Article comprising a fiber reinforced polypropylene composition

Abstract

The present invention is directed to an article comprising a fiber reinforced composition (C), said composition comprising a propylene polymer (PP), an elastomeric ethylene copolymer (E) and fibers (F).

Claims

1. An article comprising a fiber reinforced composition (C), comprising (i) 33.0 to 76.0 wt.-% of a propylene homopolymer (PP) which is at least bimodal, has a xylene cold soluble (XCS) content below 3.1 wt %, and has a melt flow rate MFR.sub.2 (230° C., 2.16 kg) determined according to ISO 1133 in the range of 30 to 250 g/10 min, (ii) 2.5 to 10.0 wt.-% of an elastomeric ethylene copolymer (E) which is a copolymer of ethylene and a C.sub.4-C.sub.10 α-olefin, having a melt flow rate MFR.sub.2 (190° C., 2.16 kg) determined according to ISO 1133 of at least 25.0 g/10 min, (iii) 1.5 to 2.0 wt.-% of an adhesion promoter (AP), and (iv) 20.0 to 50.0 wt.-% of fibers (F) based on the overall weight of the fiber reinforced composition (C), and the fiber reinforced composition (C) not containing more than 5 wt.-%, based on the total amount the fiber reinforced composition (C), of polymers other than the propylene homopolymer (PP), the elastomeric ethylene copolymer (E), and the adhesion promoter (AP).

2. The article according to claim 1, wherein the fiber reinforced composition (C) has a melt flow rate MFR.sub.2 (230° C., 2.16 kg) determined according to ISO 1133 below 100.0 g/10 min.

3. The article according to claim 1, wherein the adhesion promoter (AP) is a polar modified polypropylene (PM-PP) which is a propylene homo- or copolymer grafted with maleic anhydride having a melt flow rate MFR (190° C., 2.16 kg) determined according to ISO 1133 of at least 50.0 g/10 min.

4. The article according to claim 1, wherein the fiber reinforced composition (C) comprises the fibers (F) and the ethylene copolymer (E) in a weight ratio of 95:5 to 70:30.

5. The article according to claim 1, wherein the elastomeric ethylene copolymer (E) has a) a content of C.sub.4-C.sub.10 α-olefin of 2.0 to 25.0 mol-%, and/or b) a density below 0.900 g/cm.sup.3.

6. The article to claim 1, wherein the elastomeric ethylene copolymer (E) is a copolymer of ethylene and 1-octene.

7. The article according to claim 1, wherein the fibers (F) are selected from the group consisting of glass fibers, metal fibers, ceramic fibers, carbon fibers, and graphite fibers.

8. The article according to claim 1, wherein the fibers (F) are short fibers (SF) and/or long fibers (LF), wherein the short fibers have an average length in the range of 2.0 to 8.0 mm, and the long fibers have a length of 8.0 to 25.0 mm.

9. The article according to claim 8, wherein the short fibers are short glass fibers (SGF) and/or the long fibers are long glass fibers (LGF).

10. The article according to claim 1, comprising at least 80.0 wt.-% of the fiber reinforced composition (C), based on the overall weight of the article.

11. The article according to claim 1, wherein said article is a moulded article.

12. The article according to claim 11, wherein said moulded article is an injection moulded article.

Description

EXAMPLES

1. Measuring Methods

(1) MFR.sub.2 (230° C.) is measured according to ISO 1133 (230° C., 2.16 kg load).

(2) MFR.sub.2 (190° C.) is measured according to ISO 1133 (190° C., 2.16 kg load).

(3) The melt flow rate MFR.sub.2 (230° C.) of the propylene polymer (PP) is calculated according to equation (I)
log MFR(PP)=w(PP1).Math.log MFR(PP1)w(PP2).Math.log MFR(PP2)+w(PP3).Math.log MFR(PP3)  (I),

(4) Wherein w(PP1) is the weight fraction of the first propylene polymer (PP1) w(PP2) is the weight fraction of the second propylene polymer (PP2) w(PP3) is the weight fraction of the third propylene polymer (PP3) MFR(PP1) is the melt flow rate MFR.sub.2 (230° C., 2.16 kg) in g/10 min of the first propylene polymer (PP1) MFR(PP2) is the melt flow rate MFR.sub.2 (230° C., 2.16 kg) in g/10 min of the second propylene polymer (PP2), MFR(PP3) is the melt flow rate MFR.sub.2 (230° C., 2.16 kg) in g/10 min of the third propylene polymer (PP3), and MFR(PP) is the melt flow rate MFR.sub.2 (230° C., 2.16 kg) in g/10 min of the propylene polymer (PP)

(5) Quantification of Microstructure by NMR Spectroscopy

(6) Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content and comonomer sequence distribution of the polymers. Quantitative .sup.13C {.sup.1H} NMR spectra were recorded in the solution-state using a Bruker Advance III 400 NMR spectrometer operating at 400.15 and 100.62 MHz for .sup.1H and .sup.13C respectively. All spectra were recorded using a .sup.13C optimised 10 mm extended temperature probehead at 125° C. using nitrogen gas for all pneumatics. Approximately 200 mg of material was dissolved in 3 ml of 1,2-tetrachloroethane-d.sub.2 (TCE-d.sub.2) along with chromium-(III)-acetylacetonate (Cr(acac).sub.3) resulting in a 65 mM solution of relaxation agent in solvent (Singh, G., Kothari, A., Gupta, V., Polymer Testing 28 5 (2009), 475). To ensure a homogenous solution, after initial sample preparation in a heat block, the NMR tube was further heated in a rotatary oven for at least 1 hour. Upon insertion into the magnet the tube was spun at 10 Hz. This setup was chosen primarily for the high resolution and quantitatively needed for accurate ethylene content quantification. Standard single-pulse excitation was employed without NOE, using an optimised tip angle, 1 s recycle delay and a bi-level WALTZ16 decoupling scheme (Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag. Reson. 187 (2007) 225; Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 1128). A total of 6144 (6k) transients were acquired per spectra. Quantitative .sup.13C {.sup.1H} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals using proprietary computer programs. All chemical shifts were indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm using the chemical shift of the solvent. This approach allowed comparable referencing even when this structural unit was not present. Characteristic signals corresponding to the incorporation of ethylene were observed Cheng, H. N., Macromolecules 17 (1984), 1950).

(7) For polypropylene homopolymers all chemical shifts are internally referenced to the methyl isotactic pentad (mmmm) at 21.85 ppm.

(8) Characteristic signals corresponding to regio defects (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253; Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157; Cheng, H. N., Macromolecules 17 (1984), 1950) or comonomer were observed.

(9) The tacticity distribution was quantified through integration of the methyl region between 23.6-19.7 ppm correcting for any sites not related to the stereo sequences of interest (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443; Busico, V., Cipullo, R., Monaco, G., Vacatello, M., Segre, A. L., Macromoleucles 30 (1997) 6251).

(10) Specifically the influence of regio defects and comonomer on the quantification of the tacticity distribution was corrected for by subtraction of representative regio defect and comonomer integrals from the specific integral regions of the stereo sequences. The isotacticity was determined at the pentad level and reported as the percentage of isotactic pentad (mmmm) sequences with respect to all pentad sequences:
[mmmm]%=100*(mmmm/sum of all pentads)

(11) The presence of 2,1 erythro regio defects was indicated by the presence of the two methyl sites at 17.7 and 17.2 ppm and confirmed by other characteristic sites.

(12) Characteristic signals corresponding to other types of regio defects were not observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253). The amount of 2,1 erythro regio defects was quantified using the average integral of the two characteristic methyl sites at 17.7 and 17.2 ppm:
P.sub.21e=I.sub.e6+I.sub.e8/2

(13) The amount of 1,2 primary inserted propene was quantified based on the methyl region with correction undertaken for sites included in this region not related to primary insertion and for primary insertion sites excluded from this region:
P.sub.12=I.sub.CH3+P.sub.12e

(14) The total amount of propene was quantified as the sum of primary inserted propene and all other present regio defects:
P.sub.total=P.sub.12+P.sub.21e

(15) The mole percent of 2,1 erythro regio defects was quantified with respect to all propene:
[21e]mol %=100*(P.sub.21e/P.sub.total),

(16) For copolymers characteristic signals corresponding to the incorporation of ethylene were observed (Cheng, H. N., Macromolecules 17 (1984), 1950).

(17) With regio defects also observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253; Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157; Cheng, H. N., Macromolecules 17 (1984), 1950) correction for the influence of such defects on the comonomer content was required.

(18) The comonomer fraction was quantified using the method of Wang et. al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157) through integration of multiple signals across the whole spectral region in the .sup.13C {.sup.1H} spectra. This method was chosen for its robust nature and ability to account for the presence of regio-defects when needed. Integral regions were slightly adjusted to increase applicability across the whole range of encountered comonomer contents.

(19) For systems where only isolated ethylene in PPEPP sequences was observed the method of Wang et. al. was modified to reduce the influence of non-zero integrals of sites that are known to not be present. This approach reduced the overestimation of ethylene content for such systems and was achieved by reduction of the number of sites used to determine the absolute ethylene content to:
E=0.5(Sββ+Sβγ+Sβδ+0.5(Sαβ+Sαγ))

(20) Through the use of this set of sites the corresponding integral equation becomes:
E=0.5(I.sub.H+I.sub.G+0.5(I.sub.C+I.sub.D))

(21) using the same notation used in the article of Wang et. al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157). Equations used for absolute propylene content were not modified.

(22) The mole percent comonomer incorporation was calculated from the mole fraction:
E[mol %]=100*fE

(23) The weight percent comonomer incorporation was calculated from the mole fraction:
E[wt %]=100*(fE*28.06)/((fE*28.06)+((1−fE)*42.08))

(24) The comonomer sequence distribution at the triad level was determined using the analysis method of Kakugo et al. (Kakugo, M., Naito, Y., Mizunuma, K., Miyatake, T. Macromolecules 15 (1982) 1150). This method was chosen for its robust nature and integration regions slightly adjusted to increase applicability to a wider range of comonomer contents.

(25) Number Average Molecular Weight (M.sub.n), Weight Average Molecular Weight (M.sub.w) and Molecular Weight Distribution (MWD)

(26) Molecular weight averages (Mw, Mn), and the molecular weight distribution (MWD), i.e. the Mw/Mn (wherein Mn is the number average molecular weight and Mw is the weight average molecular weight), were determined by Gel Permeation Chromatography (GPC) according to ISO 16014-4:2003 and ASTM D 6474-99. A PolymerChar GPC instrument, equipped with infrared (IR) detector was used with 3× Olexis and 1× Olexis Guard columns from Polymer Laboratories and 1,2,4-trichlorobenzene (TCB, stabilized with 250 mg/L 2,6-Di tert butyl-4-methyl-phenol) as solvent at 160° C. and at a constant flow rate of 1 mL/min 200 of sample solution were injected per analysis. The column set was calibrated using universal calibration (according to ISO 16014-2:2003) with at least 15 narrow MWD polystyrene (PS) standards in the range of 0.5 kg/mol to 11 500 kg/mol. Mark Houwink constants for PS, PE and PP used are as described per ASTM D 6474-99. All samples were prepared by dissolving 5.0-9.0 mg of polymer in 8 mL (at 160° C.) of stabilized TCB (same as mobile phase) for 2.5 hours for PP or 3 hours for PE at max. 160° C. under continuous gentle shaking in the autosampler of the GPC instrument.

(27) DSC analysis, melting temperature (T.sub.m) and heat of fusion (H.sub.f), crystallization temperature (T.sub.c) and melt enthalpy (Hm): measured with a TA Instrument Q200 differential scanning calorimetry (DSC) on 5 to 7 mg samples. DSC is run according to ISO 11357/part 3/method C2 in a heat/cool/heat cycle with a scan rate of 10° C./min in the temperature range of −30 to +225° C. The crystallization temperature (T.sub.c) is determined from the cooling step, while melting temperature (T.sub.m) and melting enthalpy (H.sub.m) are determined from the second heating step. The crystallinity is calculated from the melting enthalpy by assuming an Hm-value of 209 J/g for a fully crystalline polypropylene (see “Section III Physical Properties of Monomers and Solvents,” Polymer Handbook, 4.sup.th Edition, Brandrup, J., Immergut, E. H., Eds., Wiley, New York, 1989, pages 1-61).

(28) The glass transition temperature Tg is determined by dynamic mechanical analysis according to ISO 6721-7. The measurements are done in torsion mode on compression moulded samples (40×10×1 mm.sup.3) between −100° C. and +150° C. with a heating rate of 2° C./min and a frequency of 1 Hz.

(29) Comonomer content in elastomer (E) was measured in a known manner based on Fourier transform infrared spectroscopy (FTIR) calibrated with .sup.13C-NMR, using Nicolet Magna 550 IR spectrometer together with Nicolet Omnic FTIR software. Films having a thickness of about 250 μm were compression molded from the samples. Similar films were made from calibration samples having a known content of the comonomer. The comonomer content was determined from the spectrum from the wave number range of from 1430 to 1100 cm.sup.−1. The absorbance is measured as the height of the peak by selecting the so-called short or long base line or both. The short base line is drawn in about 1410-1320 cm.sup.−1 through the minimum points and the long base line about between 1410 and 1220 cm.sup.−1. Calibrations need to be done specifically for each base line type. Also, the comonomer content of the unknown sample needs to be within the range of the comonomer contents of the calibration samples.

(30) Ash content is measured according to ISO 3451-1 (1997) standard.

(31) Density is measured according to ISO 1183-187. Sample preparation is done by compression moulding in accordance with ISO 1872-2:2007.

(32) Charpy notched and unnotched impact strength is determined according to ISO 179-1/1 eA and ISO 179-1/1 eU at 23° C. by using injection moulded test specimens (80×10×4 mm) as described in ISO 19069-2 unless indicated otherwise.

(33) Tensile properties were determined on injection molded dogbone specimens prepared in accordance with ISO 19069-2 unless indicated otherwise. Tensile modulus was determined according to ISO 527-1A at 1 mm/min. and 23° C. To determine stress at yield and strain at yield, a speed of 50 mm/min. was used.

(34) Instrumented falling weight test: Puncture energy, maximum force and puncture deflection was determined in the instrumented falling weight test according to ISO 6603-2 using injection moulded plaques of 60×60×3 mm in accordance with ISO 19069-2 unless indicated otherwise and a test speed of 4.4 m/s. The reported puncture energy results from an integral of the failure energy curve measured at +23° C. and −30° C.

(35) Average fiber diameter is determined according to ISO 1888:2006(E), Method B, microscope magnification of 1000.

2. Examples

(36) A. Used Materials PP1 is the commercial high flow propylene homopolymer HL504FB of Borealis AG having a melt flow rate MFR.sub.2 (230° C.) of 450 g/10 min and a glass transition temperature Tg of +0° C. PP2 is the commercial propylene homopolymer HJ120UB of Borealis AG having a melt flow rate MFR.sub.2 (230° C.) of 75 g/10 min, a density of 905 kg/m.sup.3 and a glass transition temperature Tg of +2° C. PP3 is the commercial propylene homopolymer HF955MO of Borealis AG having a melt flow rate MFR.sub.2 (230° C.) of 20 g/10 min, a density of 908 kg/m.sup.3 and a glass transition temperature Tg of +4° C. The propylene homopolymer HF955MO is α-nucleated with polyvinyl cyclohexane (polyVCH). PP4 is the commercial propylene homopolymer HK060UB of Borealis AG having a melt flow rate MFR.sub.2 (230° C.) of 125 g/10 min. E is the commercial ethylene-octene copolymer Queo8230 by Borealis having a density of 0.882 g/cm.sup.3, a melt flow rate MFR.sub.2 (190° C.) of 30.0 g/10 min and an 1-octene content of 7.5 mol-%. SF is the commercial product ECS 03 T-480H of Nippon Electric Glass Co., Ltd. having a filament diameter of 10.5 μm and a strand length of 3 mm. LF is the commercial glass fiber roving Performax SE4849 by Owens Corning. AP is the adhesion promoter SCONA TPPP 9012 GA by Scona being a polypropylene functionalized with maleic anhydride having a maleic anhydride content of 1.4 wt.-% and a MFR (190° C.) above 50 g/10 min Pigment 1 is a masterbatch comprising 1 wt.-% Remafin Schwarz P-AP (MP 99-BLACK 7-PP-30) by Clariant. Pigment 2 is the black pigment PCD PP-3719 BMB PPINJ PB25/1250 (MB 990—black 7-PP-40). AD is a composition comprising 1 part by weight of tris (2,4-di-t-butylphenyl) phosphite (Kinox-68-G by HPL Additives) and 2 parts by weight of pentaerythrityl-tetrakis(3-(3′,5′-di-tert. butyl-4-hydroxyphenyl)-propionate (Irganox 1010FF by BASF).

(37) B. Short Fiber Reinforced Compositions

(38) The following inventive examples IE1 to IE5 and comparative examples CE1 and CE2 were prepared by compounding on a co-rotating twin-screw extruder (ZSK 40 from Coperion) with an L/D ratio of 43. The following process parameters were used: throughput of 100 kg/h screw speed of 100-150 rpm barrel temperatures of 220-250° C. increasing from the feeding zone and decreasing again towards the die plate die plate with 4 mm diameter holes and 3 strands

(39) The polymer and the additives different from the short fibers were fed to the extruder and melt-kneaded in the 2.sup.nd barrel. A first kneading zone for mixing the polymer and the additives is located between the 3.sup.rd and 5.sup.th barrel. The short fibers were added in the 6th barrel using a side feeder. A second kneading zone for glass fiber dispersion is located between the 7.sup.th and 12.sup.th barrel.

(40) The composition and properties are summarized in Tables 1 and 2.

(41) TABLE-US-00001 TABLE 1 Composition of the inventive and comparative examples CE1 CE2 IE1 IE2 IE3 IE4 IE5 PP1 [wt.-%] 10.0 6.7 8.9 9.4 8.9 8.3 7.8 PP2 [wt.-%] 25.0 16.6 22.2 23.7 22.2 20.9 19.4 PP3 [wt.-%] 10.0 6.7 8.9 9.4 8.9 8.3 7.8 E [wt.-%] — 15.0 5.0 2.5 5.0 7.5 10.0 SF [wt.-%] 50.0 50.0 50.0 50.0 50.0 50.0 50.0 AP [wt.-%] 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Pigment [wt.-%] 1.0 1.0 1.0 1.0 1.0 1.0 1.0 AD [wt.-%] 2.0 2.0 2.0 2.0 2.0 2.0 2.0

(42) TABLE-US-00002 TABLE 2 Properties of the inventive and comparative examples CE1 CE2 IE1 IE2 IE3 IE4 IE5 Ash content [wt.-%] 49.9 50.9 49.1 49.4 49.8 49.6 49.8 MFR [g/10 min] 2.81 4.04 3.04 2.14 2.45 2.33 2.29 Tensile Modulus [MPa] 13016 10097 12275 12608 12210 11820 11350 Tensile Strength [MPa] 147.27 97.84 141.60 154.94 145.19 137.17 127.06 Tensile Strain at [%] 2.16 2.41 2.32 2.29 2.46 2.62 2.70 Tensile Strength Tensile Stress at [MPa] 147.27 97.70 141.38 154.94 145.14 136.92 126.77 Break Tensile Strain at [%] 2.16 2.44 2.33 2.29 2.45 2.57 2.60 Break Charpy notched [kJ/m.sup.2] 12.72 16.81 16.86 12.59 14.10 13.56 14.37 impact strength (23° C.) Charpy unnotched [kJ/m.sup.2] 62.58 55.41 63.16 60.37 63.38 61.55 60.01 impact strength (23° C.) Maximum Force [N] 1789 1681 1955 2102 2072 2186 2039 Deflection at [mm] 4.91 5.71 6.17 4.79 4.73 5.42 5.04 Maximum Force Energy to [J] 5.58 6.39 8.02 6.23 6.15 7.57 6.43 Maximum Force Puncture Deflection [mm] 5.76 7.70 7.35 5.62 6.02 6.49 6.53 Puncture Energy [J] 6.78 9.10 9.91 7.67 8.40 9.60 8.91

(43) C. Long Fiber Reinforced Compositions

(44) The compositions according to examples CE3, CE4 and IE6 to IE8 were obtained by impregnating glass rovings (LF) using an impregnating tool according to EP 0 397 505 B1 with a composition comprising the commercial high flow propylene homopolymer HL504FB of Borealis AG having a melt flow rate MFR.sub.2 (230° C.) of 450 g/10 min (PP1) and the adhesion promoter (AP) (SCONA TPPP 9012 GA by Scona). The impregnated rovings were combined and processed through a coating die where they were coated with a composition comprising the commercial propylene homopolymer HJ120UB of Borealis AG having a melt flow rate MFR.sub.2 (230° C.) of 75 g/10 min (PP2), the commercial propylene homopolymer HF955MO of Borealis AG having a melt flow rate MFR.sub.2 (230° C.) of 20 g/10 min (PP3) and the commercial ethylene-octene copolymer Queo8230 by Borealis having a density of 0.885 g/cm.sup.3 (E) in weight ratios according to Table 2. The strands were produced with a speed of 40 m/min and were immediately after production pulled through a water bath with a length of approximately 8 m. The cooled strands were then dried for a distance of about 5 m. The dried strands were then processed through a pelletiser where it was cut into granules with a length of 15 mm.

(45) The composition according to example CE5 was obtained by coating glass rovings (LF) with a composition comprising the commerical propylene homopolymer HK060UB of Borealis AG having a melt flow rate MFR.sub.2 (230° C.) of 125 g/10 min (PP3), the adhesion promoter (AP) (SCONA TPPP 9012 GA by Scona) and commercial ethylene-octene copolymer Queo8230 by Borealis having a density of 0.880 g/cm.sup.3 (E) in a weight ratio according to Table 2. The strand was processed as described above.

(46) The compositions according to examples CE6, CE7 and IE9 to IE12 were prepared analogously to the compositions according to CE3, CE4 and IE6 to IE8 with the difference that the propylene polymers and glass rovings described above were used in weight ratios according to Table 3 and that the strands were produced with a speed of 65 m/min.

(47) The properties of the inventive and comparative compositions are summarized in Tables 3 and 4.

(48) For the long fiber reinforced compositions, the test specimens for determination of the Charpy notched and unnotched impact strength, tensile properties and the instrumented falling weight test as described above were prepared in accordance with ISO 19069-2 with the following modifications: Flow front speed: 100 mm/s Mass temperature: 250° C. Hydraulic back pressure: 1 bar Holding pressure time: 30 s Cooling time: 25 s.

(49) TABLE-US-00003 TABLE 3 Composition and properties of fiber reinforced compositions containing 20.0 wt.-% long fibers CE3 CE4 CE5 IE6 IE7 IE8 PP1 [wt.-%] 34.80 27.30 33.55 32.30 29.80 PP2 [wt.-%] 34.80 27.30 33.55 32.30 29.80 PP3 [wt.-%] 8.0 8.0 8.00 8.00 8.00 PP4 [wt.-%] 65.25 E [wt.-%] 15.0 10.0 2.50 5.00 10.0 LF [wt.-%] 20.0 20.0 22.0 20.0 20.0 20.0 AP [wt.-%] 1.04 1.04 1.50 1.04 1.04 1.04 Pigment 1 [wt.-%] 0.64 0.64 0.64 0.64 0.64 Pigment 2 [wt.-%] 0.50 AD [wt.-%] 0.72 0.72 0.75 0.72 0.72 0.72 Ash content [wt.-%] 19.4 19.5 21.7 19.7 19.6 19.5 Tensile [MPa] 5712 5021 5350 5678 5543 5367 Modulus.sup.1) Tensile Strength.sup.1) [MPa] 114.4 103.6 103.0 115.2 115.3 112.1 Tensile Strain at [%] 2.60 2.75 2.56 2.65 2.75 2.73 Tensile Strength.sup.1) Tensile Stress at [MPa] 114.39 103.61 103.0 115.16 115.34 112.14 Break.sup.1) Tensile Strain at [%] 2.60 2.75 2.56 2.65 2.74 2.73 Break.sup.1) Charpy notched [kJ/m.sup.2] 14.31 18.79 16.6 13.61 14.14 16.43 impact strength (23° C.).sup.1) Charpy unnotched [kJ/m.sup.2] 43.88 59.75 52.3 51.74 57.09 55.05 impact strength (23° C.).sup.1) Maximum Force.sup.1) [N] 1748.4 1769.6 nd 1735.7 1874.0 1794.4 Deflection at [mm] 5.24 6.31 nd 5.23 6.08 5.95 Maximum Force.sup.1) Energy to [J] 5.21 7.44 nd 5.39 6.92 6.99 Maximum Force.sup.1) Puncture Deflection.sup.1) [mm] 7.59 8.75 nd 7.01 8.91 8.73 Puncture Energy.sup.1) [J] 8.32 10.8 9.96 7.75 10.6 10.65 .sup.1)determined on test specimens prepared in accordance with ISO 19069-2 with the above described modifications. nd not determined

(50) TABLE-US-00004 TABLE 4 Composition and properties of fiber reinforced compositions containing 40.0 wt.-% long fibers CE6 CE7 IE9 IE10 IE11 IE12 PP1 [wt.-%] 25.51 18.01 24.26 23.01 21.76 20.51 PP2 [wt.-%] 25.51 18.01 24.26 23.01 21.76 20.51 PP3 [wt.-%] 6.0 6.0 6.0 6.0 6.0 6.0 E [wt.-%] 15.0 2.50 5.0 7.5 10.0 LF [wt.-%] 40.0 40.0 40.0 40.0 40.0 40.0 AP [wt.-%] 1.97 1.97 1.97 1.97 1.97 1.97 Pigment 1 [wt.-%] 0.47 0.47 0.47 0.47 0.47 0.47 AD [wt.-%] 0.54 0.54 0.54 0.54 0.54 0.54 Ash content [wt.-%] 39.9 40.3 39.7 39.8 39.8 39.9 Tensile Modulus.sup.1) [MPa] 10559 9367 10337 10143 10103 9984 Tensile Strength.sup.1) [MPa] 175.2 144.9 174.2 167.3 165.8 161.5 Tensile Strain at [%] 2.20 2.28 2.25 2.24 2.28 2.29 Tensile Strength.sup.1) Tensile Stress at [MPa] 175.2 144.9 174.2 167.3 165.8 161.5 Break.sup.1) Tensile Strain at [%] 2.20 2.28 2.25 2.24 2.28 2.29 Break.sup.1) Charpy notched [kJ/m.sup.2] 26.55 29.28 29.76 32.04 30.21 33.53 impact strength (23° C.).sup.1) Charpy unnotched [kJ/m.sup.2] 83.6 74.8 80.49 82.34 80.26 76.87 impact strength (23° C.).sup.1) Maximum Force.sup.1) [N] 2498.0 2568.3 2704.2 2688.8 2659.2 2693.5 Deflection at [mm] 4.67 5.24 5.18 5.66 5.53 5.67 Maximum Force.sup.1) Energy to [J] 7.02 8.26 8.56 9.72 9.33 9.67 Maximum Force.sup.1) Puncture Deflection.sup.1) [mm] 7.58 9.88 8.49 8.60 9.19 9.50 Puncture Energy.sup.1) [J] 12.7 17.9 15.55 15.93 17.33 17.82 .sup.1)determined on test specimens prepared in accordance with ISO 19069-2 with the above described modifications.

(51) As can be gathered from Tables 2 to 4, the composition according to the comparative examples containing 15.0 wt.-% of the elastomeric compound are featured by high puncture energies and, therefore, excellent impact properties, but the tensile modulus decreases significantly compared to the comparative examples containing the same amount of fibers, but no elastomeric compound. The compositions according to the inventive examples containing 2.5 to 10.0 wt.-% of the elastomeric compound also show high puncture energies, but the tensile modulus remains on a high level. Thus, a good balance between stiffness and impact behavior is achieved.