Multilayer composite material containing special polycarbonate compositions as a matrix material

Abstract

The present invention relates to a composite material comprising one or more fibre layers composed of a fibre material and an aromatic polycarbonate-based matrix material. The fibre layer(s) is/are embedded in the matrix material. The present invention further relates to a process for producing these fibre composite materials, to multilayer composite materials comprising several layers of fibre composite material, and to the use of the composite materials for production of components or housing components or housings, and to the components, housing components or housings themselves.

Claims

1. A fibre composite material comprising at least one layer of fibre material embedded into a composition wherein the composition comprises A) at least 65% by weight of at least one aromatic polycarbonate, B) 7% by weight to 15% by weight of at least one cyclic phosphazene of formula (1) ##STR00022## where R is the same or different and is an amine radical, and in each case optionally halogenated C.sub.1- to C.sub.8-alkyl radical, C.sub.1- to C.sub.8-alkoxy radical, in each case optionally alkyl- and/or halogen-substituted C.sub.5- to C.sub.6-cycloalkyl radical, in each case optionally alkyl- and/or halogen- and/or hydroxyl-substituted C.sub.6- to C.sub.20- aryloxy radical, in each case optionally alkyl- and/or halogen-substituted C.sub.7- to C.sub.12-aralkyl radical or a halogen radical or an OH radical, k is an integer from 1 to 10, C) 0% to 11% by weight of at least one phosphorus compound of the general formula (2) ##STR00023## where R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are each independently a C.sub.1- to C.sub.8-alkyl radical, in each case optionally halogenated and in each case branched or unbranched, and/or C.sub.5- to C.sub.6-cycloalkyl radical, C.sub.6- to C.sub.20-aryl radical or C.sub.7- to C.sub.12-aralkyl radical, in each case optionally substituted by branched or unbranched alkyl and/or halogen, n is independently 0 or 1, q is an integer from 0 to 30, X is a mono- or polycyclic aromatic radical having 6 to 30 carbon atoms or a linear or branched aliphatic radical having 2 to 30 carbon atoms, each of which may be substituted or unsubstituted, and bridged or unbridged, and wherein the composition is free of anti-dripping agents and free of talc, and wherein a total of at least 14% by weight of component B+component C is present, based on the overall composition.

2. The fibre composite material according to claim 1, wherein the fibre material is selected from the group consisting of carbon fibres, glass fibres, basalt fibres and mixtures thereof.

3. The fibre composite material according to claim 1, wherein the fibre material is an endless fibre material, a woven fibre material or a knitted fibre material.

4. The fibre composite material according to claim 1, wherein the fibre material are endless fibres and the endless fibres are aligned unidirectionally.

5. The fibre composite material according to claim 1, wherein the composition comprises A) at least 75% by weight of at least one aromatic polycarbonate, B) 7% by weight to 12% by weight of at least one cyclic phosphazene of formula (1), C) 4% by weight to 10% by weight of at least one phosphorus compound of the general formula (2).

6. The fibre composite material according to claim 1, wherein the composition does not contain any inorganic fillers.

7. The fibre composite material according to claim 1, wherein the composition consists of A) 75% by weight to 87% by weight of at least one aromatic polycarbonate, B) 8% by weight to 10% by weight of at least one cyclic phosphazene of formula (1), wherein the cyclic phosphazene of component B present is at least phenoxyphosphazene, C) 5% to 7% by weight of at least one phosphorus compound of the general formula (2) wherein the only phosphorus compound of the formula (2) present is the phosphorus compound of the formula (2b) ##STR00024## with an average q value q=1.0 to 1.2, D) 0% to 10% by weight of one or more further additives other than components B and C, selected from the group consisting of UV stabilizers, IR absorbers, antioxidants, demoulding agents, flow auxiliaries, antistats, impact modifiers, colourants, thermal stabilizers, further flame retardants, and the fibre material comprises unidirectionally oriented endless carbon fibres.

8. The fibre composite material according to claim 7, wherein the sole cyclic phosphazene of the formula (1) present is phenoxyphosphazene and the proportion of cyclic phosphazene with k=1 is 50 to 98 mol %, based on the total amount of cyclic phosphazene of the formula (1).

9. A multilayer composite material comprising at least two mutually superposed layers of the fibre composite material according to claim 1.

10. The multilayer composite material according to claim 9, comprising at least three mutually superposed layers the fibre composite material which are defined relative to one another as two outer layers of fibre composite material and at least one inner layer of fibre composite material, wherein the inner layers of fibre composite material have essentially the same orientation and the orientation thereof relative to the outer layers of fibre composite material is rotated by 30° to 90° , wherein the orientation of one layer of fibre composite material is determined by the orientation of the unidirectionally aligned fibres present therein.

11. The process for producing a multilayer composite material according to claim 9, comprising the following steps: providing at least one inner layer of fibre composite material and two outer layers of fibre composite material, wherein the individual layers of fibre composite material are produced by applying a molten composition comprising A) at least 65% by weight of at least one aromatic polycarbonate, B) 7% by weight to 15% by weight of at least one cyclic phosphazene of formula (1) ##STR00025## where R is the same or different and is an amine radical, an in each case optionally halogenated C.sub.1- to C.sub.8-alkyl radical, C.sub.1- to C.sub.8-alkoxy radical, in each case optionally alkyl- and/or halogen-substituted C.sub.5- to C.sub.6-cycloalkyl radical, in each case optionally alkyl- and/or halogen- and/or hydroxyl-substituted C.sub.6- to C.sub.20-aryloxy radical, in each case optionally alkyl- and/or halogen-substituted C.sub.7- to C.sub.12-aralkyl radical or a halogen radical or an OH radical, k is an integer from 1 to 10, C) 0% to 11% by weight of at least one phosphorus compound of the general formula (2) ##STR00026## where R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are each independently a C.sub.1- to C.sub.8-alkyl radical, in each case optionally halogenated and in each case branched or unbranched, and/or C.sub.5- to C.sub.6-cycloalkyl radical, C.sub.6- to C.sub.20-aryl radical or C.sub.7- to C.sub.12-aralkyl radical, in each case optionally substituted by branched or unbranched alkyl and/or halogen, n is independently 0 or 1, q is an integer from 0 to 30, X is a mono- or polycyclic aromatic radical having 6 to 30 carbon atoms or a linear or branched aliphatic radical having 2 to 30 carbon atoms, each of which may be substituted or unsubstituted, and bridged or unbridged, to a raw fibre tape composed of fibre material that has been preheated to above the glass transition temperature of the polycarbonate, wherein the composition is applied to the raw fibre tape under pressure-shear vibration, layering the layers of fibre composite material in the desired orientation relative to one another, based on the orientation of the fibre material, bonding the layered layers of fibre composite material to form the multilayer composite material.

12. A process for producing a layer of fibre composite material according to claim 1, wherein a molten composition comprising A) at least 65% by weight of at least one aromatic polycarbonate, B) 7% by weight to 15% by weight of at least one cyclic phosphazene of formula (1) ##STR00027## where R is the same or different and is an amine radical, an in each case optionally halogenated C.sub.1- to C.sub.8-alkyl radical, C.sub.1- to C.sub.8-alkoxy radical, in each case optionally alkyl- and/or halogen-substituted C.sub.5- to C.sub.6-cycloalkyl radical, in each case optionally alkyl- and/or halogen- and/or hydroxyl-substituted C.sub.6- to C.sub.20- aryloxy radical, in each case optionally alkyl- and/or halogen-substituted C.sub.7- to C.sub.12-aralkyl radical or a halogen radical or an OH radical, k is an integer from 1 to 10, C) 0% to 11% by weight of at least one phosphorus compound of the general formula (2) ##STR00028## where R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are each independently a C.sub.1- to C.sub.8-alkyl radical, in each case optionally halogenated and in each case branched or unbranched, and/or C.sub.5- to C.sub.6-cycloalkyl radical, C.sub.6- to C.sub.20-aryl radical or C.sub.7- to C.sub.12-aralkyl radical, in each case optionally substituted by branched or unbranched alkyl and/or halogen, n is independently 0 or 1, q is an integer from 0 to 30, X is a mono- or polycyclic aromatic radical having 6 to 30 carbon atoms or a linear or branched aliphatic radical having 2 to 30 carbon atoms, each of which may be substituted or unsubstituted, and bridged or unbridged, is applied under pressure-shear vibration to a raw fibre tape composed of fibre material that has been preheated to above the glass transition temperature of the polycarbonate.

13. A housing component comprising the fibre composite material according to claim 1.

Description

(1) Further details and advantages of the invention will be apparent from the description which follows of the accompanying illustration showing preferred embodiments. The drawings show:

(2) FIG. 1 a schematic and perspective diagram of a multilayer composite material composed of three superposed layers of fibre composite material with enlarged detail, wherein the inner layer is rotated by 90° relative to the outer layers of fibre composite material,

(3) FIG. 2 a schematic and perspective diagram of a multilayer composite material composed of five superposed layers of fibre composite material, wherein the inner layers have the same orientation and their orientations are rotated by 90° relative to the outer layers of fibre composite material,

(4) FIG. 3 a schematic and perspective diagram of a multilayer composite material composed of six superposed layers of fibre composite material, wherein the inner layers have the same orientation and their orientations are rotated by 90° relative to the outer layers of fibre composite material.

(5) FIG. 1 shows a detail of a multilayer composite material 1 composed of three superposed layers of fibre composite material 2, 3, wherein the inner layer of fibre composite material 2 is rotated by 90° relative to the outer layers 3 of fibre composite material. The enlarged detail in FIG. 1 shows that each of the layers 2, 3 of the multilayer composite material comprises endless fibres 4 which are unidirectionally aligned within the respective layer and are embedded in polycarbonate-based plastic 5. The orientation of the respective layer of fibre composite material 2, 3 is determined by the orientation of the unidirectionally aligned endless fibres 4 present therein. The endless fibres 4 extend over the entire length/width of the multilayer composite material. The layers 2, 3 are uniformly bonded to one another.

(6) The multilayer composite material 1 as per FIG. 2 is composed of five superposed layers of fibre composite material 2, 3, wherein the inner layers of fibre composite material 2 have the same orientation and their orientation relative to the outer layers of fibre composite material 3 is rotated by 90°.

(7) The multilayer composite material 1 as per FIG. 3 is composed of six superposed layers of fibre composite material 2, 3, wherein the inner layers of fibre composite material 2 have the same orientation and their orientation relative to the outer layers of fibre composite material 3 is rotated by 90°.

WORKING EXAMPLES

(8) There follows a detailed description of the invention with reference to working examples, and the methods of determination described here are employed for all corresponding parameters in the present invention, in the absence of any statement to the contrary.

(9) Starting Materials: A-1: Polycarbonate from Covestro Deutschland AG. Linear polycarbonate based on bisphenol A having a melt volume flow rate MVR of 6 cm.sup.3/(10 min) (as per ISO 1133:2012-03, at a test temperature of 300° C. and 1.2 kg load). A-2: Makrolon® 3108 powder from Covestro Deutschland AG. Linear polycarbonate based on bisphenol A having a melt volume flow rate MVR of 6 cm.sup.3/(10 min) (as per ISO 1133:2012-03, at a test temperature of 300° C. and 1.2 kg load). A-3: Polycarbonate from Covestro Deutschland AG. Linear polycarbonate based on bisphenol A having a melt volume flow rate MVR of 19 cm.sup.3/(10 min) (as per ISO 1133:2012-03, at a test temperature of 300° C. and 1.2 kg load). A-4: Makrolon® 2408 powder from Covestro Deutschland AG. Linear polycarbonate based on bisphenol A having a melt volume flow rate MVR of 19 cm.sup.3/(10 min) (as per ISO 1133:2012-03, at a test temperature of 300° C. and 1.2 kg load). A-5: Linear polycarbonate based on bisphenol A and 24% by weight of 4,4-dihyroxydiphenyl having a melt volume flow rate MVR of 8 cm.sup.3/(10 min) (as per ISO 1133:2012-03, at a test temperature of 300° C. and 1.2 kg load). A-6: Polycarbonate from Covestro Deutschland AG. Linear polycarbonate based on bisphenol A having a melt volume flow rate MVR of 16 cm.sup.3/(10 min) (as per ISO 1133:2012-03, at a test temperature of 250° C. and 2.16 kg load). B: Rabitle FP-110 phenoxyphosphazene from Fushimi Pharmaceutical, Japan. C: Bisphenol A bis(diphenylphosphate) from Remy GmbH & Co. KG, Germany. D: potassium perfluorobutanesulfonate from Lanxess AG, Leverkusen. Fibres: Pyrofil TRH50 60M carbon fibres from Mitsubishi Rayon Co., Ltd. having an individual filament diameter of 7 μm, a density of 1.81 g/cm.sup.3 and a tensile modulus of 250 GPa. 60 000 individual filaments are supplied in a roving as an endless spool.

(10) Preparation of the Compositions

(11) The polycarbonate compositions described in the examples which follow were produced by compounding in an Evolum EV32HT extruder from Clextral (France) with a screw diameter of 32 mm. The screw set used was L7-8.2 at a throughput of 40-70 kg/h. The speed was 200-300 rpm at a melt temperature of 240-320° C. (according to the composition).

(12) The pellets of the test formulations detailed were dried in a Labotek DDM180 dry air dryer at 80° C. for 4 hours.

(13) Production of the Layers of the Fibre Composite Material/the Multilayer Composite Material:

(14) Production of a Fibre Composite Material Layer

(15) The fibre composite material layers were produced in an experimental setup as described in DE 10 2011 005 462 B3.

(16) The rovings of the above-described fibres were rolled out with constant spool tension from a creel and spread out by means of a spreading apparatus to give a raw fibre tape of individual filaments of width 60 mm in a torsion-free manner.

(17) The raw fibre tape was heated to a temperature above the glass transition temperature of the respective pellets.

(18) The pellets of the respective experimental formulations were melted in an Ecoline 30×25d extruder from Maschinenbau Heilsbronn GmbH and conducted through melt channels to slot dies arranged above and below and transverse to the running direction of the fibre tape. The temperature in the melt zones of the extruder was about 280° C. to 300° C. After emerging from the slot dies, the respective melt encountered the heated raw fibre tape, with contact of the raw fibre tape with the melt on both sides. The raw fibre tape that had been contacted with melt, having been heated further by means of a permanently heated plate, was transported to vibration shoes that were again heated. By means of pressure-shear vibration by means of the vibration shoe as described in DE 10 2011 005 462 B3, the respective melts were introduced into the raw fibre tape. The result was fibre composite material layers of width 60 mm which, after passing through chill rolls, were rolled up.

(19) Assembly of the Fibre Composite Material Layers—Part 1

(20) The composite material layers of width 60 mm were welded at their edges by means of an experimental setup, as described in DE 10 2011 090 143 A1, to give broader tapes of width 480 mm, with all individual filaments still arranged in the same direction. The consolidated composite material layers were rolled up again.

(21) Some of the assembled tapes from part 1 were subdivided into square sections orthogonally to the fibre orientation with a guillotine.

(22) Assembly of the Fibre Composite Material Layers—Part 2

(23) These square sections were consolidated at their original outer edges with a sealing bar to give a continuous composite material layer, and this process resulted in a fibre-reinforced composite material layer in which the orientation for all filaments was the same and was rotated by 90° in relation to the roll-off direction of the composite material layer. The composite material layer that had been consolidated in this way was rolled up.

(24) Production of the Organosheets

(25) All the organosheets examined hereinafter consisted of 4 fibre composite material layers, with 2 outer fibre composite material layers having the same fibre orientation and 2 inner fibre composite material layers having the same fibre orientation, the fibre orientation of the inner fibre composite material layers having been rotated by 90° in relation to the fibre orientation of the outer fibre composite material layers.

(26) For this purpose, fibre composite material layers having corresponding orientation were rolled out and laid one on top of another in the sequence described above. Thereafter, the stack was supplied to a PLA 500 interval heating press from BTS Verfahrenstechnik GmbH and pressed at a temperature above the glass transition temperature of the impregnation formulations to give an organosheet.

(27) The pressure applied across the surface here was 10 bar. The temperature in the heating zone was 280° C. and the temperature in the cooling zone was 100° C. In addition, the advance rate per cycle was 30 mm and the cycle time was 10 sec.

(28) This resulted in samples having total thicknesses of 0.7 mm. The fibre composite material layers used for production of the organosheets accordingly had thicknesses of 175 μm. The fibre volume content of the composite material layers was about 50% by volume per fibre composite material layer.

(29) The organosheets thus produced were used to prepare samples with a Mutronic Diadisc 5200 tabletop circular saw. This involved preparing samples parallel to the fibre orientation in the outer layers, referred to hereinafter as 0° orientation, and transverse to the fibre orientation in the outer layers, referred to hereinafter as 90° orientation.

(30) Methods:

(31) Melt volume flow rate (MVR) was determined according to ISO 1133:2012-03 (at a test temperature of 270° C. or 300° C., mass 1.2 kg) using a Zwick 4106 instrument from Zwick Roell. The abbreviation MRV here means the initial melt volume flow rate (after preheating for 7 minutes); the abbreviation IMVR20′ means the melt volume flow rate after 20 minutes.

(32) Melt viscosity was determined in accordance with ISO 11443:2005 with a Göttfert Visco-Robo 45.00 instrument.

(33) The thickness of the multilayer composite materials that result after joining was determined using a commercially available micrometer. The result reported is the arithmetic mean of 5 individual measurements at different positions.

(34) The fire characteristics were measured according to UL94 V on bars of dimensions 127 mm×12.7 mm×organosheet thickness [mm]. For this purpose, multilayer composite materials composed of four layers of fibre composite material were analysed. The fibre material was unidirectionally oriented carbon fibres as described above.

(35) Compositions and Results:

(36) TABLE-US-00001 TABLE 1 Examples Formulation E1 E2 E3 E4 E5 E6 E7 A-1 % by wt. 63.00 63.00 A-2 % by wt. 20.00 20.00 A-3 % by wt. 63.00 65.00 65.00 A-4 % by wt. 20.00 20.00 20.00 20.00 20.00 A-5 % by wt. A-6 % by wt. 63.00 65.00 B % by wt. 10.00 10.00 10.00 10.00 8.00 10.00 8.00 C % by wt. 7.00 7.00 7.00 7.00 7.00 5.00 7.00 D % by wt. Tests MVR (300° C., 1.2 kg) cm.sup.3/(10 min) 26.5 31.9 66.6 n.m. 63.6 63.3 n.m. IMVR20′ (300° C., 1.2 kg) 26.5 33.0 74.5 n.m. 63.5 61.8 n.m. ΔMVR/IMVR20′ (300° C., 1.2 kg) 0.0 1.1 7.9 n.m. −0.1 −1.5 n.m. MVR (270° C., 1.2 kg) cm.sup.3/(10 min) 10.7 14.1 32.7 80.1 28.5 28.8 63.4 IMVR20′ (270° C., 1.2 kg) 11.1 16.5 35.5 81.3 28.4 28.7 62.4 ΔMVR/IMVR20′ (270° C., 1.2 kg) 0.4 2.4 2.8 1.2 −0.1 −0.1 −1.0 Melt viscosity at 260° C. eta 50 Pa .Math. s 365 406 185 94 407 323 211 eta 100 Pa .Math. s 363 393 183 91 327 274 161 eta 200 Pa .Math. s 361 368 179 88 284 253 133 eta 500 Pa .Math. s 319 314 170 82 233 223 115 eta 1000 Pa .Math. s 258 251 150 76 194 189 102 eta 1500 Pa .Math. s 218 211 134 70 169 164 94 eta 5000 Pa .Math. s 105 103 77 48 91 88 UL94V(organosheet, 0.7 mm, 0°) (48 h, 23° C.) V0 V0 V0 V0 V0 V0 (7 d, 70° C.) V0 V0 V0 V0 V0 V0 Overall assessment V0 V0 V0 V0 V0 V0 UL94V on (organosheet, 0.7 mm, 90°) (48 h, 23° C.) V0 V0 V0 V0 V0 V0 (7 d, 70° C.) V0 V0 V0 V0 V0 V0 Overall assessment V0 V0 V0 V0 V0 V0 Formulation E8 E9 CE1 CE2 CE3 CE4 A-1 % by wt. A-2 % by wt. A-3 % by wt. 74.87 76.87 A-4 % by wt. 20.00 20.00 20.00 20.00 20.00 20.00 A-5 % by wt. 63.00 65.00 69.80 67.00 A-6 % by wt. B % by wt. 10.00 8.00 3.00 5.00 6.00 C % by wt. 7.00 7.00 5.00 5.00 7.00 D % by wt. 0.13 0.13 0.20 Tests MVR (300° C., 1.2 kg) cm.sup.3/(10 min) 43.9 37.7 26.6 22.1 23.0 32.6 IMVR20′ (300° C., 1.2 kg) 43.8 36.8 27.5 22.2 22.7 31.9 ΔMVR/IMVR20′ (300° C., 1.2 kg) −0.1 −0.9 0.9 0.1 −0.3 −0.7 MVR (270° C., 1.2 kg) cm.sup.3/(10 min) 19.8 16.5 10.4 8.1 9.0 13.9 IMVR20′ (270° C., 1.2 kg) 19.9 16.6 10.5 8.3 9.0 14.1 ΔMVR/IMVR20′ (270° C., 1.2 kg) 0.1 0.1 0.1 0.2 0.0 0.2 Melt viscosity at 260° C. eta 50 Pa .Math. s 519 505 575 655 813 519 eta 100 Pa .Math. s 428 439 547 646 803 470 eta 200 Pa .Math. s 358 393 523 628 732 439 eta 500 Pa .Math. s 295 320 452 542 571 371 eta 1000 Pa .Math. s 235 258 361 421 411 291 eta 1500 Pa .Math. s 198 217 299 344 321 244 eta 5000 Pa .Math. s 98 105 139 158 151 114 UL94V(organosheet, 0.7 mm, 0°) (48 h, 23° C.) V0 V0 * V1 V0 V0 (7 d, 70° C.) V0 V0 * V1 V1 V1 Overall assessment V0 V0 * V1 V1 V1 UL94V on (organosheet, 0.7 mm, 90°) (48 h, 23° C.) V0 V0 * failed V1 V1 (7 d, 70° C.) V0 V0 * failed V0 V0 Overall assessment V0 V0 * failed V1 V1 * no processing as matrix material possible n.m.: not measurable failed: no UL94 class

(37) The results show that it is possible only with the compositions used in accordance with the invention to attain a V0 classification coupled with good processibility and usability of the composition as a matrix material; the compositions according to the comparative examples did not give organosheets that attained a V0 classification or were not a suitable matrix material for the production of organosheets for lack of processibility.