Polymer composition with improved paint adhesion

Abstract

The invention is directed at a polypropylene composition comprising a heterophasic propylene copolymer, a plastomer and an inorganic filler. Furthermore, the invention directed at an article comprising the polypropylene composition and the use of the polypropylene composition to improve the adhesion performance of an article.

Claims

1. A polypropylene composition (C) comprising (a) 55 to 95 parts per weight of a heterophasic propylene copolymer (HECO); (b) 1 to 20 parts per weight of a plastomer (PL); and (c) 4 to 25 parts per weight of an inorganic filler (F); based on the total parts per weight of compounds (a), (b) and (c); wherein the heterophasic propylene copolymer (HECO) has an amount of xylene cold soluble (XCS) fraction in the range of 22 to 45 wt. %; and wherein the inorganic filler (F) is mica having a median particle size (D.sub.50) in the range of 1.5 to 8.0 μm.

2. The polypropylene composition (C) according to claim 1, wherein the polypropylene composition (C) has: (a) a melt flow rate MFR.sub.2 (230° C., 2.16 kg) measured according to ISO 1133 of at least 2 g/10 min; and/or (b) xylene soluble (XCS) fraction having an intrinsic viscosity (IV) of at least 3.0 dl/g.

3. The polypropylene composition (C) according to claim 1, wherein the polypropylene composition (C) has: (a) a tensile modulus measured according to ISO 527-2 of at least 1000 MPa; and/or (b) a tensile strength at yield measured according to ISO 527-2 of at least 5 MPa; and/or (c) a tensile stress at break measured according to ISO 527-2 of at least 5 MPa; and/or (d) a tensile elongation at break measured according to ISO 527-2 of not more than 100%; and/or (e) a Charpy Impact Strength (NIS+23) measured according to ISO 179-1eA:2000 at +23° C. of at least 20 kJ/m.sup.2; and/or (f) a Charpy Impact Strength (NIS-20) measured according to ISO 179-1eA:2000 at −20° C. of at least 2 kJ/m.sup.2.

4. The polypropylene composition (C) according to claim 1, wherein the heterophasic propylene copolymer (HECO) comprises (a) 70 to 98 parts per weight of a first heterophasic propylene copolymer (HECO1); and (b) 2 to 30 parts per weight of a second heterophasic propylene copolymer (HECO2); wherein the first heterophasic propylene copolymer (HECO1) differs from the second heterophasic propylene copolymer (HECO2) in the comonomer content of the xylene cold soluble (XCS) fraction and/or in the intrinsic viscosity (IV) of the xylene cold soluble (XCS) fraction.

5. The polypropylene composition (C) according to claim 4, wherein the first heterophasic propylene copolymer (HECO1) and the second heterophasic propylene copolymer (HECO2) together fulfil in-equation (I):
C.sub.x(XCS)[HECO1]/C.sub.x(XCS)[HECO2]>1.0  (I) wherein C.sub.x (XCS) [HECO1] is the comonomer content of the xylene cold soluble (XCS) fraction of the first heterophasic propylene copolymer (HECO1) and C.sub.x (XCS) [HECO2] is the comonomer content of the xylene cold soluble (XCS) fraction of the second heterophasic propylene copolymer (HECO2).

6. The polypropylene composition (C) according to claim 4, wherein the first heterophasic propylene copolymer (HECO1) and the second heterophasic propylene copolymer (HECO2) together fulfil in-equation (II):
IV(XCS)[HECO2]/IV(XCS)[HECO1]>1.0  (II) wherein IV (XCS) [HECO1] is the intrinsic viscosity (IV) of the xylene cold soluble (XCS) fraction of the first heterophasic propylene copolymer (HECO1) and IV (XCS) [HECO2] is the intrinsic viscosity (IV) of the xylene cold soluble (XCS) fraction of the second heterophasic propylene copolymer (HECO2).

7. The polypropylene composition (C) according to claim 1, wherein the heterophasic propylene copolymer (HECO) comprises (a) 5 to 30 parts per weight of a first heterophasic propylene copolymer (HECO1); (b) 5 to 30 parts per weight of a second heterophasic propylene copolymer (HECO2); and (c) 40 to 90 parts per weight of a third heterophasic propylene copolymer (HECO3); wherein the first heterophasic propylene copolymer (HECO1) differs from the second heterophasic propylene copolymer (HECO2) in comonomer content of the xylene cold soluble (XCS) fraction and/or the intrinsic viscosity (IV) of the xylene cold soluble (XCS) fraction; and wherein the third heterophasic propylene copolymer (HECO3) has a higher melt flow rate MFR.sub.2 (230° C., 2.16 kg) measured according to ISO 1133 than the first heterophasic propylene copolymer (HECO1) and the second heterophasic propylene copolymer (HECO2) respectively.

8. The polypropylene composition (C) according to claim 7, wherein (a1) the first heterophasic propylene copolymer (HECO1) and the second heterophasic propylene copolymer (HECO2) together fulfil in-equation (I):
C.sub.x(XCS)[HECO1]/C.sub.x(XCS)[HECO2]>1.0  (I) wherein C.sub.x (XCS) [HECO1] is the comonomer content of the xylene cold soluble (XCS) fraction of the first heterophasic propylene copolymer (HECO1); C.sub.x (XCS) [HECO2] is the comonomer content of the xylene cold soluble (XCS) fraction of the second heterophasic propylene copolymer (HECO2); and/or (a2) the first heterophasic propylene copolymer (HECO1) and the second heterophasic propylene copolymer (HECO2) together fulfil in-equation (II):
IV(XCS)[HECO2]/IV(XCS)[HECO1]>1.0  (II) wherein IV (XCS) [HECO1] is the intrinsic viscosity (IV) of the xylene cold soluble (XCS) fraction of the first heterophasic propylene copolymer (HECO1); IV (XCS) [HECO2] is the intrinsic viscosity (IV) of the xylene cold soluble (XCS) fraction of the second heterophasic propylene copolymer (HECO2); and (b) the first heterophasic propylene copolymer (HECO1), the second heterophasic propylene copolymer (HECO2) and the third heterophasic propylene copolymer (HECO3) together fulfil in-equation (III):
2×MFR[HECO3]/MFR[HECO1]+[MFR[HECO2]>1.0  (III) wherein MFR [HECO1] is the melt flow rate MFR.sub.2 (230° C., 2.16 kg) measured according to ISO 1133 of the first heterophasic propylene copolymer (HECO1); MFR [HECO2] is the melt flow rate MFR.sub.2 (230° C., 2.16 kg) measured according to ISO 1133 of the second heterophasic propylene copolymer (HECO2); and MFR [HECO3] is the melt flow rate MFR.sub.2 (230° C., 2.16 kg) measured according to ISO 1133 of the third heterophasic propylene copolymer (HECO3).

9. The polypropylene composition (C) according to claim 1, wherein the plastomer (PL) is an elastomeric ethylene copolymer (EC) comprising units derivable from ethylene and at least one C.sub.4 to C.sub.20 α-olefin.

10. The polypropylene composition (C) according to claim 1, wherein the polypropylene composition (C) does not comprise other polymers besides the heterophasic propylene copolymer (HECO) and and the plastomer (PL) in an amount exceeding 5 wt.-%, based on the weight of the polypropylene composition (C).

11. The polypropylene composition (C) according to claim 1, wherein the heterophasic propylene copolymer (HECO) and and the plastomer (PL) are the only polymers present in the the polypropylene composition (C).

12. An article comprising the polypropylene composition (C) according to claim 1.

13. A method of enhancing paint adhesion of a moulded article comprising utilizing the polypropylene composition (C) according to claim 1 in producing the moulded article.

Description

EXAMPLES

(1) 1. Definitions/Measuring Methods

(2) The following definitions of terms and determination methods apply for the above general description of the invention as well as to the below examples unless otherwise defined.

(3) Quantification of Microstructure by NMR Spectroscopy

(4) Quantitative nuclear-magnetic resonance (NMR) spectroscopy is used to quantify the isotacticity and regio-regularity of the polypropylene homopolymers.

(5) Quantitative .sup.13C{.sup.1H} R spectra were recorded in the solution-state using a Bruker Advance III 400 R 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 probe head at 125° C. using nitrogen gas for all pneumatics.

(6) For polypropylene homopolymers approximately 200 mg of material was dissolved in 1,2-tetrachloroethane-d.sub.2 (TCE-d.sub.2). To ensure a homogenous solution, after initial sample preparation in a heat block, the R tube was further heated in a rotatory 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 needed for tacticity distribution quantification (Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443; Busico, V.; Cipullo, R., Monaco, G., Vacatello, M., Segre, A. L., Macromolecules 30 (1997) 6251). Standard single-pulse excitation was employed utilising the NOB and 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, 11289). A total of 8192 (8 k) transients were acquired per spectra.

(7) Quantitative .sup.13C {.sup.1H} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals using proprietary computer programs.

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

(9) 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.

(10) 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., Macromolecules 30 (1997) 6251).

(11) 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)

(12) 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. 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).

(13) 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

(14) 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

(15) 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

(16) 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)

(17) Characteristic signals corresponding to the incorporation of ethylene were observed (as described in Cheng, H. N., Macromolecules 1984, 17, 1950) and the comonomer fraction calculated as the fraction of ethylene in the polymer with respect to all monomer in the polymer.

(18) The comonomer fraction was quantified using the method of W-J. Wang and S. Zhu, Macromolecules 2000, 33 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) The mole percent comonomer incorporation was calculated from the mole fraction.

(20) The weight percent comonomer incorporation was calculated from the mole fraction.

(21) Melt Flow Rate MFR.sub.2 (230° C.) was measured at 230° C. under a load of 2.16 kg according to ISO 1133.

(22) Melt Flow Rate MFR2 (190° C.) was measured at 190° C. under a load of 2.16 kg according to ASTM D1238.

(23) Xylene Cold Soluble (XCS) Fraction was measured at 25° C. according ISO 16152; first edition; 2005-07-01.

(24) Intrinsic Viscosity as measured according to DIN ISO 1628/1, October 1999 (in Decalin at 135° C.).

(25) Tensile Modulus; Tensile Stress at Break were measured according to ISO 527-2 (cross head speed=1 mm/min; 23° C.) using injection molded specimens as described in EN ISO 1873-2 (dog bone shape, 4 mm thickness)

(26) Tensile Elongation at Break; Tensile Strength at Yield were measured according to ISO 527-2 (cross head speed=50 mm/min; 23° C.) using injection molded specimens as described in EN ISO 1873-2 (dog bone shape, 4 mm thickness).

(27) Charpy Notched Impact Strength at +23° C. (NIS+23) was measured according to ISO 179-1eA:2000, using injection molded bar test specimens of 80×10×4 mm.sup.3 prepared in accordance with EN ISO 1873-2.

(28) Charpy Notched Impact Strength at −20° C. (NIS-20) was measured according to ISO 179-1eA:2000, using injection molded bar test specimens of 80×10×4 mm.sup.3 prepared in accordance with EN ISO 1873-2.

(29) Cut-Off Particle Size D.sub.95 (Sedimentation) was calculated from the particle size distribution [wt. %] as determined by gravitational liquid sedimentation according to ISO 13317-3 (Sedigraph).

(30) Cut-Off Particle Size D.sub.98 (Sedimentation) was calculated from the particle size distribution [wt. %] as determined by gravitational liquid sedimentation according to ISO 13317-3 (Sedigraph).

(31) Median Particle Size D.sub.50 (Sedimentation) was calculated from the particle size distribution [wt.-%] as determined by gravitational liquid sedimentation according to ISO 13317-3 (Sedigraph).

(32) BET Surface Area was measured according to DIN 66131/2 with nitrogen (N.sub.2).

(33) Adhesion is characterized as the resistance of the pre-fabricated scratch template to pressure-water jetting according to DIN 55662 (Method C).

(34) Injection moulded sample plates (150 mm×80 mm×2 mm) were cleaned with Zeller Gmelin Divinol® 1262. Subsequently the surface was activated via flaming where a burner with a speed of 670 mm/s spreads a mixture of propane (9 l/min) and air (180 l/min) in a ratio of 1:20 on the polymer substrate. Afterwards, the polymer substrate was coated with 2 layers, i.e. a base coat (Iridium Silver Metallic 117367) and a clear coat (Carbon Creations® 107062). The step of flaming was performed two times.

(35) A steam of hot water with temperature T was directed for time t at distance d under angle α to the surface of the test panel. Pressure of the water jet results from the water flow rate and is determined by the type of nozzle installed at the end of the water pipe.

(36) The following parameters were used:
T(water)=60° C.; t=60 s; d=100 mm, α=90°, water flow rate 11.3 l/min, nozzle type=MPEG 2506.

(37) The adhesion was assessed by quantifying the failed or delaminated painted area per test line. For each example 5 panels (150 mm×80 mm×2 mm) have been tested. The panels were produced by injection moulding with 240° C. melt temperature and 50° C. mold temperature. The flow front velocity was 100 mm/s and 400 mm/s respectively. On each panel certain lines were used to assess the paintability failure in [mm.sup.2]. For this purpose, an image of the test point before and after steam jet exposure was taken. Then the delaminated area was calculated with an image processing software. The average failed area for 5 test lines on 5 test specimens (i.e. in total the average of 25 test points) was reported as median failed area.

(38) SD is the standard deviation which is determined according to the following formula:

(39) $\mathrm{Sample}\mathrm{Standard}\mathrm{Deviation}=\sqrt{\frac{{\Sigma \left(x-\stackrel{\_}{x}\right)}^2}{\left(n-1\right)}}$

(40) wherein

(41) x are the observed values;

(42) x is the mean of the observed values; and

(43) n is the number of observations.

(44) Preparation of the Heterophasic Propylene Copolymer (HECO1)

(45) Catalyst Preparation:

(46) First, 0.1 mol of MgCl.sub.2×3 EtOH was suspended under inert conditions in 250 ml of decane in a reactor at atmospheric pressure. The solution was cooled to −15° C. and 300 ml of cold TiCl.sub.4 were added, while maintaining the temperature at said level. Then, the temperature of the slurry was increased slowly to +20° C. At this temperature, 0.02 mol of dioctylphthalate (DOP) was added to the slurry. After the addition of the phthalate, the temperature was raised to +135° C. within 90 minutes and the slurry was allowed to stand for 60 minutes. Then, additional 300 ml of TiCl.sub.4 were added and the temperature was kept at +135° C. for 120 minutes. Subsequently, the catalyst was filtered from the liquid and washed six times with 300 ml heptane at 80° C. The solid catalyst component was filtered and dried.

(47) The catalyst and its general concept of preparation is described e.g. in WO 87/07620, WO 92/19653, WO 92/19658 and EP 0 491 566, EP 591224 and EP 586390.

(48) VCH Modification:

(49) The catalyst was further modified. 35 ml of mineral oil (Paraffinum Liquidum PL68) were added to a 125 ml stainless steel reactor followed by 0.82 g of triethyl aluminium (TEAL) and 0.33 g of dicyclopentyl dimethoxy silane (donor D) under inert conditions at room temperature. After 10 minutes 5.0 g of the catalyst described above (Ti content 1.4 wt.-%) was added. After 20 minutes 5.0 g of vinylcyclohexane (VCH) were added. The temperature was increased to +60° C. within 30 minutes and was kept for 20 hours. Finally, the temperature was decreased to +20° C. and the concentration of unreacted VCH in the oil/catalyst mixture was analysed and was found to be 200 ppm weight. As external donor di(cyclopentyl) dimethoxy silane (donor D) was used.

(50) Polymer Preparation:

(51) The heterophasic propylene copolymer (HECO1) is prepared in a slurry reactor (SL) and multiple gas phase reactors connected in series (1.sup.st GPR, 2.sup.nd GPR and 3.sup.rd GPR). The conditions applied and the properties of the products obtained are summarized in Table 1.

(52) TABLE-US-00001 TABLE 1 Preparation of the heterophasic propylene copolymer (HECO1) HECO1 Prepolymerization TEAL/Ti [mol/mol] 220 TEAL/Do [mol/mol] 7.3 Temperature [° C.] 30 Residence time [h] 0.08 Loop Temperature [° C.] 72 Split [%] 25 H2/C3 [mol/kmol] 15 C2/C3 [mol/kmol] 0 MFR.sub.2 [g/10 min] 55 XCS [wt.-%] 2.0 C2 [mol-%] 0 1.sup.st GPR Temperature [° C.] 80 Pressure [kPa] 2231 Split [%] 40 H2/C3 [mol/kmol] 150 C2/C3 [mol/kmol] 0 MFR.sub.2 [g/10 min] 55 XCS [wt.-%] 2.0 C2 [mol-%] 0 2.sup.nd GPR Temperature [° C.] 70 Pressure [kPa] 2291 Split [%] 20 C2/C3 [mol/kmol] 584 H2/C2 [mol/kmol] 117 MFR.sub.2 [g/10 min] 20 XCS [wt.-%] 20 IV (XCS) [dl/g] nd C2 (XCS) [mol-%] nd C2 [mol-%] 18 3rd GPR Temperature [° C.] 85 Pressure [kPa] 142 Split [%] 15 C2/C3 [mol/kmol] 585 H2/C2 [mol/kmol] 93 MFR.sub.2 [g/10 min] 11 XCS [wt.-%] 30 IV (XCS) [dl/g] 3.5 C2 (XCS) [mol-%] 50 C2 [mol-%] 19 C2 ethylene content H2/C3 hydrogen/propylene ratio C2/C3 ethylene/propylene ratio H2/C2 hydrogen/ethylene ratio 1.sup.st 2.sup.nd 3.sup.rd GPR 1.sup.st 2.sup.nd 3.sup.rd gas phase reactor Loop loop reactor TEAL/Ti TEAL/Ti ratio TEAL/Do TEAL/Donor ratio MFR.sub.2 melt flow rate XCS xylene cold soluble fraction C2 (XCS) ethylene content of the xylene cold soluble fraction IV (XCS) intrinsic viscosity of the xylene cold soluble fraction nd not determined

(53) The properties of the products obtained from the individual reactors naturally are not determined from homogenized material but from reactor samples (spot samples). The properties of the final resin are measured on homogenized material.

(54) Preparation of the Heterophasic Propylene Copolymer (HECO2)

(55) Catalyst Preparation:

(56) The catalyst applied for the preparation of the heterophasic propylene copolymer (HECO2) is the same catalyst as the catalyst applied for the preparation of the heterophasic propylene copolymer (HECO1).

(57) Polymer Preparation:

(58) The heterophasic propylene copolymer (HECO2) is prepared in a slurry and multiple gas phase reactors connected in series. The conditions applied and the properties of the products obtained are summarized in Table 2.

(59) TABLE-US-00002 TABLE 2 Preparation of the heterophasic propylene copolymer (HECO2) HECO2 Loop Temperature [° C.] 76 Split [%] 5 H2/C3 [mol/kmol] 25 C2/C3 [mol/kmol] 0 MFR.sub.2 [g/10 min] 160 XCS [wt.-%] nd C2 [mol-%] 0 1.sup.st GPR Temperature [° C.] 80 Pressure [kPa] 2400 Split [%] 40 H2/C3 [mol/kmol] 45 C2/C3 [mol/kmol] 0 MFR.sub.2 [g/10 min] 55 XCS [wt.-%] nd C2 [mol-%] 0 2.sup.nd GPR Temperature [° C.] 67 Pressure [kPa] 2100 Split [%] 15 C2/C3 [mol/kmol] 242 H2/C2 [mol/kmol] 23 MFR.sub.2 [g/10 min] 20 XCS [wt.-%] 20 IV (XCS) [dl/g] >4.0 C2 (XCS) [mol-%] 28 C2 [mol-%] 10 3rd GPR Temperature [° C.] 67 Pressure [kPa] 1500 Split [%] 10 C2/C3 [mol/kmol] 250 H2/C2 [mol/kmol] 22 MFR.sub.2 [g/10 min] 7 XCS [wt.-%] 27 IV (XCS) [dl/g] 6.3 C2 (XCS) [mol-%] 28 C2 [mol-%] 12 C2 ethylene content H2/C3 hydrogen/propylene ratio C2/C3 ethylene/propylene ratio H2/C2 hydrogen/ethylene ratio 1.sup.st 2.sup.nd 3.sup.rd GPR 1.sup.st 2.sup.nd 3.sup.rd gas phase reactor Loop loop reactor TEAL/Ti TEAL/Ti ratio TEAL/Do TEAL/Donor ratio MFR.sub.2 melt flow rate XCS xylene cold soluble fraction C2 (XCS) ethylene content of the xylene cold soluble fraction IV (XCS) intrinsic viscosity of the xylene cold soluble fraction nd not determined

(60) Preparation of the Heterophasic Propylene Copolymer (HECO3)

(61) Catalyst Preparation:

(62) The catalyst applied for the preparation of the heterophasic propylene copolymer (HECO3) is the same catalyst as the catalyst applied for the preparation of the heterophasic propylene copolymer (HECO1).

(63) Polymer Preparation:

(64) The heterophasic propylene copolymer (HECO3) is prepared in a slurry and multiple gas phase reactors connected in series. The conditions applied and the properties of the products obtained are summarized in Table 3.

(65) TABLE-US-00003 TABLE 3 Preparation of the heterophasic propylene copolymer (HECO3) HECO3 Loop Temperature [° C.] 72 Split [%] 29 H2/C3 [mol/kmol] 21 C2/C3 [mol/kmol] 0 MFR.sub.2 [g/10 min] 115 XCS [wt.-%] nd C2 [mol-%] 0 1.sup.st GPR Temperature [° C.] 85 Pressure [kPa] 2500 Split [%] 36 H2/C3 [mol/kmol] 204 C2/C3 [mol/kmol] 0 MFR.sub.2 [g/10 min] 115 XCS [wt.-%] nd C2 [mol-%] 0 2.sup.nd GPR Temperature [° C.] 75 Pressure [kPa] 2000 Split [%] 22 C2/C3 [mol/kmol] 701 H2/C2 [mol/kmol] 85 MFR.sub.2 [g/10 min] 40 XCS [wt.-%] 20 IV (XCS) [dl/g] 3.1 C2 (XCS) [mol-%] 50 C2 [mol-%] 12 3rd GPR Temperature [° C.] 85 Pressure [kPa] 1400 Split [%] 13 C2/C3 [mol/kmol] 699 H2/C2 [mol/kmol] 129 MFR.sub.2 [g/10 min] 2 XCS [wt.-%] 29 IV (XCS) [dl/g] 3.1 C2 (XCS) [mol-%] 50 C2 [mol-%] 19 C2 ethylene content H2/C3 hydrogen/propylene ratio C2/C3 ethylene/propylene ratio H2/C2 hydrogen/ethylene ratio 1.sup.st 2.sup.nd 3.sup.rd GPR 1.sup.st 2.sup.nd 3.sup.rd gas phase reactor Loop loop reactor TEAL/Ti TEAL/Ti ratio TEAL/Do TEAL/Donor ratio MFR.sub.2 melt flow rate XCS xylene cold soluble fraction C2 (XCS) ethylene content of the xylene cold soluble fraction IV (XCS) intrinsic viscosity of the xylene cold soluble fraction nd not determined

(66) The properties of the products obtained from the individual reactors naturally are not determined from homogenized material but from reactor samples (spot samples). The properties of the final resin are measured on homogenized material.

Preparation of the Examples

(67) The Inventive Examples IE1, IE2, IE3, IE4 and IE5 and the Comparative Examples CE1, CE2 and CE3 were prepared by melt blending with a twin-screw extruder such as the Coperion STS-35 twin-screw extruder from the Coperion (Nanjing) Corporation, China. The twin-screw extruder runs at an average screw speed of 400 rpm with a temperature profile of zones from 180 to 250° C.

(68) The Inventive Examples IE1, IE 2, IE3, IE4 and IE5 and the Comparative Examples CE1, CE2 and CE3 are based on the recipe summarized in Table 4.

(69) TABLE-US-00004 TABLE 4 The recipe for preparing the inventive and comparative examples Exam- ple CE1 CE2 CE3 IE1 IE2 IE3 IE4 IE5 HECO1 [wt %]* 73.15 76.65 15.00 73.15 76.65 68.65 15.00 15.00 HECO2 [wt %]*  7.50 10.00  7.50 10.00 10.00 HECO3 [wt %]* 50.15 50.15 50.15 Plasto- [wt %]*  9.00  3.50  9.00  9.00 mer1 Plasto- [wt %]*  3.50  7.50  7.50 11.50 mer2 Filler1 [wt %]* 15.00 Filler2 [wt %]* 15.00 15.00 19.00 15.00 Filler3 [wt %]* 15.00 15.00 Filler4 [wt %]* 15.00 *rest to 100 wt.-% are additives in regular levels, including polymeric carrier material, antioxidants and UV-stabilizer, such as Octadecyl 3-(3′,5′-di-tert. butyl-4-hydroxyphenyl)propionate in form of the commercial antioxidant “Irganox 1076” of BASF, Germany, CAS-no. 2082-79-3, colorants, such as carbon black in form of the masterbatch “Cabot Plasblak ® PE1639 (40% carbon black)” of the Cabot Corporation. “Plastomer1” is the commercial product Engage ® 8100 of The Dow Chemical Company, which is an ethylene/1-octene copolymer having a melt flow rate MFR.sub.2 (190° C., 2.16 kg) of 1.0 g/10 min and a density of 0.870 g/cm.sup.3. “Plastomer2” is the commercial product Queo ® 8201Borealis AG, which is an ethylene/1-octene copolymer having a melt flow rate MFR.sub.2 (190° C., 2.16 kg) of 1.1 g/10 min and a density of 0.883 g/cm.sup.3. “Filler1” is the commercial product Jetfine ® T1CA of Imerys LLC, which is talc having an average particle size (D.sub.50) of 1.3 μm, a cutoff particle size (D.sub.95) of 4.2 μm. “Filler2” is the commercial product MicaFort ® PW80 of LKAB Minerals AB, which is mica having an average particle size (D.sub.50) of 5.4 μm, a cutoff particle size (D.sub.98) of 29.8 μm. “Filler3” is the commercial product Jetfine3 ® CA of Imerys LLC, which is talc having an average particle size (D.sub.50) of 1.0 μm, a cutoff particle size (D.sub.59) of 3.5 μm. “Filler4” is the commercial product Luzenac ® A20 of Imerys LLC, which is talc having an average particle size (D.sub.50) of 3.3 μm, a cutoff particle size (D.sub.59) of 9.4 μm

(70) The properties of the Inventive Examples IE1, IE 2, IE3, IE4 and IE5 and the Comparative Examples CE1, CE2 and CE3 are summarized in Table 5.

(71) TABLE-US-00005 TABLE 5 Properties of the inventive and comparative compositions Example CE1 CE2 CE3 IE1 IE2 IE3 IE4 IE5 MFR.sub.2 [g/10 min] 10.0 8.0 10.8 8.5 8.3 nd 11.3 10.8 XCS [wt.-%]* 28.6 31.1 30.9 28.6 31.1 32.5 30.9 30.9 IV (XCS) [dl/g] 3.7 33 3.4 3.7 3.3  3.2 3.4 3.4 TM [MPa] 1635 1508 1625 1924 1766 nd 2025 1473 TS@Yield [MPa] 18.8 17.1 18.2 18.9 17.4 nd 18.6 17.6 TS@Break [MPa] 13.0 12.1 12.6 11.7 11.4 nd 12.2 12.2 TE@Break [%] 94 78 72 36 38 nd 37 65 NIS + 23 [kJ/m.sup.2] 63.6 72.0 55.9 31.6 40.7 nd 30.3 48.8 NIS − 20 [kJ/m.sup.2] 8.4 10.0 8.6 5.7 7.8 nd 6.0 8.0 *based on the total weight of the composition “MFR.sub.2” is the melt flow rate “XCS” is xylene cold soluble (XCS) fraction “IV(XCS)” is the intrinsic viscosity of the xylene cold soluble (XCS) fraction “TS@Yield” is the tensile strength at yield “TS@Break” is the tensile stress at break “TE@Break” is the tensile elongation at break “NIS + 23” is the charpy notched impact strength at +23° C. “NIS − 20” is the charpy notched impact strength at −20° C. “nd” is a value which has not been determined

(72) The adhesion performance of the Inventive Examples IE1, IE 2, IE3, IE4 and IE5 and the Comparative Examples CE1, CE2 and CE3 is summarized in Table 6.

(73) TABLE-US-00006 TABLE 6 Adhesion performance of the inventive and comparative compositions Example CE1 CE2 CE3 IE1 IE2 IE3 IE4 IE5 Paintability (100 mm/s Flow Front Mean DA [mm.sup.2] 20  1 19 16  3  3  0 22 Median DA [mm.sup.2]  3  0  0  3  0  0  0  0 SD [mm.sup.2] 28  3 34 22  5  7  0 35 Paintability (400 mm/s Flow Front Mean DA [mm.sup.2] 94 81 70 13 18 31 35 33 Median DA [mm.sup.2] 88 87 64 10 14 11 20 29 SD [mm.sup.2] 54 58 59 12 19 44 38 33 “Mean DA” is the mean delamination area “Median DA” is the median delamination area “SD” is the standard deviation