00 90.00 90.00 90.00 A-2 [wt %] 10.00 8.00 7.80 7.60 7.40 7.80 7.60 7.40 7.80 7.60 7.40 G-1 [wt %] — — 0.20 0.40 0.60 — — — — — — G-2 [wt %] — — — — — 0.20 0.40 0.60 — — — D [wt %] — — — — — — — — 0.20 0.40 0.60 C-4 [wt %] — 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Tests: MVR [cm.sup.3/10 min] 10.6 4.2 6.1 8.6 11.6 4.3 4.7 5.3 9.6 11.8 26.1 IMVR20′ [cm.sup.3/10 min] 10 4.1 6.4 10.1 14.3 4.3 5 5.4 10.2 13.5 27.2 Vicat VSTB50 [° C.] 147.2 148.2 145 142.9 140.6 146.5 145.2 143.6 145.2 142.9 139.4
[0171] Table 3a reports important properties regarding Inventive Compositions 64 to 66. Comparative Examples 56V to 63V are presented in juxtaposition. The table reveals that the compositions according to the comparative examples, which do not contain any diglycerol ester, have distinctly worse melt volume flow rates MVR.
TABLE-US-00011 TABLE 3b Inventive compositions comprising carbon nanotubes and Comparative Examples 67V to 74V Example 67V 68V 69V 70V 71V 72V 73V 74V 75 76 77 A-3 [wt %] 90.00 90.00 90.00 90.00 90.00 90.00 90.00 90.00 90.00 90.00 90.00 A-2 [wt %] 10.00 7.00 6.80 6.60 6.40 6.80 6.60 6.40 6.80 6.60 6.40 G-1 [wt %] — — 0.20 0.40 0.60 — — — — — — G-2 [wt %] — — — — — 0.20 0.40 0.60 — — — D [wt %] — — — — — — — — 0.20 0.40 0.60 C-4 [wt %] 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Tests: MVR [cm.sup.3/10 min] 10.2 2.2 3.7 5.7 8.2 2.5 2.8 3.2 4.9 15.7 17.7 IMVR20′ [cm.sup.3/10 min] 10.2 2.3 4.0 6.9 10.1 2.7 2.9 3.1 5.4 14.2 19.3 Delta MVR/ 0.0 0.1 0.3 1.2 1.9 0.2 0.1 −0.1 0.5 −1.5 1.6 IMVR20′ Vicat VSTB50 [° C.] 147.5 148.8 145.9 143.3 140.5 146.9 145.6 143.5 145.2 142.7 139.6
[0172] Table 3b reports important properties regarding Inventive Compositions 75 to 77. Comparative Examples 67V to 74V are presented in juxtaposition. The table reveals that the compositions according to the comparative examples, which do not contain any diglycerol ester, have distinctly worse melt volume flow rates MVR.
TABLE-US-00012 TABLE 3c Inventive compositions comprising carbon nanotubes and Comparative Examples 78V to 83V Example 78V 79V 80V 81V 82V 83V 84 A-3 [wt %] 90.00 90.00 90.00 90.00 90.00 90.00 90.00 A-2 [wt %] 10.00 6.00 5.40 5.80 5.60 5.40 5.40 G-1 [wt %] — — 0.60 — — — — G-2 [wt %] — — — 0.20 0.40 0.60 — D [wt %] — — — — — — 0.60 C-4 [wt %] — 4.00 4.00 4.00 4.00 4.00 4.00 Tests: MVR [cm.sup.3/10 min] 10.1 0.9 4.5 0.7 1.6 1.7 11.7 IMVR20′ [cm.sup.3/10 min] 10.0 0.9 5.3 0.8 1.7 1.7 11.6 Vicat VSTB50 [° C.] 146.8 148.3 140.3 147.1 145.3 144 140.5
[0173] Table 3c reports important properties regarding Inventive Composition 84. Comparative Examples 78V to 83V, in particular 80V and 83V, are presented in juxtaposition. The table reveals that the compositions according to the comparative examples, which do not contain any diglycerol ester, have distinctly worse melt volume flow rates MVR.