MULTILAYER FILM WITH IMPROVED PROPERTIES

Abstract

The present invention relates to a multilayer film comprising at least two outer layers (A) and (C) and at least one core layer (B), at least one of the outer layers (A) and/or (C) comprises component a1), whereas the other outer layer comprises component a1) or a2), whereby component a1) is a terpolymer of propylene, ethylene and one C4 to C10 α-olefin; whereby said terpolymer a1) has an ethylene content in the range of 0.1 to 8.0 wt.-% based on the total weight of the terpolymer a1); a C4 to C10 α-olefin content in the range of 0.1 to 16.0 wt.-% based on the total weight of the terpolymer a1); and a melt flow rate MFR2 measured according to ISO 1133 (230° C., 2.16 kg load) in the range of 0.5 to 12.0 g/10 min; component a2) is a polypropylene having a melting temperature of at least 150° C.; and layer (B) comprises a heterophasic propylene copolymer b), said heterophasic propylene copolymer b) comprises a matrix being a random propylene copolymer b1) and an elastomeric propylene copolymer b2) dispersed in said matrix; whereby the heterophasic propylene copolymer b) has a melt flow rate MFR2 measured according to ISO 1133 (230° C., 2.16 kg load) in the range of 0.3 to 20.0 g/10 min; a xylene cold soluble content (XCS) determined according ISO 16152 (25° C.) in the range of 16.0 to 50.0 wt.-%; and a comonomer content in the range of 11.5 to 21.0 mol-%. In addition, the present invention relates to the use of the multilayer film according to the present invention for soft packaging applications, preferably pouches for food packaging, for medical applications or for pharmaceutical applications.

Claims

1: A multilayer film comprising at least two outer layers (A) and (C) and at least one core layer (B), at least one of the outer layers (A) and/or (C) comprises component a1), whereas the other outer layer comprises component a1) or a2), whereby: component a1) is a terpolymer of propylene, ethylene and one C4 to C10 α-olefin; whereby said terpolymer a1) has; an ethylene content in the range of 0.1 to 8.0 wt. % based on the total weight of the terpolymer a1); a C4 to C10 α-olefin content in the range of 0.1 to 16.0 wt. % based on the total weight of the terpolymer a1); and a melt flow rate MFR.sub.2 measured according to ISO 1133 (230° C., 2.16 kg load) in the range of 0.5 to 12.0 g/10 min; component a2) is a polypropylene having a melting temperature of at least 150° C.; and layer (B) comprises a heterophasic propylene copolymer b), said heterophasic propylene copolymer b) comprises a matrix being a random propylene copolymer b1) and an elastomeric propylene copolymer b2) dispersed in said matrix; whereby the heterophasic propylene copolymer b) has: a melt flow rate MFR.sub.2 measured according to ISO 1133 (230° C., 2.16 kg load) in the range of 0.3 to 20.0 g/10 min; a xylene cold soluble content (XCS) determined according ISO 16152 (25° C.) in the range of 16.0 to 50.0 wt. %; and a comonomer content in the range of 11.5 to 21.0 mol %.

2: The multilayer film according to claim 1, wherein component a1): has a melting temperature (Tm) determined by differential scanning calorimetry (DSC) of not higher than 145° C.; and/or has a glass transition temperature (Tg) determined by dynamic mechanical analysis (DMA) in the range of −12 to +5° C.; and/or has a crystallization temperature (Tc) determined by differential scanning calorimetry (DSC) of equal or higher than 90° C.; and/or is a terpolymer of ethylene, propylene and 1-butene.

3: The multilayer film according to claim 1, wherein component a1) has: an ethylene content in the range of 0.3 to 5.0 wt. % based on the total weight of the terpolymer a1); and/or a C4 to C10 α-olefin content in the range of 0.5 to 12.0 wt. % based on the total weight of the terpolymer a1), whereby the α-olefin preferably is 1-butene; and/or a melt flow rate MFR.sub.2 measured according to ISO 1133 (230° C., 2.16 kg load) in the range of 2.0 to 10.0 g/10 min; and/or a molecular weight distribution (Mw/Mn) of more than 3.0.

4: The multilayer film according to claim 1, wherein component a2) is a propylene homopolymer having: a melting temperature of at least 158° C.; and/or a melt flow rate MFR.sub.2 (230° C., 2.16 kg) in the range of 0.5 to 20.0 g/10 min; or component a2) is a propylene copolymer having: a melting temperature of at least 150° C.; and/or a comonomer content of not more than 3.5 wt. %; and/or a melt flow rate MFR.sub.2 (230° C., 2.16 kg) in the range of 0.5 to 20.0 g/10 min.

5: The multilayer film according to claim 1, wherein: the heterophasic propylene copolymer b) has: a Charpy Notched Impact Strength as defined by in-equation (I):
NIS>60−23.0×ln(MFR)  (I) wherein “NIS” is the Charpy Notched Impact Strength according to ISO 179-1eA:2000 at 23° C. [in kJ/m.sup.2] of the heterophasic propylene copolymer b); and “MFR” is the MFR.sub.2 (230° C./2.16 kg) [in g/10 min] of the heterophasic propylene copolymer b); and/or at least two glass transition temperatures Tg(1) and Tg(2), the first glass transition temperature Tg(1) relates to the matrix b1) while the second glass transition temperature Tg(2) relates to the dispersed elastomeric propylene copolymer b2), wherein further the second glass transition temperature Tg(2) fulfills in-equation (II);
Tg(2)>21.0−2.0×C(XCS)  (II) wherein Tg(2) is the second glass transition temperature of the heterophasic propylene copolymer b); and C(XCS) is the comonomer content [in mol %] of the xylene cold soluble fraction (XCS) of the heterophasic propylene copolymer (b).

6: The multilayer film according to claim 1, wherein: the heterophasic propylene copolymer b) has: a melt flow rate MFR.sub.2 measured according to ISO 1133 (230° C., 2.16 kg load) in the range of 0.5 to 15.0 g/10 min; and/or a xylene cold soluble content (XCS) determined according ISO 16152 (25° C.) in the range of 16.0 to 35.0 wt. %; and/or a comonomer content in the range of 12.0 to 19.0 mol %; and/or a C2-content in the range of 2.0 to 15.0 wt. % based on the overall weight of component b); and/or a C2C3 random copolymer matrix and a disperse C2C3 elastomer phase.

6: The multilayer film according to claim 1, wherein: the comonomers of the random propylene copolymer b1) and/or the comonomers of the elastomeric propylene copolymer b2) are ethylene and/or C.sub.4 to C.sub.8 α-olefin.

7: The multilayer film according to claim 1: layers (A) and (C) comprise different materials and layer (C) comprises component a2) selected from the group consisting of a polypropylene homopolymer, a random propylene copolymer and mixtures thereof.

8: The multilayer film according to claim 1, wherein: at least one of layers (A), (B) or (C) comprises at least one plastomer as component c) and component c) is a plastomer comprising ethylene having a density in the range of 0.860 to 0.930 g/cm.sup.3 having a MFR.sub.2 (190° C., 2.16 kg) determined according to ISO 1133 in the range of 0.1 to 40.0 g/10 min.

9: The multilayer film according to claim 1, wherein: the components according to layers (A), (B) and/or (C) each independently from each other comprise additives selected from the group consisting of slip agents, UV-stabiliser, pigments, antioxidants, nucleating agents and mixtures thereof; and/or the components according to layer (A), (B) and/or (C) each independently from each other comprise admixtures selected from the group consisting of pigments, fillers, antiblocking agents and mixtures thereof.

10: The multilayer film according to claim 1, wherein: the content of component a1) or component a2) in layer (A) is in the range of 80 to 100 wt. % based on the overall weight of layer (A) and the content of component c) in layer (A) is in the range of 0 to 20 wt. %, whereby the weight portions of components a1) or a2) and c) add up to 100 wt. %; and/or the content of component a1) or component a2) in layer (C) is in the range of 80 to 100 wt. %; and/or the content of component b) in layer (B) is in the range of 60 to 100 wt. % based on the overall weight of layer (B) and the content of component c) in layer (B) is in the range of 0 to 40 wt. %, whereby the weight portions of components b) and c) add up to 100 wt. %; and/or the content of component c) in layer (B) is in the range of 0 to 40 wt. % based on the overall weight of layer (C); and/or the content of component c) in layer (C) is in the range of 0 to 20 wt. % based on the overall weight of layer (C).

11: The multilayer film according to claim 1, wherein: the multilayer film consists of 3 layers; wherein layers A) and C) are different; and/or the multilayer film consists of 3 layers; wherein layers A) and C) consist of the same materials; and/or the multilayer film is a cast film; and/or layer (B) has a thickness in the range of 45 to 95% with respect to the total thickness of the multilayer film; and/or the multilayer film has a total thickness in the range of 20 to 300 μm.

13: The multilayer film according to claim 1, wherein: the multilayer film consists of layers (A), (B) and (C); whereby layer (A) comprises a terpolymer a1) of propylene, ethylene and 1-butene having: an ethylene content in the range of 0.1 to 8.0 wt. % based on the total weight of the terpolymer a1); a C4-content in the range of 0.1 to 16.0 wt. % based on the total weight of the terpolymer a1); and a melt flow rate MFR.sub.2 measured according to ISO 1133 (230° C., 2.16 kg load) in the range of 0.5 to 12.0 g/10 min; and layer (B) comprises a heterophasic propylene copolymer b), said heterophasic propylene copolymer b) comprises a matrix being a random propylene copolymer b1) and an elastomeric propylene copolymer b2) dispersed in said matrix; whereby the heterophasic propylene copolymer b) has: a melt flow rate MFR.sub.2 measured according to ISO 1133 (230° C., 2.16 kg load) in the range of 0.3 to 20.0 g/10 min; a xylene cold soluble content (XCS) determined according ISO 16152 (25° C.) in the range of 16.0 to 50.0 wt. %; a comonomer content in the range of 11.5 to 21.0 mol %; and a C2-content in the range of 3 to 12 wt. % based on the overall weight of component b);  layer (C) comprises a polypropylene homopolymer a2), said polypropylene homopolymer a2) has: a melt flow rate MFR.sub.2 measured according to ISO 1133 (230° C., 2.16 kg load) in the range of 0.3 to 20.0 g/10 min; and a xylene cold soluble content (XCS) determined according ISO 16152 (25° C.) in the range of 0.1 to 8.0 wt. %.

14: The multilayer film according to claim 1, wherein: layer (A) comprises 2 to 10 wt. % based on the overall weight of layer (A) of a copolymer of ethylene and 1-octene having: a density in the range of 0.860 to 0.930 g/cm.sup.3; and a MFR.sub.2 (190° C., 2.16 kg) determined according to ISO 1133 in the range from 0.1 to 40.0 g/10 min; and/or layer (B) comprises 10 to 35 wt. % based on the overall weight of layer (B) of a copolymer of ethylene and 1-octene having: a density in the range of 0.860 to 0.930 g/cm.sup.3; and a MFR.sub.2 (190° C., 2.16 kg) determined according to ISO 1133 in the range from 0.1 to 40.0 g/10 min.

15. (canceled)

Description

EXPERIMENTAL PART

[0119] A. Measuring Methods

[0120] 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.

[0121] Melt Flow Rate

[0122] The melt flow rate (MFR) was determined according to ISO 1133—Determination of the melt mass-flow rate (MFR) and melt volume-flow rate (MVR) of thermoplastics—Part 1: Standard method and is indicated in g/10 min. The MFR is an indication of the flowability, and hence the processability, of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer. The MFR.sub.2 of polyethylene is determined at a temperature of 190° C. and a load of 2.16 kg. The MFR.sub.2 of polypropylene is determined at a temperature of 230° C. and a load of 2.16 kg.

[0123] Comonomer Content of 1-Octene of a Linear Low Density Polyethylene (LLDPE)

[0124] Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content of the polymers.

[0125] Quantitative .sup.13C{.sup.1H} NMR spectra recorded in the molten-state using a Bruker Avance III 500 NMR spectrometer operating at 500.13 and 125.76 MHz for .sup.1H and .sup.13C respectively. All spectra were recorded using a .sup.13C optimised 7 mm magic-angle spinning (MAS) probehead at 150° C. using nitrogen gas for all pneumatics. Approximately 200 mg of material was packed into a 7 mm outer diameter zirconia MAS rotor and spun at 4 kHz. This setup was chosen primarily for the high sensitivity needed for rapid identification and accurate quantification (Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, H. W., Wilhelm, M., Macromol. Chem. Phys. 2006; 207:382; Parkinson, M., Klimke, K., Spiess, H. W., Wilhelm, M., Macromol. Chem. Phys. 2007; 208:2128; Castignolles, P., Graf, R., Parkinson, M., Wilhelm, M., Gaborieau, M., Polymer 50 (2009) 2373; NMR Spectroscopy of Polymers: Innovative Strategies for Complex Macromolecules, Chapter 24, 401 (2011)). Standard single-pulse excitation was employed utilising the transient NOE at short recycle delays of 3 s (Pollard, M., Klimke, K., Graf, R., Spiess, H. W., Wilhelm, M., Sperber, O., Piel, C., Kaminsky, W., Macromolecules 2004; 37:813; Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, H. W., Wilhelm, M., Macromol. Chem. Phys. 2006; 207:382.) and the RS-HEPT decoupling scheme (Filip, X., Tripon, C., Filip, C., J. Mag. Resn. 2005, 176, 239; Griffin, J. M., Tripon, C., Samoson, A., Filip, C., and Brown, S. P., Mag. Res. in Chem. 2007 45, S1, S198). A total of 1024 (1k) transients were acquired per spectrum. This setup was chosen due its high sensitivity towards low comonomer contents.

[0126] Quantitative .sup.13C{.sup.1H} NMR spectra were processed, integrated and quantitative properties determined using custom spectral analysis automation programs. All chemical shifts are internally referenced to the bulk methylene signal (δ+) at 30.00 ppm (J. Randall, Macromol. Sci., Rev. Macromol. Chem. Phys. 1989, C29, 201.).

[0127] Characteristic signals corresponding to the incorporation of 1-octene were observed (J. Randall, Macromol. Sci., Rev. Macromol. Chem. Phys. 1989, C29, 201; Liu, W., Rinaldi, P., McIntosh, L., Quirk, P., Macromolecules 2001, 34, 4757; Qiu, X., Redwine, D., Gobbi, G., Nuamthanom, A., Rinaldi, P., Macromolecules 2007, 40, 6879) and all comonomer contents calculated with respect to all other monomers present in the polymer.

[0128] Characteristic signals resulting from isolated 1-octene incorporation i.e. EEOEE comonomer sequences, were observed. Isolated 1-octene incorporation was quantified using the integral of the signal at 38.37 ppm. This integral is assigned to the unresolved signals corresponding to both .sub.*B6 and .sub.*βB6B6 sites of isolated (EEOEE) and isolated double non-consecutive (EEOEOEE) 1-octene sequences respectively. To compensate for the influence of the two .sub.*βB6B6 sites the integral of the ββB6B6 site at 24.7 ppm is used:

O=I.sub.*B6+*βB6B6−2*I.sub.ββB6B6

[0129] Characteristic signals resulting from consecutive 1-octene incorporation, i.e. EEOOEE comonomer sequences, were also observed. Such consecutive 1-octene incorporation was quantified using the integral of the signal at 40.57 ppm assigned to the ααB6B6 sites accounting for the number of reporting sites per comonomer:

OO=2*I.sub.ααB6B6

[0130] Characteristic signals resulting from isolated non-consecutive 1-octene incorporation, i.e. EEOEOEE comonomer sequences, were also observed. Such isolated non-consecutive 1-octene incorporation was quantified using the integral of the signal at 24.7 ppm assigned to the ββB6B6 sites accounting for the number of reporting sites per comonomer:

OEO=2*I.sub.ββB6B6

[0131] Characteristic signals resulting from isolated triple-consecutive 1-octene incorporation, i.e. EEOOOEE comonomer sequences, were also observed. Such isolated triple-consecutive 1-octene incorporation was quantified using the integral of the signal at 41.2 ppm assigned to the ααγB6B6B6 sites accounting for the number of reporting sites per comonomer:

OOO=3/2*I.sub.ααγB6B6B6

[0132] With no other signals indicative of other comonomer sequences observed the total 1-octene comonomer content was calculated based solely on the amount of isolated (EEOEE), isolated double-consecutive (EEOOEE), isolated non-consecutive (EEOEOEE) and isolated triple-consecutive (EEOOOEE) 1-octene comonomer sequences:

O.sub.total=O+OO+OEO+OOO

[0133] Characteristic signals resulting from saturated end-groups were observed. Such saturated end-groups were quantified using the average integral of the two resolved signals at 22.84 and 32.23 ppm. The 22.84 ppm integral is assigned to the unresolved signals corresponding to both 2B6 and 2S sites of 1-octene and the saturated chain end respectively. The 32.23 ppm integral is assigned to the unresolved signals corresponding to both 3B6 and 3S sites of 1-octene and the saturated chain end respectively. To compensate for the influence of the 2B6 and 3B6 1-octene sites the total 1-octene content is used:

S=(½)*(I.sub.2S+2B6+I.sub.3S+3B6−2*O.sub.total)

[0134] The ethylene comonomer content was quantified using the integral of the bulk methylene (bulk) signals at 30.00 ppm. This integral included the γ and 4B6 sites from 1-octene as well as the δ.sup.+ sites. The total ethylene comonomer content was calculated based on the bulk integral and compensating for the observed 1-octene sequences and end-groups:

E.sub.total=(½)*[I.sub.bulk+2*O+1*OO+3*OEO+0*OOO+3*S]

[0135] It should be noted that compensation of the bulk integral for the presence of isolated triple-incorporation (EEOOOEE) 1-octene sequences is not required as the number of under and over accounted ethylene units is equal.

[0136] The total mole fraction of 1-octene in the polymer was then calculated as:

fO=(O.sub.total/(E.sub.total+O.sub.total)

[0137] The total comonomer incorporation of 1-octene in mol percent was calculated from the mole fraction in the standard manner:

O[mol %]=100*fO

[0138] The mole percent ethylene incorporation was calculated from the formula:

E[mol %]=100−O[mol %].

[0139] Comonomer Content of C3C2 Polymers

[0140] Quantitative nuclear-magnetic resonance (NMR) spectroscopy was further 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).

[0141] With characteristic signals corresponding to 2,1 erythro regio defects observed (as described in L. Resconi, L. Cavallo, A. Fait, F. Piemontesi, Chem. Rev. 2000, 100 (4), 1253, in Cheng, H. N., Macromolecules 1984, 17, 1950, and in W-J. Wang and S. Zhu, Macromolecules 2000, 33 1157) the correction for the influence of the regio defects on determined properties was required. Characteristic signals corresponding to other types of regio defects were not observed.

[0142] 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.

[0143] 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))

[0144] 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))

[0145] 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.

[0146] The mole percent comonomer incorporation was calculated from the mole fraction:

E[mol %]=100*fE

[0147] The weight percent comonomer incorporation was calculated from the mole fraction:

E[wt %]=100*(fE*28.06)/((fE*28.06)+((1−fE)*42.08))

[0148] The comonomer sequence distribution at the triad level was determined using the analysis method of Kakugo et a1. (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.

[0149] Comonomer Content in Poly(Propylene-Co-Ethylene-Co-Butene) Terpolymers (Component a1)

[0150] Quantitative .sup.13C{.sup.1H} NMR spectra are recorded in the molten-state using a Bruker Advance III 500 NMR spectrometer operating at 500.13 and 125.76 MHz for .sup.1H and .sup.13C respectively. All spectra were recorded using a 13C optimised 7 mm magic-angle spinning (MAS) probehead at 180° C. using nitrogen gas for all pneumatics. Approximately 200 mg of material was packed into a 7 mm outer diameter zirconia MAS rotor and spun at 4.5 kHz. This setup was chosen primarily for the high sensitivity needed for rapid identification and accurate quantification {klimke06, parkinson07, castignolles09}. Standard single-pulse excitation was employed utilising the NOE at short recycle delays {pollard04, klimke06} and the RS-HEPT decoupling scheme{fillip05,griffin07}. A total of 1024 (1k) transients were acquired per spectra.

[0151] Quantitative .sup.13C{.sup.1H} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals. All chemical shifts are internally referenced to the methyl isotactic pentad (mmmm) at 21.85 ppm.

[0152] Characteristic signals corresponding to regio defects were not observed {resconi00}. The amount of propene was quantified based on the main Sαα methylene sites at 44.1 ppm:

Ptotal=I.sub.Sαα

[0153] Characteristic signals corresponding to the incorporation of 1-butene were observed and the comonomer content quantified in the following way. The amount of isolated 1-butene incorporated in PPBPP sequences was quantified using the integral of the αB2 sites at 44.1 ppm accounting for the number of reporting sites per comonomer:

B=I.sub.αB2/2

[0154] The amount consecutively incorporated 1-butene in PPBBPP sequences was quantified using the integral of the ααB2 site at 40.5 ppm accounting for the number of reporting sites per comonomer:

BB=2*I.sub.ααB2

[0155] The total 1-butene content was calculated based on the sum of isolated and consecutively incorporated 1-butene:

Btotal=B+BB

[0156] The total mole fraction of 1-butene in the polymer was then calculated as:

fB=(Btotal/(Etotal+Ptotal+Btotal)

[0157] Characteristic signals corresponding to the incorporation of ethylene were observed and the comonomer content quantified in the following way. The amount isolated ethylene incorporated in PPEPP sequences was quantified using the integral of the Say sites at 37.9 ppm accounting for the number of reporting sites per comonomer:

E=I.sub.Sαγ/2

[0158] With no sites indicative of consecutive incorporation observed the total ethylene comonomer content was calculated solely on this quantity:

Etotal=E

[0159] The total mole fraction of ethylene in the polymer was then calculated as:

fE=(Etotal/(Etotal+Ptotal+Btotal)

[0160] The mole percent comonomer incorporation was calculated from the mole fractions:

B[mol %]=100*fB

E[mol %]=100*fE

[0161] The weight percent comonomer incorporation was calculated from the mole fractions:

B[wt %]=100*(fB*56.11)/((fE*28.05)+(fB*56.11)+((1−(fE+fB))*42.08))

E[wt %]=100*(fE*28.05)/((fE*28.05)+(fB*56.11)+((1−(fE+fB))*42.08))

LITERATURE

[0162] klimke06 [0163] Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, H. W., Wilhelm, M., Macromol. Chem. Phys. 2006; 207:382.

[0164] parkinson07 [0165] Parkinson, M., Klimke, K., Spiess, H. W., Wilhelm, M., Macromol. Chem. Phys. 2007; 208:2128.

[0166] pollard04 [0167] Pollard, M., Klimke, K., Graf, R., Spiess, H. W., Wilhelm, M., Sperber, O., Piel, C., Kaminsky, W., Macromolecules 2004; 37:813.

[0168] filip05 [0169] Filip, X., Tripon, C., Filip, C., J. Mag. Resn. 2005, 176, 239.

[0170] griffin07 [0171] Griffin, J. M., Tripon, C., Samoson, A., Filip, C., and Brown, S. P., Mag. Res. in Chem. 2007 45, S1, S198.

[0172] castignolles09 [0173] Castignolles, P., Graf, R., Parkinson, M., Wilhelm, M., Gaborieau, M., Polymer 50 (2009) 2373.

[0174] busico01 [0175] Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443.

[0176] busico97 [0177] Busico, V., Cipullo, R., Monaco, G., Vacatello, M., Segre, A. L., Macromoleucles 30 (1997) 6251.

[0178] zhou07 [0179] Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag. Reson. 187 (2007) 225.

[0180] busico07 [0181] Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 1128.

[0182] resconi00 [0183] Resconi, L., Cavallo, L., Fait, A., Piemontesi, F., Chem. Rev. 2000, 100, 1253.

[0184] Quantification of Microstructure by NMR Spectroscopy (Component b)

[0185] 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-(111)-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.

[0186] 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 (see Cheng, H. N., Macromolecules 17 (1984), 1950).

[0187] With characteristic signals corresponding to 2,1 erythro regio defects observed (as described in L. Resconi, L. Cavallo, A. Fait, F. Piemontesi, Chem. Rev. 2000, 100 (4), 1253, in Cheng, H. N., Macromolecules 1984, 17, 1950, and in W-J. Wang and S. Zhu, Macromolecules 2000, 33 1157) the correction for the influence of the regio defects on determined properties was required. Characteristic signals corresponding to other types of regio defects were not observed.

[0188] 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.

[0189] 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))

[0190] 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))

[0191] 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.

[0192] The mole percent comonomer incorporation was calculated from the mole fraction:

E[mol %]=100*fE

[0193] The weight percent comonomer incorporation was calculated from the mole fraction:

E[wt %]=100*(fE*28.06)/((fE*28.06)+((1−fE)*42.08))

[0194] The comonomer sequence distribution at the triad level was determined using the analysis method of Kakugo et a1. (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.

[0195] The relative content of isolated to block ethylene incorporation was calculated from the triad sequence distribution using the following relationship (equation (I)):

[00001]$\begin{array}{cc}I\left(E\right)=\frac{fPEP}{\left(fEEE+fPEE+fPEP\right)}\times 100& \left(I\right)\end{array}$

[0196] wherein

[0197] I(E) is the relative content of isolated to block ethylene sequences [in %];

[0198] fPEP is the mol fraction of propylene/ethylene/propylene sequences (PEP) in the sample;

[0199] fPEE is the mol fraction of propylene/ethylene/ethylene sequences (PEE) and of ethylene/ethylene/propylene sequences (EEP) in the sample;

[0200] fEEE is the mol fraction of ethylene/ethylene/ethylene sequences (EEE) in the sample.

[0201] Number Average Molecular Weight (M.sub.n), Weight Average Molecular Weight (M.sub.w) and Molecular Weight Distribution (M.sub.w/M.sub.n)

[0202] The weight average molecular weight M.sub.w and the molecular weight distribution (M.sub.w/M.sub.n), wherein M.sub.n is the number average molecular weight and M.sub.w is the weight average molecular weight) is measured by a method based on ISO 16014-1:2003 and ISO 16014-4:2003. A Waters Alliance GPCV 2000 instrument, equipped with refractive index detector and online viscosimeter was used with 3×TSK-gel columns (GMHXL-HT) from TosoHaas and 1,2,4-trichlorobenzene (TCB, stabilized with 200 mg/L 2,6-Di tert butyl-4-methyl-phenol) as solvent at 145° C. and at a constant flow rate of 1 mL/min. 216.5 μL of sample solution were injected per analysis. The column set was calibrated using relative calibration with 19 narrow MWD polystyrene (PS) standards in the range of 0.5 kg/mol to 11500 kg/mol and a set of well characterized broad polypropylene standards. All samples were prepared by dissolving 5 to 10 mg of polymer in 10 mL (at 160° C.) of stabilized TCB (same as mobile phase) and keeping for 3 hours with continuous shaking prior sampling in into the GPC instrument.

[0203] Xylene Cold Solubles (XCS)

[0204] The xylene soluble (XS) fraction as defined and described in the present invention is determined in line with ISO 16152 as follows: 2.0 g of the polymer were dissolved in 250 ml p-xylene at 135° C. under agitation. After 30 minutes, the solution was allowed to cool for 15 minutes at ambient temperature and then allowed to settle for 30 minutes at 25+/−0.5° C. The solution was filtered with filter paper into two 100 ml flasks. The solution from the first 100 ml vessel was evaporated in nitrogen flow and the residue dried under vacuum at 90° C. until constant weight is reached. The xylene soluble fraction (percent) can then be determined as follows:

[0205] XS %=(100*m*V.sub.0)/(m.sub.0*v); m.sub.0=initial polymer amount (g); m=weight of residue (g); V.sub.0=initial volume (ml); v=volume of analysed sample (ml).

[0206] Melting Temperature T.sub.m and Crystallization Temperature T.sub.c

[0207] The parameters are determined with a TA Instrument Q2000 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. Crystallization temperature (T.sub.c) is determined from the cooling step, while the melting temperature (T.sub.m) is determined from the second heating step. Melting and crystallization temperatures were taken as the peaks of endotherms and exotherms.

[0208] Glass Transition Temperature Tg

[0209] 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.

[0210] Hot Tack Force

[0211] The hot-tack force was determined according to ASTM F1921-12 Method B on a J&B Hot-Tack Tester on a 100 μm thickness film produced on a three-layer cast film co-extrusion line as described below. All film test specimens were prepared in standard atmospheres for conditioning and testing at 23° C. and 50% relative humidity. The minimum conditioning time of test specimen in standard atmosphere before start testing is at least 16 h. The minimum storage time between extrusion of film sample and start testing is at least 88 h. The hot tack measurement determines the strength of heat seals formed in the 5 films, immediately after the seal has been made and before it cools to ambient temperature. The hot-tack measurement was performed under the following conditions.

[0212] Film Specimen width: 25 mm

[0213] Seal bar length: 50 mm

[0214] Seal bar width: 5 mm

[0215] Seal bar shape: flat

[0216] Seal Pressure: 0.15 N/mm.sup.2

[0217] Seal Time: 1 sec

[0218] Cool time: 0.2 sec

[0219] Peel Speed: 200 mm/sec

[0220] Start temperature: 90° C.

[0221] End temperature: 140° C.

[0222] Increments: 5° C.

[0223] The hot tack force was measured as a function of temperature within the temperature range and with temperature increments as indicated above. The number of test specimens were at least 3 specimens per temperature. The output of this method is a hot tack curve; a force vs. temperature curve. The Hot Tack force is evaluated from the curve as the highest force (maximum peak value) with failure mode “peel”, the Hot tack temperature is the one associated to that force.

[0224] Sealing Initiation Temperature (SIT); (Sealing End Temperature (SET), Sealing Range)

[0225] The method determines the sealing temperature range (sealing range) of polypropylene films, in particular blown films or cast films. The sealing temperature range is the temperature range, in which the films can be sealed according to conditions given below. The lower limit (heat sealing initiation temperature (SIT)) is the sealing temperature at which a sealing strength of 5+/−0.5 N is achieved. The upper limit (sealing end temperature (SET)) is reached, when the films stick to the sealing device. The sealing range was determined on a J&B Universal Sealing Machine Type 3000 with a 100 μm thickness film produced on a three-layer cast film co-extrusion line as described below with the following further parameters:

[0226] Specimen width: 25 mm

[0227] Seal Pressure: 0.67 N/mm2

[0228] Seal Time: 1 sec

[0229] Cool time: 30 sec

[0230] Peel Speed: 42 mm/sec

[0231] Start temperature: 80° C.

[0232] End temperature: 150° C.

[0233] Increments: 5° C.

[0234] Specimen is sealed A to A at each sealbar temperature and seal strength (force) is determined at each step. The temperature is determined at which the seal strength reaches 5+/−0.5 N. The Sealing range curves are presented in FIG. 1.

[0235] Tensile Modulus and Tensile Strength

[0236] Tensile modulus and tensile strength in machine direction (MD) and transverse direction (TD) was determined according to ISO 527-3 at 23° C. on 100 μm cast films produced as described below. Testing was performed at a cross head speed of 1 mm/min for the linear modulus range, and at 10 mm/min for higher deformations.

[0237] Instrumented Puncture Test

[0238] The impact strength of films is determined by the instrumented puncture test according to ISO 7765-2 at 0° C. on a 100 μm thickness film produced on a three-layer cast film co-extrusion line as described below. The energy to peak [J/mm] represents the energy absorption in failure up to the peak force [N/mm], while the relative total penetration energy [J/mm] is the total integral that a film can absorb before it breaks, using a test speed of 4.4 m/s. All values are normalized by the film thickness. The higher these values are, the tougher is the material.

[0239] Protrusion Puncture Test

[0240] The resistance of the films to slow puncture is determined by the protrusion puncture resistance test according to ASTM D5748 at 23° C. on a 100 μm thickness film produced on a three-layer cast film co-extrusion line as described below. Both the energy to maximum force [J/mm] and the energy to break [J/mm] are recorded at a test speed of 250 mm/min.

[0241] B. Materials Used

[0242] Terpolymer, Component a1)

[0243] The terpolymer used in the sealing layer of the inventive examples is the polymer TP2 used in inventive example IE2 and comparative example CE2 of WO 2018/069263 A1, based on a non-phthalate Ziegler-Natta catalyst as described for example in WO 2012/007430 A1. This terpolymer has a 1-butene content of 8.9 wt.-%, an ethylene content of 1.0 wt.-% and an MFR 230° C./2.16 kg of 7.1 g/10 min.

[0244] RAHECO, Component b)

[0245] The RAHECO used in the core layer of the inventive examples is the polymer of comparative example CE4 of WO 2019/038395 A1, based on the non-phthalate Ziegler-Natta catalyst of WO 2015/117948 A1, haxing an XCS content of 20 wt.-%, a total ethylene content of 8.0 wt.-% and an MFR 230° C./2.16 kg of 7.0 g/10 min.

[0246] HECO

[0247] The HECO used in the core layer of the comparative examples is the polymer of inventive example IE2b (visbroken) of WO 2018/138235 A1 having an XCS content of 15.5 wt.-%, a total ethylene content of 6.8 wt.-% and an MFR 230° C./2.16 kg of 5.7 g/10 min.

[0248] Random PP (RE216CF)

[0249] RE216CF is an ethylene-propylene random copolymer having a melting temperature of 145° C., available from Borealis AG, Austria (density: 905 kg/m.sup.3, MFR 230° C./2.16 kg=11.0 g/10 min).

[0250] PPH (HD601CF), Component a2)

[0251] HD601CF is a polypropylene homopolymer available from Borealis AG, Austria (density: 910 kg/m.sup.3, MFR 230° C./2.16 kg=8.0 g/10 min).

[0252] Vistamaxx 6202 (Vistamaxx)

[0253] Vistamaxx 6202 is a metallocene-based propylene copolymer having an ethylene content of 15 wt.-%, available from ExxonMobil Chemical, USA (density: 862 kg/m.sup.3, MFR 200° C./2.16 kg=20 g/10 min).

[0254] Plastomer (Queo 8203), Component c)

[0255] Queo 8203 is an ethylene-based octene plastomer available from Borealis AG, Austria (density: 883 kg/m.sup.3, MFR 190° C./2.16 kg=3.0 g/10 min).

[0256] C. Manufacturing of Multilayer Films

[0257] The multilayer films according to the Inventive Examples (IE) and the Comparative Examples (CE) have been produced on a multilayer cast film line equipped with 3 extruders. All three extruders were equipped with a notched feeding zone and a 3-zone screw with mixing and shear parts. The diameter of the cylinder of extruder A is 40 mm and the screw length 25D. Extruder B has a cylinder diameter of 60 mm and a screw length of SOD and extruder C a cylinder diameter of 45 mm and a screw length of 25D. Each extruder was fed by a gravimetric dosing system. A feed block with lamellas and following distribution was used as co-extrusion adapter: Extruder A 10% (skin layer), extruder C 80% (core layer) and extruder B 10% (inner layer). A coat hanger die with automatic die gap regulation was used, die width 800 mm and die gap 0.5 mm. The chill roll unit has a diameter of 450 mm and the 2nd cooling roll 250 mm. The detailed processing parameters are shown in Table 1 below. Table 2 summarizes the produced multilayer films, which all had an overall thickness of 100 μm.

TABLE-US-00001 TABLE 1 Processing conditions for three layer cast films. Extruder A Extruder C Extruder B Layer [μm] 10 80 10 thickness Layer Outer layer (A) Core layer (B) Outer layer (C) Melt ° C. 250 260  250 temperature Melt Bar 45 45 45 pressure Screw U/min 8 45 6 speed output Kg/h 6 48 6 Coex 260 adapter temperature Die 250 temperature Chill roll ° C. 12 temperature 2.sup.nd cooling ° C. 21 roll temperature Take off m/min 7.4 speed winder

TABLE-US-00002 TABLE 2 Produced multilayer films. IE1 IE2 CE1 CE2 CE3 Layer Terpoly- Terpolymer Random Random Random (A) mer Plastomer PP PP PP Amount 100 95 100 100 100 [wt.-%]  5 Layer RAHECO RAHECO HECO HECO HECO (B) Plastomer Vistamaxx Plastomer Plastomer Amount 100 75  50  75  60 [wt.-%] 25  50  25  40 Layer PPH PPH PPH PPH PPH (C) Amount 100 100  100 100 100 [wt.-%] Total 100 100  100 100 100 Thickness [μm]

[0258] D. Results

TABLE-US-00003 TABLE 3 Properties of the multilayer films. Unit IE1 IE2 CE1 CE2 CE3 Hot Tack Force N 3.91 6.38 3.95 3.56 2.44 Hot Tack Temperature ° C. 105 100 126 110 100 Max. Force N 31.41 24.95 20.71 23.83 25.25 SIT ° C. 110 108 123 122 122 Tensile test Tensile Modulus MD MPa 471 416 274 535 440 Tensile Modulus TD MPa 442 379 228 471 384 Tensile Strength MD MPa 37 36 29 40 34 Tensile Strength TD MPa 30 32 31 30 32 Instrumented puncture test Energy to Peak J/mm 10.8 27.9 21.8 27.9 25.6 Peak Force N/mm 1052 1155 1045 1185 1141 Total Penetration J/mm 17.4 28.5 22.8 28.6 26.3 Protrusion resistance test Energy to Break J/mm 85 98 73 85 83 Energy to Maximum Force J/mm 77 75 53 62 60

[0259] E. Discussion of the Results

[0260] Table 3 summarizes the tests conducted with the multilayer films according to the Inventive Examples IE1 and IE2 and the Comparative Examples CE1 to CE3. When comparing the data, it is necessary to take into account, that IE2 and all Comparative Examples contain a plastomer, whereas IE1 is free of plastomers. The skilled person is well aware that the plastomer influences the properties of the films, therefore IE2 is suited for a comparison of the properties with the films according to the Comparative Examples. However, IE1 demonstrates that films with very good sealing properties are also obtainable without the presence of a plastomer in one of the layers.

[0261] From Table 3 can be gathered that the multilayer films IE1 and IE2 according to the present invention have a lower sealing initiation temperature (=SIT) than the multilayer films according to the Comparative Examples CE1 to CE3. In addition, it is possible to increase the Hot Tack Force of the multilayer films according to the present invention by addition of a plastomer (comparison of IE2 with IE1). The multilayer film according to IE2 shows a significantly higher Hot Tack Force than the multilayer films according to the Comparative Examples. Furthermore, the multilayer films according to the present invention IE1 and IE2 have a reduced Hot Tack Temperature and an increased Max. Force compared to CE1 to CE3.

[0262] In addition, the multilayer films according to IE1 and IE2 show a higher Energy to Break and Energy to Maximum Force than the multilayer films according to the Comparative Examples, whereas the remaining mechanical properties are approximately at the same level.

[0263] To sum it up, the sealing properties of the multilayer films according to the Inventive Examples IE1 and IE2 are much better than for the multilayer films according to Comparative Examples CE1 to CE3 and the multilayer films according to the present invention show improved mechanical properties, especially Energy to Break and Energy to Maximum Force.