Polyethylene composition for film layers

Abstract

The present invention relates to a composition comprising metallocene catalyzed multimodal linear low density polyethylene (mLLDPE) and HDPE recoverable, the use of the composition in film applications and a film comprising the polymer composition of the invention.

Description

[0001] The present invention relates to a composition comprising metallocene-catalyzed multimodal linear low density polyethylene (mLLDPE) and HDPE recyclate, the use of the composition in film applications and a film comprising the polymer composition of the invention.

[0002] Polyolefins, especially polyethylene and polypropylene, are increasingly consumed in large quantities in a wide range of applications including packaging of food and other goods.

[0003] Polyethylene-based materials are a particular problem, as these are widely used in packaging. Considering the huge amounts of waste collected compared to the amount of waste recycled into the stream, there is still great potential for the intelligent reuse of plastic waste streams and for the mechanical recycling of plastic waste.

[0004] Therefore, it is important to form a circular economy that gives plastic waste a second life, i.e. recycling it. This not only prevents plastic waste from remaining in the environment, but also restores its value.

[0005] In addition, the European Commission confirmed in 2017 that it would focus on plastic production and use. The EU's goals are: 1) by 2025, at least 55% of all plastic packaging in the EU should be recycled; 2) by 2030, all plastic packaging on the EU market should be reusable or easily recyclable. This has prompted brand owners and plastic converters to seek solutions using recyclables or a mix of virgin / recyclables.

[0006] Therefore, incorporating polymers obtained from waste into the manufacture of new products is becoming increasingly important, i.e. where waste plastics, such as post-consumer recyclate (PCR), can be transformed into a resource for new plastic products. Thus, environmental and economic aspects can be combined when recycling and reusing waste plastic materials.

[0007] However, recycled plastics are often of lower quality than virgin plastics due to degradation, contamination and mixing of different plastics.

[0008] In addition, compositions containing recycled polyolefin materials generally have properties that are much worse than those of virgin materials, unless the amount of recycled polyolefin added to the final composition is extremely low. For example, such materials generally have limited impact strength and poor mechanical properties, and therefore, they cannot meet consumer requirements.

[0009] Mixing recycled plastic with virgin plastic is a common practice to improve the quality of recycled plastic.

[0010] Based on this, it is an object of the present invention to provide a polyethylene-based composition allowing the use of recycled HDPE, which can be used to produce films having good properties, in particular good mechanical properties such as impact resistance and stiffness.

[0011] Furthermore, it should be possible to add higher amounts of recyclables to the composition.

[0012] The present inventors have now found that blends of metallocene-catalyzed multimodal linear low density polyethylene (mLLDPE) prepared with specific metallocene catalysts and having a specific polymer design with HDPE recyclate (i.e. polyethylene recycled blends) provide films with an improved balance of properties, particularly in terms of stiffness (i.e. tensile modulus) and impact resistance, such as dart impact strength. Summary of the invention

[0013] The present invention therefore relates to a composition comprising

[0014] (I) 50.0 to 99.0 wt% of a metallocene-catalyzed multimodal linear low density polyethylene (mLLDPE), based on the total weight of the composition, the metallocene-catalyzed multimodal linear low density polyethylene (mLLDPE) consisting of

[0015] (i) 30.0 to 70.0 wt% of an ethylene-1-butene polymer component (A) based on the total weight of mLLDPE and

[0016] (ii) 70.0 to 30.0 wt% of an ethylene-1-hexene polymer component (B), based on the total weight of the mLLDPE,

[0017] wherein the ethylene-1-butene polymer component (A) has

[0018] ●925 to 960 kg / m 3 Density in the range of 1.0 to 100.0 g / 10min (ISO 1183) and MFR in the range of 1.0 to 100.0 g / 10min 2 (190℃, 2.16kg, ISO 1133);

[0019] The ethylene-1-hexene polymer component (B) has

[0020] 880 to 915 kg / m 3 Density in the range (ISO 1183) and MFR in the range of 0.001 to 1.0 g / 10min 2 (190°C, 2.16kg, ISO 1133); and

[0021] Among them, multimodal linear low density polyethylene (mLLDPE) has

[0022] 910 to 923 kg / m 3 Density in the range (ISO 1183),

[0023] ●MFR in the range of 0.1 to 1.2 g / 10min 2 (190°C, 2.16kg, ISO 1133), and

[0024] ●MFR in the range of 5.0 to 75.0 g / 10min 21 (190°C, 21.6kg, ISO 1133), and

[0025] MFR in the range of 35.0 to 60.0 21 / MFR 2 ratio; and

[0026] (II) 1.0 to 50.0 wt% of a polyethylene recycled blend (PCR), based on the total weight of the composition, having

[0027] (i) MFR in the range of 0.1 to 10.0 g / 10 min 5 (ISO1133, 5.0 kg; 190°C), and

[0028] (ii) 950 to 970 kg / m 3 Density within the range (ISO1183), and

[0029] (iii) a C2 fraction in an amount greater than 95.0 wt% as measured by NMR of the d2-tetrachloroethylene soluble fraction, and

[0030] (iv) a homopolymer fraction (HPF) having a content ranging from 80.0 to 91.0 wt% based on PCR as determined by chemical composition analysis by cross fractionation chromatography (CFC), and

[0031] (v) a PCR-based copolymer fraction (CPF) content in the range of 9.0 to 20.0 wt% as determined by chemical composition analysis by cross fractionation chromatography (CFC), and

[0032] (vi) optionally a PCR-based iso-PP fraction (IPPF) content in the range of 0.0 to 2.0 wt% as determined according to chemical composition analysis by cross fractionation chromatography (CFC), wherein the iso-PP fraction (IPPF) is defined as the polymer fraction eluting at a temperature of 104°C and above, wherein the homopolymer fraction (HPF), the copolymer fraction (CPF) and the iso-PP fraction (IPPF) add up to 100 wt%, and

[0033] (vii) 0.01 to 2.00 wt% inorganic residue (measured by TGA) relative to the total polyethylene recycled blend, and

[0034] (viii) 10m by OCS counting instrument 2 OCS gels having a size of 100 to 299 microns measured in the range of 500 to 5000 counts / square meter; wherein

[0035] (ix) CIELAB color space (L * a * b * )for

[0036] -L * 75.0 to 86.0;

[0037] -a * -5.0 to 0.0;

[0038] -b * 5.0 to less than 25.0

[0039] or

[0040] (x) CIELAB color space (L * a * b * )for

[0041] -L * Above 86.0 to 97.0;

[0042] -a * -5.0 to 0.0;

[0043] -b * 0.0 to less than 5.0.

[0044] In one embodiment of the present invention, the ethylene-1-butene polymer component (A) of the metallocene-catalyzed multimodal linear low density polyethylene (mLLDPE) consists of an ethylene polymer fraction (A-1) and an ethylene polymer fraction (A-2), wherein the density (ISO 1133) of fractions (A-1) and (A-2) is in the range of 925 to 960 kg / m 3 Within the range and MFR 2 (190°C, 2.16 kg, ISO 1133) is in the range of 1.0 to 150 g / 10 min, and wherein the density and / or MFR of the ethylene polymer parts (A-1) and (A-2) is 2 (190°C, 2.16kg, ISO 1133) can be the same or different.

[0045] Unexpectedly, such compositions provide films having an excellent combination of stiffness and impact resistance (ie, tensile modulus and dart drop strength).

[0046] The present invention therefore further relates to a film comprising at least one layer comprising the composition according to the invention.

[0047] The specific design of the metallocene-catalyzed multimodal linear low density polyethylene (mLLDPE) thus allows for the addition of more recyclables and still provides a film with a good impact / stiffness balance.

[0048] definition

[0049] Where the term "comprising" is used in the present description and claims, it does not exclude other, not specifically stated, elements of major or minor functional importance. For the purposes of the present invention, the term "consisting of" is considered to be a preferred embodiment of the term "comprising". If a group is defined hereinafter as comprising at least a certain number of embodiments, this is also to be understood as disclosing the group, which preferably consists only of these embodiments.

[0050] Whenever the terms "including" or "having" are used, these terms are meant to be equivalent to "comprising" as defined above.

[0051] When an indefinite or definite article is used when referring to a singular noun, for example "a", "an" or "the", this includes a plural of that noun unless otherwise stated.

[0052] Metallocene-catalyzed multimodal polyethylene is defined in the present invention as a multimodal polyethylene prepared in the presence of a metallocene catalyst with at least two different comonomers selected from alpha-olefins having from 4 to 10 carbon atoms.

[0053] In contrast to Ziegler Natta catalysis, polyethylene polymers produced in the presence of metallocene catalysts have characteristics that distinguish them from Ziegler Natta materials. In particular, the comonomer distribution is more uniform. This can be shown using TREF or Crystaf techniques. Catalyst residues can also be indicative of the catalyst used. For example, Ziegler Natta catalysts do not contain Zr or Hf Group (IV) metals.

[0054] For the purposes of the present invention, "linear low density polyethylene (LLDPE) comprising a polyethylene component (A) and a polyethylene component (B)" means that the LLDPE is produced in at least a two-stage sequential polymerization process, wherein component (A) is produced first and then, in a subsequent polymerization step, component (B) is produced in the presence of component (A) to produce the LLDPE, or vice versa, i.e. component (B) is produced first and then, in a subsequent polymerization step, component (A) is produced in the presence of component (B) to produce the LLDPE.

[0055] LLDPE produced in a multistage process is also known as an "in-situ" blend or a "reactor" blend. The resulting final product consists of an intimate mixture of polymers from two or more reactors whose different molecular weight distribution curves together form a molecular weight distribution curve with a broad maximum or two or more maxima, i.e., the final product is a multimodal polymer mixture.

[0056] In the context of a multimodal polyethylene, the term "multimodal" refers herein to multimodality with respect to the melt flow rate (MFR) of the ethylene polymer components (A) and (B), i.e. the ethylene polymer components (A) and (B) have different MFR values. The multimodal polyethylene may further have multimodality with respect to one or more other properties between the ethylene polymer components (A) and (B) and between the fractions (A-1) and (A-2), as described below.

[0057] Linear low density polyethylene (LLDPE) is defined in the present invention as having a density of 910 to 923 kg / m 3 range of polyethylene.

[0058] The multimodal linear low density polyethylene (mLLDPE) of the present invention as defined above, below or in the claims is herein also referred to as "mLLDPE" for short.

[0059] The ethylene-1-butene polymer component (A) and the ethylene-1-hexene polymer component (B), when both are mentioned, are also referred to as "ethylene polymer components (A) and (B)".

[0060] The following preferred embodiments, properties and subgroups of mLLDPE and its ethylene polymer components (A) and (B), and its ethylene polymer parts (A-1) and (A-2), and the films of the present invention including their preferred ranges are independently generalizable such that they can be used in any order or combination to further define the preferred embodiments of the mLLDPE and articles of the present invention.

[0061] For the purpose of this specification and the subsequent claims, the term "polyethylene recovery blend (PCR)" is defined as the presence of at least two different polyethylenes, such as two high density polyethylenes of different densities. For example, bimodal polyethylene obtained from two reactors operating under different conditions constitutes a polyethylene blend, in this case an in situ blend of the two reactor products.

[0062] It goes without saying that polyethylene blends obtained from consumer waste will include a variety of polyethylenes. In addition to being contaminated with other plastics (mainly polypropylene, polystyrene, polyamide, polyester), wood, paper, limonene, aldehydes, ketones, fatty acids, metals and / or stabilizer long-term decomposition products may also be found. It goes without saying that such contamination is undesirable.

[0063] It should be understood that the polyethylene recycled blend of the present invention is not a cookie-cutter blend like some commercially available recyclables.The polyethylene recycled blend according to the present invention should be different from the virgin blend.

[0064] The term "C2 moiety" refers to repeating -[C2H4]- units derived from ethylene, present in a linear backbone and short chain branches, as measured by quantitative 13C{1H} NMR spectroscopy, wherein the repeating means at least two units.

[0065] The C2 part can be calculated as follows

[0066] wtC2 portion = fCC2 total * 100 / (fCC2 total + fCPP)

[0067] in

[0068] fCC2 total = (Iddg – ItwoB4) + (IstarB1 * 6)+(IstarB2 * 7)+(ItwoB4 * 9)

[0069] +(IthreeB5 * 10)+((IstarB4plus-ItwoB4-IthreeB5) * 7)+(I3s * 3) and

[0070] fCPP=Isαα * 3

[0071] Details are given in the experimental section.

[0072] Due to the presence of HDPE, LDPE or LLDPE, polyethylene homopolymers and polyethylene copolymers in the recycled blends, analytical separation becomes an essential means for characterization. An appropriate method is the chemical composition analysis by cross fractionation chromatography (CFC). This method has been described and successfully implemented by Polymer Char, Valencia Technology Par, Gustave Eiffel 8, Paterna E-46980 Valencia, Spain. The chemical composition analysis by cross fractionation chromatography (CFC) allows fractionation into a homopolymer fraction (HPF) and a copolymer fraction (CPF) and possible iso-PP (IPPF). The homopolymer fraction (HPF) is a fraction that includes polyethylene similar to homopolymer-HDPE. The copolymer fraction (CPF) is a fraction similar to polyethylene HDPE copolymers, but may also include LDPE (respectively LLDPE) fractions. The iso-PP fraction (IPPF) includes isotactic polypropylene and is defined as the polymer fraction eluting at temperatures of 104°C and above. The homopolymer fraction (HPF), the copolymer fraction (CPF) and any iso-PP fraction (IPPF) added up to 100 wt. %. It goes without saying that 100 wt. % refers to the material that is soluble in a cross fractionation chromatography (CFC) experiment.

[0073] In addition to the chemical composition analysis by cross fractionation chromatography (CFC), the polyethylene blend according to the invention is characterized in that the amount of C2 fraction measured by NMR of the d2-tetrachloroethylene soluble fraction is greater than 95.0 wt%, preferably greater than 97.0 wt%. The percentages refer to the d2 tetrachloroethylene soluble fraction used for the NMR experiment. The term "C2 fraction" is equal to the polymer fraction obtainable from ethylene monomer units, i.e. not obtained from propylene monomer units.

[0074] The upper limit of the "C2 fraction" is 100 wt%.

[0075] Composition

[0076] The composition of the present invention comprises

[0077] (I) 50.0 to 99.0 wt%, preferably 60.0 to 95.0 wt%, more preferably 70.0 to 90.0 wt% of a metallocene-catalyzed multimodal linear low density polyethylene (mLLDPE), and

[0078] (II) 1.0 to 50.0 wt%, preferably 5.0 to 40.0 wt%, more preferably 10.0 to 30.0 wt% of a polyethylene recycled blend (PCR).

[0079] Preferably, the amounts of (I) and (II) added together are at most 100.0 wt%.

[0080] (I) Multimodal mLLDPE and ethylene polymer components (A) and (B) and ethylene polymer fractions (A-1) and (A-2)

[0081] The metallocene-catalyzed multimodal linear low density polyethylene (mLLDPE) is referred to herein as "multimodal" because the ethylene-1-butene polymer component (A) (optionally including ethylene polymer fractions (A-1) and (A-2)) and the ethylene-1-hexene polymer component (B) are produced under different polymerization conditions, resulting in different melt flow rates (MFR, e.g. MFR 2 ). That is, the multimodal mLLDPE has at least an MFR of about the ethylene polymer components (A) and (B). 2 The differences are multimodal.

[0082] In an embodiment of the present invention, the ethylene-1-butene polymer component (A) consists of ethylene polymer parts (A-1) and (A-2).

[0083] As mentioned above, the MFR of the ethylene polymer components (A) and (B) 2 Different from each other.

[0084] MFR of ethylene-1-butene polymer component (A) 2 In the range of 1.0 to 100.0 g / 10 min, preferably 8.0 to 80.0 g / 10 min, more preferably 10.0 to 70.0 g / 10 min, even more preferably 12.0 to 60.0 g / 10 min.

[0085] MFR of ethylene-1-hexene polymer component (B) 2 In the range of 0.001 to 1.0 g / 10 min, preferably 0.002 to 0.8 g / 10 min, more preferably 0.003 to 0.5 g / 10 min, even more preferably 0.003 to 0.2 g / 10 min.

[0086] In the case where the ethylene-1-butene polymer component (A) consists of ethylene polymer fractions (A-1) and (A-2), the MFR of the ethylene polymer fractions (A-1) and (A-2) is 2 May be different from each other or may be the same.

[0087] MFR of ethylene polymer parts (A-1) and (A-2) 2 In the range of 1.0 to 150.0 g / 10 min, preferably 8.0 to 120.0 g / 10 min, more preferably 10.0 to 100.0 g / 10 min, even more preferably 12.0 to 90.0 g / 10 min, such as 15.0 to 85.0 g / 10 min.

[0088] In one embodiment of the present invention, the MFR of the ethylene polymer portion (A-2) is 2 Equal to or preferably higher than the MFR of the ethylene polymer portion (A-1) 2 .

[0089] Therefore, the MFR of part (A-2) 2 MFR of part (A-1) 2 The ratio of MFR 2 (A-2) / MFR 2 (A-1) is in the range of ≥1.0 to 100, preferably 1.5 to 50, more preferably 2.0 to 10.

[0090] MFR of multimodal mLLDPE 2 In the range of 0.1 to 1.2 g / 10 min, preferably 0.2 to 1.0 g / 10 min, more preferably 0.2 to 0.8 g / 10 min.

[0091] The MFR of the multimodal mLLDPE 21 (190° C., 21.6 kg, ISO 1133) is in the range of 5.0 to 75.0 g / 10 min, preferably 8.0 to 50.0 g / 10 min, more preferably 10.0 to 30.0 g / 10 min.

[0092] MFR of multimodal mLLDPE 21 / MFR 2 The ratio is in the range of 35.0 to 60.0, preferably 40.0 to 55.0, more preferably 42.0 to 50.0.

[0093] Of course, in addition to the MFR of the ethylene polymer components (A) and (B) 2 In addition to the multimodality of (ie the difference between) the density of the ethylene polymer components (A) and (B), the multimodal mLLDPE of the invention may also be multimodal, for example with respect to the density of the ethylene polymer components (A) and (B).

[0094] Preferably, the density of the ethylene polymer component (A) is different from, preferably higher than, the density of the ethylene polymer component (B).

[0095] The density of the ethylene polymer component (A) is 925 to 960 kg / m 3 , preferably 930 to 955 kg / m 3 , more preferably 932 to 952 kg / m 3 The density of the ethylene polymer component (B) is in the range of 880 to 915 kg / m 3 , preferably 890 to 905 kg / m 3 within the range.

[0096] The density of the polymer parts (A-1) and (A-2) is 925 to 960 kg / m 3 , preferably 930 to 958 kg / m 3 , more preferably 935 to 955 kg / m 3 , such as 940 to 952 kg / m 3 within the range.

[0097] The densities of the polymer parts (A-1) and (A-2) may be the same as or may be different from each other.

[0098] The density of multimodal mLLDPE is between 910 and 923 kg / m 3 , preferably 912 to 922 kg / m 3 , more preferably 914 to 922 kg / m 3 , even more preferably 915 to 921 kg / m 3 within the range.

[0099] More preferably, the multimodal mLLDPE has at least 2 , the comonomer types are multimodal (i.e. there is a difference between them) and the density with respect to the ethylene polymer components (A) and (B) is multimodal (i.e. there is a difference between them), as defined above, below or in the claims, the claims including any preferred ranges or embodiments of the polymer composition.

[0100] Within the scope of the present invention, the first polymer portion (A-1) and the second ethylene polymer portion (A-2) of the ethylene-1-butene polymer component (A) are present in a weight ratio of 4:1 to 1:4, for example 3:1 to 1:3, or 2:1 to 1:2, or about 1:1.

[0101] The ethylene-1-butene polymer component (A) is present in an amount of 30.0 to 70.0 wt%, preferably in an amount of 32.0 to 55.0 wt%, even more preferably in an amount of 34.0 to 48.0 wt%, based on the multimodal mLLDPE.

[0102] Thus, the ethylene-1-hexene polymer component (B) is present in an amount of 70.0 to 30.0 wt%, preferably in an amount of 68.0 to 45.0 wt%, more preferably in an amount of 66.0 to 52.0 wt%, based on the multimodal mLLDPE.

[0103] The metallocene-catalyzed multimodal mLLDPE can be produced in a two-stage process, which preferably comprises a slurry reactor (loop reactor), wherein the slurry (loop) reactor is connected in series to a gas phase reactor (GPR), wherein ethylene polymer component (A) is produced in the loop reactor and ethylene polymer component (B) is produced in the GPR in the presence of ethylene polymer component (A) to produce the multimodal mLLDPE.

[0104] In case the ethylene component (A) of the multimodal mLLDPE consists of ethylene polymer fractions (A-1) and (A-2), the multimodal mLLDPE can be produced in a three-stage process, which preferably comprises a first slurry reactor (loop reactor 1), wherein the first slurry loop reactor is connected in series to a further slurry reactor (loop reactor 2) such that the first ethylene polymer fraction (A-1) produced in loop reactor 1 is fed to loop reactor 2, where the second ethylene polymer fraction (A-2) is produced in the presence of the first fraction (A-1). Thus, loop reactor 2 is connected in series to a gas phase reactor (GPR) such that the ethylene polymer fraction (A) leaving the second slurry reactor is fed to the GPR to produce a trimodal mLLDPE. In this case, the reaction conditions in the two slurry reactors are selected such that an MFR 2 and / or products that differ in density.

[0105] Such processes are described inter alia in WO 2016198273, WO 2021009189, WO 2021009190, WO 2021009191 and WO 2021009192. Full details on how to prepare suitable metallocene-catalyzed multimodal mLLDPE can be found in these references.

[0106] A suitable process is the Borstar PE process or the Borstar PE 3G process.

[0107] Therefore, the metallocene-catalyzed multimodal mLLDPE according to the invention is preferably produced in a loop-loop-gas phase cascade. Such a polymerization step may be preceded by a prepolymerization step. The purpose of the prepolymerization is to polymerize a small amount of polymer onto the catalyst at low temperature and / or low monomer concentration. By prepolymerization, the performance of the catalyst in slurry can be improved and / or the properties of the final polymer can be modified. The prepolymerization step is preferably carried out in slurry.

[0108] When there is a prepolymerization step, the catalyst components are preferably all introduced into the prepolymerization step. However, when the solid catalyst component and the cocatalyst can be fed separately, it is possible that only a part of the cocatalyst is introduced into the prepolymerization stage, while the rest is introduced into the subsequent polymerization stage. Moreover, in this case, it is necessary to introduce so much cocatalyst into the prepolymerization stage in order to obtain a sufficient polymerization reaction therein.

[0109] It is to be understood that within the scope of the present invention the amount of polymer produced in the prepolymerisation is within 1 to 5 wt% relative to the final metallocene-catalysed multimodal mLLDPE. This is counted as part of the ethylene polymer component (A).

[0110] catalyst

[0111] The metallocene-catalyzed multimodal mLLDPE used in the method of the present invention is mLLDPE prepared using a metallocene catalyst. The metallocene catalyst comprises a metallocene complex and a cocatalyst. The metallocene compound or complex is also referred to herein as an organometallic compound (C).

[0112] The organometallic compound (C) comprises a transition metal (M) from Groups 3 to 10 of the Periodic Table of Elements (IUPAC 2007) or from the actinides or lanthanides.

[0113] According to the present invention, the term "organometallic compound (C)" includes any metallocene or non-metallocene compound of a transition metal, which carries at least one organic (coordinating) ligand and exhibits catalytic activity alone or together with a cocatalyst. Transition metal compounds are well known in the art, and the present invention encompasses compounds of metals from Groups 3 to 10, e.g. Groups 3 to 7, or Groups 3 to 6, e.g. Groups 4 to 6, of the Periodic Table (IUPAC 2007), as well as lanthanides or actinides.

[0114] In one embodiment, the organometallic compound (C) has the following formula (I):

[0115]

[0116] Wherein each X is independently a halogen atom, C 1-6 -alkyl, C 1-6 - alkoxy, phenyl or benzyl;

[0117] Each Het is independently a monocyclic heteroaromatic group containing at least one heteroatom selected from O or S;

[0118] L is -R'2Si-, wherein each R' is independently a C1-20-hydrocarbon group or a C1-10-alkyl group substituted with an alkoxy group having 1 to 10 carbon atoms;

[0119] M is Ti, Zr or Hf;

[0120] Each R 1 Same or different, is C 1-6 -alkyl or C 1-6 - alkoxy;

[0121] Each n is 1 to 2;

[0122] Each R 2 Same or different, is C 1-6 -alkyl, C 1-6 -alkoxy or -Si(R) 3 Group;

[0123] Each R is optionally replaced by 1 to 3 C 1-6 -alkyl substituted C 1-10 -alkyl or phenyl; and each p is 0 to 1.

[0124] Preferably, the compound of formula (I) has the following structure (I')

[0125]

[0126] Wherein each X is independently a halogen atom, C 1-6 -alkyl, C 1-6 -alkoxy, phenyl or benzyl; L is Me 2 Si-;

[0127] Each R 1 Same or different and C 1-6 - alkyl, for example methyl or tert-butyl;

[0128] Each n is 1 to 2;

[0129] R 2 Yes-Si(R) 3 Alkyl; each p is 1;

[0130] Each R is C 1-6 -alkyl or phenyl.

[0131] Highly preferred complexes of formula (I) or (I') are

[0132]

[0133] Most preferably, the complex dimethylsilanediylbis[2-(5-trimethylsilylfuran-2-yl)-4,5-dimethylcyclopentadien-1-yl]zirconium dichloride is used as the organometallic compound (C) of the following formula (I).

[0134] More preferably, the ethylene polymer components (A) and (B) of the multimodal mLLDPE are prepared using, ie in the presence of, the same metallocene catalyst.

[0135] To form the catalyst, a cocatalyst, also called an activator, well known in the art is used. Cocatalysts containing Al or B are well known and can be used here. Preferably, aluminoxanes (such as MAO) and / or boron-based cocatalysts (such as borates) are used.

[0136] The metallocene-catalyzed multimodal mLLDPE may contain other polymer components and optional additives and / or fillers. In case the metallocene-catalyzed multimodal mLLDPE contains other polymer components, the amount of the other polymer components typically varies between 3.0 and 20.0 wt%, based on the total amount of the metallocene-catalyzed multimodal mLLDPE and the other polymer components.

[0137] Optional additives and fillers and the amounts used are conventional in the field of film applications. Examples of such additives are, inter alia, antioxidants, processing stabilizers, UV stabilizers, pigments, fillers, antistatic additives, antiblocking agents, nucleating agents, acid scavengers and polymer processing aids (PPAs).

[0138] It is to be understood herein that any additives and / or fillers may optionally be added to a so-called masterbatch comprising the respective additive and a carrier polymer.

[0139] (II) Polyethylene recycled blend (PCR)

[0140] In addition to the metallocene-catalyzed multimodal mLLDPE, the composition of the invention also comprises a polyethylene recycled blend (PCR).

[0141] Melt flow rate MFR of the polyethylene recycled blend (PCR) according to the present invention 5 (ISO 1133, 5.0 kg; 190 ° C) is typically in the range of 0.1 to 10 g / 10 min. The melt flow rate can be affected by segmenting post-consumer plastic waste streams, for example but not limited to: originating from extended producer responsibility programs such as the German DSD, or sorting out a large number of pre-sorted fractions from municipal solid waste and recombining them in an appropriate way. Typically MFR 5 In the range of 0.5 to 5.0 g / 10 min, preferably 0.7 to 4.0 g / 10 min, most preferably 1.0 to 3.0 g / 10 min.

[0142] The polyethylene recycled blend (PCR) according to the present invention has a C2 fraction higher than 95.0 wt%, preferably higher than 97.0 wt%, more preferably higher than 98.0 wt%, most preferably higher than 99.0 wt%, as measured by NMR of the d2-tetrachloroethylene soluble fraction.

[0143] Typically, recycling properties can be assessed by the presence of one or more of the following:

[0144] (1) an inorganic residue content higher than 0.01 wt% (measured by thermogravimetric analyzer); at the same time, 10 m2 OCS gels with sizes ranging from 100 to 299 microns were measured in the range of 500 to 5000 counts / m2 for the membrane;

[0145] Alternatively or in combination

[0146] (2) limonene in an amount of 0.5 ppm or more as determined by using solid phase microextraction (HS-SPME-GC-MS);

[0147] Alternatively or in combination

[0148] (3) Fatty acids selected from the group consisting of acetic acid, butyric acid, valeric acid and hexanoic acid, the total amount of which is 10 ppm or more as measured by using solid phase microextraction (HS-SPME-GC-MS).

[0149] In embodiments of the present invention, options (2) and (3) are preferred.

[0150] "Fatty acids selected from the group consisting of acetic acid, butyric acid, valeric acid and caproic acid" means that the individual amounts of acetic acid, butyric acid, valeric acid and caproic acid (determined in ppm by HS-SPME-GC-MS) are added together.

[0151] The detection limit of limonene in solid phase microextraction (HS-SPME-GC-MS) is below 0.1 ppm, which means that trace amounts of these substances can be easily determined and their recovery properties can be determined.

[0152] It goes without saying that the content of inorganic residues, gels, limonene and fatty acids should be as low as possible.

[0153] Particularly preferred is that limonene is present in an amount of 0.1 to 25 ppm, even more preferably 0.1 to 20 ppm, as determined by using solid phase microextraction (HS-SPME-GC-MS); and / or the total amount of fatty acids consisting of the group of acetic acid, butyric acid, valeric acid and caproic acid is present in a total amount of at least 10 to 500 ppm, more preferably 10 to 300 ppm, most preferably 10 to 180 ppm, as determined by using solid phase microextraction (HS-SPME-GC-MS).

[0154] With regard to color, two embodiments can be distinguished: an essentially colorless blend and an essentially white blend.

[0155] CIELAB color space (L * a * b * )for

[0156] L *From 75.0 to 86.0;

[0157] a * From -5.0 to 0.0;

[0158] b * From 5.0 to less than 25.0

[0159] CIELAB color space (L * a * b * )for

[0160] L * from above 86.0 to 97.0;

[0161] a * From -5.0 to 0.0;

[0162] b * From 0.0 to below 5.0.

[0163] The polyethylene recycled blend (PCR) according to the invention is preferably characterized by an odor (VDA270-B3) of 2.5 or less, preferably 2.0 or less. It should be understood that many commercial recycled grades that do not report an odor are actually even unacceptable in this respect, since the sniff test proposed by VDA270 is prohibited due to the presence of problematic or toxic substances.

[0164] The polyethylene recycled blend (PCR) according to the present invention has one or more of the following OCS gel count properties (for 10 m 2 Membrane measurement):

[0165] Size 300 to 599 microns: 100 to 2500 counts / m²

[0166] Size 600 to 1000 microns: 5 to 200 counts / m²

[0167] Size greater than 1000 microns: 1 to 40 counts / m²

[0168] OCS gels are given in counts / m2, calculated as 10m 2 The average value of the membrane.

[0169] In another aspect, the polyethylene recycled blend (PCR) according to the present invention has a tensile modulus (ISO 527-2, crosshead speed 1 mm / min; 23° C.) of at least 825 MPa, preferably at least 850 MPa, most preferably at least 910 MPa, measured using injection molded specimens as described in EN ISO 1873-2 (dog bone shape, 4 mm thickness). Typically the tensile modulus will not be higher than 1100 MPa.

[0170] It is also preferred that the polyethylene recycled blend (PCR) has no units derived from isotactic polypropylene when subjected to NMR analysis as described in the specification.

[0171] In another preferred aspect, the polyethylene recycled blend (PCR) according to the present invention has a LAOS-NLF 1000% (190°C) of 2.1 to 2.9, preferably 2.2 to 2.7, most preferably 2.3 to 2.6. LAOS–NLF 1000% is a rheological measure of the long chain branching content, defined as

[0172]

[0173] in

[0174] G 1 ' is the first-order Fourier coefficient

[0175] G 3 ' is the third-order Fourier coefficient

[0176] A medium or low value of 1000% for LAOS-NLF indicates very low, i.e. practically negligible, amounts of LDPE or LLDPE. LAOS-NLF further indicates a nonlinear polymer structure. In addition to sorting LDPE and LLDPE, LAOS-NLF can also be influenced by blending several recycling streams from different sources (e.g. different states) (after determining the value).

[0177] The polyethylene recycled blend (PCR) according to the present invention preferably has a shear thinning factor (STF) higher than 46.0, more preferably between 48.0 and 60.0.

[0178]

[0179] The shear thinning factor (STF) indicates the processability of polyethylene. The shear thinning factor (STF) can also be influenced by mixing predetermined material flows.

[0180] On the other hand, the polyethylene blend according to the present invention preferably has a polydispersity index (PI) higher than 2.0, more preferably from 2.1 to 2.7,

[0181]

[0182] Where Gc is the crossover modulus, which is the value of the shear storage modulus G' when it is equal to the shear loss modulus G". The polydispersity index (PI) is a rheological measure of the breadth of the molecular weight distribution.

[0183] Higher values, for example above 2.0 or in the range of 2.1 to 2.7, are preferred from the viewpoint of processability, in particular moldability.

[0184] The polyethylene recycled blend according to the present invention is preferably in the form of pellets. Pelletization helps to reduce the content of volatile matter and also helps homogenization.

[0185] The Charpy notched impact strength of the polyethylene recycled blend according to the present invention is preferably higher than 35.0 kJ / m at 23°C. 2 , more preferably above 45 kJ / m at 23°C 2 At -20°C, the Charpy notched impact strength of the polyethylene blend according to the present invention is preferably higher than 18.0 kJ / m at 23°C. 2 , more preferably higher than 22 kJ / m 2 .

[0186] The yield tensile stress is preferably higher than 25.0 MPa.

[0187] The method for providing the polyethylene recycling blend according to the present invention is very demanding. The method comprises the following steps:

[0188] i) providing post-consumer plastic waste, preferably high purity polyethylene from individual waste collection or municipal solid waste collection;

[0189] ii) Sorting out items made of polystyrene, polyamide, polypropylene, metal, paper and wood, thus providing post-consumer plastic materials;

[0190] iii) sorting out colored items, thereby providing a post-consumer plastic material mainly comprising white bottles, white yogurt cups, white jars, colorless panels, colorless parts, etc., and steps ii) and iii) can be combined or performed separately;

[0191] iv) optionally sorting out impurities by manual inspection

[0192] receiving two streams of polyethylene material therefrom, a first stream being substantially transparent and a second stream being substantially white;

[0193] v) grinding the two streams separately, washing in aqueous solutions containing various detergents, and then drying, exhausting and screening to obtain two pretreated streams;

[0194] vi) further sorting the two pretreated streams (both; separately) to remove non-polyolefin and color fractions;

[0195] vii) extruding into small pellets;

[0196] viii) optional aeration, which is preferably carried out at a temperature in the range of 100-130°C by preheating the post-consumer plastic to this temperature using an air stream having a temperature of at least 100°C for at least 20 hours.

[0197] Aeration is usually necessary but can be skipped in specific circumstances.

[0198] Odor control and assessment can be achieved by a variety of methods. Demets, Ruben et al. provide a review, "Development and application of an analytical method to quantify odour removal in plastic waste recycling processes." Resources, Conservation and Recycling 161 (2020): 104907, which is incorporated herein by reference.

[0199] If necessary, inorganic residues can be reduced by solution technology. OCS gel counting parameters can be controlled to avoid contaminants, such as pigments from colored materials, etc. Manual sorting is preferably assisted by NIR spectroscopy, which is also easily available in the form of small portable equipment. This allows the polypropylene content to be suppressed to a minimum. The density can be affected by reducing the amount of relatively flexible polyethylene products. The relative amount of the homopolymer part (HPF) and the copolymer part (CPF) can be controlled by wind conversion (this machine is also called a wind screen), which uses air flow to separate the material into different streams according to the size, shape and especially weight of the particles. For example, polyethylene films (i.e. LLDPE / LDPE with a relatively high copolymer fraction (CPF)) can be eliminated. CIELAB is controlled by a combination of color sorting and elimination of non-polyethylene polymer impurities.

[0200] The film of the present invention

[0201] The film of the present invention comprises at least one layer comprising a composition as described above. The film may be a monolayer film comprising the composition or a multilayer film, wherein at least one layer comprises the composition. The terms "monolayer film" and "multilayer film" have well-known meanings in the art.

[0202] The monolayer film or the layers of the multilayer film of the present invention may consist of the composition of the present invention itself or of a blend of said composition with other polymers. In the case of a blend, any other polymer is different from the metallocene-catalyzed multimodal mLLDPE and is preferably a polyolefin. Some of the above-mentioned additives, such as processing aids, may optionally be added to the metallocene-catalyzed multimodal mLLDPE during the film preparation process.

[0203] Preferably, at least one layer of the present invention comprises at least 50 wt%, more preferably at least 60 wt%, even more preferably at least 70 wt%, yet more preferably at least 80 wt% of the composition of the present invention.Most preferably, said at least one layer of the film of the present invention consists of the composition.

[0204] Thus, the films of the invention may comprise a single layer (ie a monolayer) or may be multilayer.Multilayer films typically and preferably comprise at least 3 layers.

[0205] The film is preferably produced by any conventional film extrusion process known in the art, including cast film and blown film extrusion. Most preferably, the film is a blown film or cast film, especially a blown film. For example, blown film is produced by extruding through an annular die and blowing into a tubular film by forming bubbles, which burst between rollers after solidification. The film can then be cut, cut or converted (e.g., folded) as required. Traditional film production techniques can be used in this regard. If preferred blown film or cast film is a multilayer film, each layer is typically coextruded. The technician will know suitable extrusion conditions.

[0206] The film according to the present invention may be subjected to post-treatment processes such as surface modification, lamination or orientation processes, etc. Such orientation processes may be uniaxial (MDO) or biaxial orientation, wherein uniaxial orientation is preferred.

[0207] In another preferred embodiment, the film is non-oriented.

[0208] The resulting film can have any thickness conventional in the art. The thickness of the film is not important and depends on the end use. Therefore, the film can have, for example, 300 μm or less, typically 6 to 200 μm, preferably 10 to 180 μm, for example 20 to 150 μm or 20 to 120 μm. If desired, the polymer of the present invention can achieve a thickness of less than 100 μm, for example less than 50 μm. It is also possible to produce a film of the present invention with a thickness even less than 20 μm while maintaining good mechanical properties.

[0209] Furthermore, the present invention also relates to the use of the inventive preparation as packaging material, in particular as packaging material for secondary packaging, which does not require food approval or even non-food primary packaging.

[0210] The films of the invention are characterized by a dart drop impact strength (DDI) of at least 700 g to at most 1500 g, preferably 750 g to at most 1400 g, more preferably 800 g to at most 1300 g, measured according to ISO 7765-1:1988, method A on a 40 μm single layer test blown film.

[0211] Furthermore, the films according to the invention have good stiffness (tensile modulus measured on 40 μm monolayer test blown films according to ISO 527-3), ie >250 MPa (in both directions).

[0212] Thus, the tensile modulus of films comprising the composition of the present invention in the machine direction (MD) and transverse direction (TD) (measured according to ISO 527-3 on a 40 μm single layer test blown film) may further range from >250 MPa to 600 MPa, preferably from 260 MPa to 550 MPa, more preferably from 280 to 500 MPa.

[0213] The present invention will be further described with reference to the following non-limiting examples.

[0214] Determination method

[0215] Unless otherwise stated in the description or the experimental section, the following methods were used to determine the properties of the polymers (including parts and components thereof) and / or any sample preparations thereof as described in the text or in the experimental section.

[0216] Melt flow rate:

[0217] The melt flow rate (MFR) is measured according to ISO 1133 and is expressed in g / 10 min. The MFR of polyethylene is measured at 190°C. The MFR can be measured at different loads, for example 2.16 kg (MFR 2 )、5kg(MFR 5 ) or 21.6kg(MFR 21 ).

[0218] MFR of component B and part (A-2) 2 Calculation

[0219] logA=x·logB+(1-x)·logC

[0220]

[0221] For component B:

[0222] B = MFR of component (A) 2

[0223] C = MFR of component (B) 2

[0224] A = Final MFR of multimodal linear low density polyethylene (mLLDPE) 2 (mixture)

[0225] X = weight fraction of component (A)

[0226] For part (A-2):

[0227] B = MFR of the first part (A-1) 2

[0228] C = MFR of the second part (A-2) 2

[0229] A = Final MFR of the cyclic polymer (= component (A)) 2 (mixture)

[0230] X = weight fraction of the first part (A-1)

[0231] density

[0232] The density of polymers is measured according to ISO 1183 and is expressed in kg / m 3 Given, the sample preparation was carried out according to ISO 1872-2.

[0233] C2 moiety determined by NMR spectroscopy and general microstructure including “continuous C3” and short chain branches

[0234] A Bruker AVNEO 400 MHz NMR spectrometer was used to analyze the 1 H and 13 C was operated at 400.15 and 100.62 MHz and quantitative data were recorded in solution. 13 C{ 1 H}NMR spectra. All spectra were obtained using 13 C was recorded at 125 °C using a 10 mm extended temperature probe optimized for temperature measurement. All pneumatic devices used nitrogen. Approximately 200 mg of material was mixed with approximately 3 mg of BHT (2,6-di-tert-butyl-4-methylphenol CAS 128-37-0) and chromium (III) acetylacetonate (Cr(acac) 3 ) were dissolved in about 3 mg of 1,2-tetrachloroethane-d 2 (TCE-d 2) to obtain a 60 mM solution of the relaxation agent in the solvent {singh09}. To ensure a homogeneous solution, the NMR tube was further heated in a rotary oven for at least 1 hour after the initial sample preparation in a heat block. The tube was rotated at a frequency of 10 Hz when inserted into the magnet. Standard single pulse excitation without NOE was used, using an optimized tip angle, a 1 second recycle delay and a dual-level WALTZ16 decoupling scheme {zhou07, busico07}. A total of 6144 (6k) transients were obtained for each spectrum.

[0235] Quantitative 13 C{ 1 The H} NMR spectra were processed, integrated, and the relevant quantitative properties were determined from the integration using a proprietary computer program. All chemical shifts were indirectly referenced to the central methylene of the ethylene block (EEE) at 30.00 ppm using the chemical shift of the solvent. Characteristic signals corresponding to polyethylene and polypropylene with different short chain branches (B1, B2, B4, B5, B6plus) were observed {randall89, brandolini00}.

[0236] Characteristic signals corresponding to the presence of polyethylene were observed, and the polyethylene contained isolated B1 branches (starB1 33.3ppm), isolated B2 branches (starB2 39.8ppm), isolated B4 branches (twoB4 23.4ppm), isolated B5 branches (threeB5 32.8ppm), all branches longer than 4 carbons (starB4plus 38.3ppm) and the third carbon from the end of the saturated aliphatic chain (3s 32.2ppm). If one or another structural element is not observed, it is excluded from the equation. The combined intensity of the ethylene backbone methine carbon (dd 30.0ppm), γ-carbon (g 29.6ppm), 4s and threeB4 carbon (compensated later) is between 30.9ppm and 29.3ppm, excluding Tββ from polypropylene. The amount of C2 related carbon is quantified using all mentioned signals according to the following equation:

[0237] f C2总计 =(Iddg-ItwoB4)+(IstarB1 * 6)+(IstarB2 * 7)+(ItwoB4 * 9)

[0238] +(IthreeB5 * 10)+((IstarB4plus-ItwoB4-IthreeB5) * 7)+(I3s* 3)

[0239] While characteristic signals corresponding to the presence of polypropylene (PP, continuous C3) were observed at 46.7 ppm, 29.0 ppm, and 22.0 ppm, the amount of PP-related carbon was quantified using the Sαα integral at 46.6 ppm:

[0240] f PP =Isαα * 3

[0241] The weight percentage of C2 fraction and polypropylene can be quantified according to the following equation:

[0242] wt C2部分 =fC C2总计 * 100 / (fC C2总计 +fC PP )

[0243] wt PP =fC PP * 100 / (fC C2总计 +fC PP )

[0244] Characteristic signals corresponding to the various short chain branches are observed and quantified as their weight percentage of the relevant branch will be the alpha olefin, first quantifying the weight fraction of each:

[0245] fwtC2=fC C2总计 –(IstarB1 * 3)–(IstarB2 * 4)–(ItwoB4 * 6)–

[0246] (IthreeB5 * 7)

[0247] fwtC3 (separation C3) = IstarB1 * 3

[0248] fwtC4=IstarB2 * 4

[0249] fwtC6=ItwoB4 * 6

[0250] fwtC7=IthreeB5 * 7

[0251] Normalization of all weight fractions results in the quantity of weight percentages of all relevant branches:

[0252] fsumwt％总计 =fwtC2+fwtC3+fwtC4+fwtC6+fwtC7+fC PP

[0253] wtC2 total = fwtC2*100 / fsum wt％总计

[0254] wtC3 total = fwtC3*100 / fsum wt％总计

[0255] wtC4 total = fwtC4*100 / fsum wt％总计

[0256] wtC6 total = fwtC6*100 / fsum wt％总计

[0257] wtC7 total = fwtC7*100 / fsum wt％总计

[0258] zhou07

[0259] Zhou,Z.,Kuemmerle,R.,Qiu,X.,Redwine,D.,Cong,R.,Taha,A.,Baugh,D.Winniford,B.,J.Mag.Reson.187(2007)225.

[0260] busico07

[0261] Busico,V.,Carbonniere,P.,Cipullo,R.,Pellecchia,R.,Severn,J.,Talarico,G.,Macromol.Rapid Commun.2007,28,1128.

[0262] singh09

[0263] Singh,G.,Kothari,A.,Gupta,V.,Polymer Testing 28 5(2009),475.

[0264] randall89

[0265] J. Randall, Macromol. Sci., Rev. Macromol. Chem. Phys. 1989, C29, 201.

[0266] brandolini00

[0267] AJBrandolini, DDHills, NMR Spectra of Polymers and PolymerAdditives, Marcel Dekker Inc., 2000.

[0268] CFC polymer composition analysis - determination of homopolymer fraction (HPF), copolymer fraction (CPF) and iso-PP fraction (IPPF)

[0269] The chemical composition distribution at a certain elution temperature (polymer crystallinity in solution) as well as the determination of the molecular weight distribution and the corresponding molecular weight averages (Mn, Mw and Mv) were determined by fully automated cross-fractionation chromatography (CFC) as described in Ortin A., Monrabal B., Sancho-Tello J., Macromol. Symp., 2007, 257, 13-28.

[0270] Cross-fractionation chromatography (TREF xSEC) was performed using a CFC instrument (PolymerChar, Valencia, Spain). The concentration was monitored using a quad band IR5 infrared detector (PolymerChar, Valencia, Spain). The polymer was dissolved at 160°C for 180 minutes at a concentration of approximately 0.4 mg / ml.

[0271] To avoid injection of gels and polymers that are not soluble in TCB at 160°C, such as PET and PA, the weighed samples were loaded into a stainless steel mesh MW 0.077 / D 0.05 mm.

[0272] After the sample was completely dissolved, an aliquot of 0.5 ml was loaded into the TREF column and stabilized at 110°C for 60 min. A temperature of 60°C was reached by applying a constant cooling rate of 0.07°C / min to allow the polymer to crystallize and precipitate. The following temperature steps were used for the discontinuous elution process: (60, 65, 69, 73, 76, 79, 80, 82, 85, 87, 89, 90, 91, 92, 93, 94, 95, 95, 96, 97, 98, 99, 100, 102, 104, 107, 120, 130).

[0273] In the second dimension, GPC analysis used 3PL Olexis columns and 1x Olexis Guard columns from Agilent (Church Stretton, UK) as stationary phases. 1,2,4-Trichlorobenzene (TCB, stabilized with 250 mg / L 2,6-di-tert-butyl-4-methylphenol) was applied as eluent at a constant flow rate of 1 mL / min at 150°C. The column set was calibrated using universal calibration (according to ISO 16014-2:2003) with at least 15 narrow MWD polystyrene (PS) standards ranging from 0.5 kg / mol to 11500 kg / mol. The following Mark Houwink constants were used to convert PS molecular weights to PE molecular weight equivalents.

[0274] K PS =19x 10 -3 mL / g, α PS =0.655

[0275] K PE =39x 10 -3 mL / g, α PP =0.725

[0276] A third order polynomial fit was used to fit the calibration data. Data processing was performed using software provided by PolymerChar and the CFC instrument.

[0277] Calculation of the homopolymer fraction (HPF), copolymer fraction (CPF) and iso-PP fraction (IPPF).

[0278] The definitions of the homopolymer fraction (HPF), copolymer fraction (CPF) and iso-PP fraction (IPPF) are as follows:

[0279] 100% = CPF + HPF + IPPF

[0280] The IPPF fraction is defined as the polymer fraction eluting at temperatures of 104°C and above.

[0281] Due to the slight dependence of the TREF curve on the low MW portion, the molecular weight limit of the low MW limit depends on the elution temperature (T el ). Use the following formula to determine the low MW limit:

[0282] Lower MW limit (for HPF part) = 0.0125 * T el +2.875

[0283] Taking this into account, the HPF fraction was calculated using the following method.

[0284]

[0285] Among them, H ij It is the 2D differential distribution at the corresponding elution temperature (Tel) i and logM value j obtained using the corresponding data processing software.

[0286] Inorganic residues

[0287] The inorganic residues were determined by TGA according to DIN ISO 11358-1:2014 using a TGADiscovery TGA5500. Approximately 10-30 mg of material were placed in a platinum pan. The sample was heated under nitrogen at a heating rate of 20°C / min. At 850°C, the ash content was evaluated in wt%.

[0288] OCS Gel

[0289] Cast film samples with a thickness of about 70 μm were extruded and inspected using a CCD (charge coupled device) camera, image processor and evaluation software (instrument: OCS-FSA100, supplier OCS GmbH (Optical Control Systems)). Film defects were measured and classified according to their circle diameter. 2 The films were analyzed and the values ​​per square meter were calculated as average values.

[0290] Cast film preparation, extrusion parameters:

[0291] 1. Output 25±4g / min

[0292] 2. Extruder temperature curve: 200-210-210-200 (melting temperature 224°C)

[0293] 3. Film thickness is about 70μm

[0294] 4. Cooling roller temperature 80℃

[0295] 5. Airknife 6400NI / h (volume)

[0296] Technical data of extruder:

[0297] 1. Screw type: 3-zone, nitrification

[0298] 2. Screw diameter: 25mm

[0299] 3. Screw length: 25D

[0300] 4. Feeding area: 10D

[0301] 5. Compression area: 4D + output area 11D

[0302] 6. Mould 150mm

[0303] According to size (μm) / m 2 Classify defects:

[0304] 100-299μm

[0305] 300-599μm

[0306] 600-999μm

[0307] 1000μm and above

[0308] CIELAB color space (L * a * b * )

[0309] In CIE L * a * b * In uniform color space, measured according to DIN EN ISO 11664-4, the color coordinates are: L * —brightness coordinate; a * —Red / Green coordinate, +a * Indicates red, -a * Indicates green; b * —Yellow / blue coordinate, +b * Indicates yellow, -b * Indicates blue. * 、a * and b * The coordinate axes define the three-dimensional CIE color space. Standard Konica / MinoltaColorimeter CM-3700A.

[0310] Assessing recyclable properties

[0311] Limonene content

[0312] Quantification of limonene was performed as described in the experimental part of EP 3757152.

[0313] Fatty acid detection

[0314] Fatty acid quantification was performed using headspace solid phase microextraction (HS-SPME-GC-MS) by standard addition.

[0315] 50 mg of ground sample was weighed in a 20 mL headspace vial, and after adding different concentrations of limonene and a glass-coated magnetic stirring bar, the vial was closed with a magnetic cap lined with silicone / PTFE. A 10 μL microcapillary was used to add known concentrations of a diluted free fatty acid mixture (acetic acid, propionic acid, butyric acid, valeric acid and caproic acid, optionally octanoic acid) standard to the sample at three different levels. 0, 50, 100 and 500 ng were added to equal 0 mg / kg, 1 mg / kg, 2 mg / kg and 10 mg / kg of each acid. For quantification, ion 60 obtained in SIM mode was used for all acids except propionic acid, where ion 74 was used.

[0316] GCMS parameters:

[0317] Column: 20m ZB Wax plus 0.25 * 0.25

[0318] Syringe: 5:1 split, split liner with glass liner, 250°C

[0319] Temperature program: 40℃(1min)@6℃ / min to 120℃, @15℃ to 245℃(5min)

[0320] Carrier: Helium 5.0, Linear velocity 40cm / s, Constant current

[0321] MS: Single quadrupole, direct interface, 220°C interface temperature

[0322] Acquisition: SIM scan mode

[0323] Scan parameters: 46-250amu 6.6 scans / second

[0324] SIM parameters: m / z 60, 74, 6.6 scans / sec.

[0325] Metal

[0326] Determined by X-ray fluorescence (XRF).

[0327] Benzene content

[0328] By HS GC-MS 80℃ / 2h, described as follows

[0329] Static Headspace Analysis

[0330] The parameters for the static headspace gas chromatography-mass spectrometry (HS / GC / MS) method are presented here.

[0331] Weigh 4.000 ± 0.100 g of sample in a 20 ml sealed vial and seal tightly with a PTFE cap.

[0332] The mass spectrometer was operated in scan mode and a total ion chromatogram (TIC) was recorded for each analysis. Further details on applicable method parameters and data evaluation are as follows:

[0333] -HS parameters (Agilent G1888 Headspace Sampler)

[0334]

[0335]

[0336] Low jitter

[0337] -GC parameters (Agilent 7890AGC system)

[0338]

[0339] -MS parameters (Agilent 5975C inert XL MSD)

[0340]

[0341] - Software / Data Evaluation

[0342] MSD ChemStation E.02.02.1431

[0343] MassHunter GC / MS Acquisition B.07.05.2479

[0344] AMDIS GC / MS Analysis Version 2.71

[0345] NIST Mass Spectral Library Version 2.0g

[0346] -AMDIS deconvolution parameters

[0347]

[0348]

[0349] Data evaluation:

[0350] The TIC data were further deconvoluted with the help of AMDIS software (see parameters above) and compared with a custom target library based on a mass spectral library (NIST). In the custom target library, the respective mass spectra of selected substances (e.g. benzene) were included. Substances were accepted as “tentative identifications” only if the identified peaks showed a minimum match factor of 80 and an experienced mass spectrometer confirmed the match.

[0351] In this study, the statement "below the detection limit (<LOD)" refers to the case where the matching factor is below 80 (AMDIS) or the peak itself cannot even be identified. The results only refer to the measured samples, the measurement time, and the applied parameters.

[0352] Odor VDA270-B3

[0353] VDA270 is the determination of the odor characteristics of motor vehicle trim materials. The odor is determined according to Variant B3 of VDA270 (2018). After lifting the lid of the can as little as possible, each assessor evaluates the odor of each sample according to the VDA270 scale. The six-level (hexamerous scale) consists of the following grades: Grade 1: Not perceivable, Grade 2: Perceivable, not disturbing, Grade 3: Clearly perceivable, but not disturbing, Grade 4: Disturbing, Grade 5: Strongly disturbing, Grade 6: Unacceptable. The assessors remain calm during the evaluation and are not allowed to bias each other by discussing individual results during the test. They are also not allowed to adjust their evaluations after testing another sample. For statistical reasons (as accepted by VDA270), the assessors are forced to use the full steps in the evaluation. Therefore, the odor grade is based on the average of all individual evaluations and is rounded to an integer.

[0354] Rheological measurements

[0355] Dynamic shear measurement (frequency sweep measurement)

[0356] The characterization of the polymer composition or the melt of the polymer by dynamic shear measurement as described above or below complies with ISO standards 6721-1 and 6721-10. The measurements are carried out on an Anton Paar MCR501 stress-controlled rotational rheometer equipped with a 25 mm parallel plate geometry. The measurements are carried out on compression-molded plates using a nitrogen atmosphere and setting the strain within the linear viscoelastic range. The oscillatory shear test is carried out at 190 °C using a frequency range between 0.01 and 600 rad / s, and the gap is set to 1.3 mm.

[0357] Other details are described in paragraph (i) of the experimental section of EP 3757152.

[0358] The shear thinning factor (STF) is defined as

[0359]

[0360] These values ​​were determined by means of a single-point interpolation procedure defined in the Rheoplus software. In cases where a given G* value was not reached experimentally, it was determined by extrapolation using the same procedure as before. Also in this case (interpolation or extrapolation), the options "Interpolate y-values ​​of parameter to x-values" and "Logarithmic interpolation type" in Rheoplus were applied (see above).

[0361] Large Amplitude Oscillatory Shear (LAOS)

[0362] The nonlinear viscoelastic behavior under shear flow is studied using large amplitude oscillatory shear. This method requires applying a sinusoidal strain amplitude γ with a given angular frequency ω for a given time t. 0 . If the applied sinusoidal strain is high enough, a nonlinear response will result. In this case, the stress σ is a function of the applied strain amplitude, time, and angular frequency. Under these conditions, the nonlinear stress response is still a periodic function; however, it can no longer be expressed by a single harmonic sinusoid. The stress [0-0] resulting from the nonlinear viscoelastic response can be represented by a Fourier series that includes higher harmonic contributions:

[0363] σ(t,ω,γ 0 )=γ 0 .∑ n [G′ n (ω,γ 0 ).sin(nωt)+G″ n (ω,γ 0 ).cos (nωt)] (1)

[0364] Where, σ-stress response

[0365] t-time

[0366] ω-Frequency

[0367] γ 0 -Strain amplitude

[0368] n - number of harmonics

[0369] G′ n -nth order elastic Fourier coefficient

[0370] G″ n -nth order viscosity Fourier coefficient

[0371] The nonlinear viscoelastic response was analyzed using large amplitude oscillatory shear (LAOS). Time sweep measurements were performed on an Alpha Technologies RPA2000 rheometer in combination with a standard double cone die. During the measurements, the test chamber was sealed and a pressure of approximately 6 MPa was applied. LAOS tests were performed at an applied temperature of 190°C, an angular frequency of 0.628 rad / s and a strain of 1000%. To ensure that steady-state conditions were achieved, the nonlinear response was determined only after at least 20 cycles were completed for each measurement. The large amplitude oscillatory shear nonlinear factor (LAOS_NLF) is defined as follows:

[0372]

[0373] Among them G 1 ′-first-order Fourier coefficient

[0374] G 3 ′-third-order Fourier coefficient

[0375] [1] JMDealy, KFWissbrun, Melt Rheology and Its Role in Plastics Processing: Theory and Applications; edited by Van Nostrand Reinhold, New York (1990).

[0376] [2] S. Filipe, Non-Linear Rheology of Polymer Melts, AIP Conference Proceedings1152, pages 168-174 (2009).

[0377] [3] M. Wilhelm, Macromol. Mat. Eng. 287, 83-105 (2002).

[0378] [4] S. Filipe, K. Hofstadler, K. Klimke, ATTran, Non-Linear Rheological Parameters for Characterization of Molecular Structural Properties in Polyolefins, Proceedings of Annual European Rheology Conference, 135 (2010).

[0379] [5] S. Filipe, K. Klimke, ATTran, J. Reussner, Proceedings of Novel Non-Linear Rheological Parameters for Molecular Structural Characterization of Polyolefins, Novel Trends in Rheology IV, Zlin, Check Republik (2011).

[0380] [6] K.Klimke, S.Filipe, ATTran, Non-linear rheological parameters for characterization of molecular structural properties in polyolefins, Proceedings of European Polymer Conference, Granada, Spain (2011).

[0381] Dart Drop Intensity (DDI)

[0382] DDI was measured according to ISO 7765-1:1988 / Method A on films (non-oriented films and laminates) produced as shown below. This test method covers the determination of the energy that will cause film failure under specified conditions of impact with a dart falling freely from a specified height, which will cause 50% of the test specimens to fail (Step Method A). A uniform increment of the missile mass was used during the test, and after each specimen test, the missile weight was reduced or increased by a uniform increment depending on the observed result (failure or no failure) of the specimen.

[0383] Standard conditions:

[0384] Adjustment time: >96h at 50±2℃±10%rh

[0385] Test temperature: 23℃

[0386] Dart head material: phenolic resin

[0387] Dart diameter: 38mm

[0388] Drop height: 660mm

[0389] Result: Impact failure weight -50% [g]

[0390] Tensile modulus

[0391] Tensile modulus (E-Mod (MPa)) was measured according to ISO 527-3 on film samples with a thickness of 40 μm prepared as described in Film sample preparation, at a crosshead speed of 1 mm / min for the modulus in the longitudinal / transverse direction.

[0392] Membrane sample preparation

[0393] A Collin 30 laboratory scale monolayer blown film line was used to prepare test films with a thickness of 40 μm consisting of the composition of the present invention and the respective comparative compositions. The film samples were produced at 194° C., a blow ratio of 1:2.5, and a frost line distance of 120 mm.

[0394] Experimental Section

[0395] Example Preparation

[0396] I) mLLDPE

[0397] Cat. Example: Preparation of Catalysts for Examples IE1 and IE2 of the Present Invention and Comparative Examples CE1 and CE2

[0398] SiO2 loading:

[0399] 10 kg of silica (PQ Corporation ES757, calcined at 600°C) was added from a feed bucket and inerted in the reactor until O 2 Levels reached below 2ppm.

[0400] Preparation of MAO / tol / MC:

[0401] At 25°C (oil circulation temperature) and 95rpm stirring, a 30wt% MAO toluene solution (14.1kg) was added from a balance to another reactor, followed by toluene (4.0kg). After adding toluene, the stirring speed was increased from 95rpm to>200rpm, with a stirring time of 30 minutes. Metallocene racemic-dimethylsilanediylbis{2-(5-(trimethylsilyl)furan-2-yl)-4,5-dimethylcyclopentadiene-1-yl}zirconium dichloride 477g was added from a metal cylinder, followed by 4kg toluene rinse (total toluene was 8.0kg). The reactor stirring speed was changed to 95rpm for MC feeding, returned to 200rpm and continued for 3h reaction time. After the reaction time, the MAO / tol / MC solution was transferred to a feed container.

[0402] Preparation of catalyst:

[0403] The reactor temperature was set to 10°C (oil circulation temperature) and stirring was adjusted to 40 rpm during the addition of MAO / tol / MC. MAO / tol / MC solution (22.2 kg) was added over 205 min, followed by a stirring time of 60 min (oil circulation temperature set to 25°C). After stirring, the "dry mix" was stabilized at 25°C (oil circulation temperature) for 12 h with a stirring speed of 0 rpm. The reactor was rotated 20° (back and forth) and stirred several times per hour at a speed of 5 rpm.

[0404] After stabilization, the catalyst was dried at 60°C (oil circulation temperature) for 2 h under a 2 kg / h nitrogen flow, followed by drying under vacuum for 13 h (same nitrogen flow rate, stirring at 5 rpm). The dried catalyst was sampled and the HC content was measured using a Sartorius moisture analyzer (model MA45) in a glove box using thermogravimetry. The target HC level was <2% (actual 1.3%).

[0405] Polymerization: Multimodal mLLDPE of ethylene with 1-butene and 1-hexene comonomers for IE and CE

[0406] The Borstar pilot plant has a three-reactor set-up (Loop 1 – Loop 2 – GPR1) and a prepolymerization loop reactor.

[0407] The multimodal mLLDPE according to the invention (mLLDPE-1) as well as the comparative multimodal mLLDPEs (mLLDPE-2, mLLDPE-3) were produced by using the polymerization conditions given in Table 1.

[0408] Table 1: Polymerization conditions

[0409]

[0410]

[0411] The polymer was mixed with 2400 ppm of Irganox B561 (supplied by BASF) and 270 ppm of Dynamar FX 5922 (supplied by 3M), compounded and extruded into pellets by using a JSW extruder under a nitrogen atmosphere so that SEI was 230 kWh / kg and the melt temperature was 250°C.

[0412] Table 2: Material properties of multimodal mLLDPE

[0413]

[0414] Multimodal mLLDPE was blended with polyethylene recycled blend (PCR) and converted into blown films.

[0415] For CE3, Total was used Supertough 22ST05: metallocene polyethylene; density 921kg / m 3 , MFR 2 0.5g / 10min.

[0416] II) Polyethylene recycled blend (PCR)

[0417] Multiple post-consumer plastic waste HDPE streams from a separate plastic waste collection (a municipal facility providing specific HDPE collection) were roughly sorted based on polymer properties and color. Impurities were further separated by manual inspection. Two streams were received, namely a stream of a colorless fraction and a stream of a white fraction. The colorless fraction stream (separately) was ground, washed in an aqueous solution with various detergents, then dried and screened to obtain a pretreated stream. The pretreated stream was further sorted to reduce the colored fraction and non-polyolefins. After preheating the matrix particles to at least 100°C, the particles were extruded into pellets and aerated in air at 120°C for 22 hours. A substantially colorless PCR was obtained. Table 3 shows the results for the final material.

[0418] All examples were subjected to polymer composition analysis by CFC.

[0419] Table 3: Characteristics of colorless PCR

[0420]

[0421]

[0422] Table 4: Blend and film properties

[0423]

[0424] As can be clearly seen from the above table, the films of the examples of the present invention consisting of the compositions of the present invention show a good combination of stiffness and impact resistance.

[0425] If MFR 2 Too high, and MFR 21 / MFR 2 If the ratio is too low (mLLDPE-2, CE1), the stiffness may be good, but the impact strength is very low.

[0426] If mLLDPE according to the invention is used, the stiffness / impact resistance is significantly improved. It is even better than CE2 and CE3, which are "virgin" materials without any PCR.

Claims

1. A composition comprising: (I) 50.0 to 99.0 wt% of a metallocene-catalyzed linear low-density polyethylene (mLLDPE), based on the total weight of the composition, wherein the metallocene-catalyzed linear low-density polyethylene (mLLDPE) consists of (i) 30.0 to 70.0 wt% of an ethylene-1-butene polymer component (A) based on the total weight of mLLDPE and (ii) 70.0 to 30.0 wt% of an ethylene-1-hexene polymer component (B), based on the total weight of the mLLDPE, wherein the ethylene-1-butene polymer component (A) has ·925 to 960 kg / m 3 Density in the range of 1.0 to 100.0 g / 10min (ISO 1183) and MFR in the range of 1.0 to 100.0 g / 10min 2 (190℃, 2.16kg, ISO 1133); The ethylene-1-hexene polymer component (B) has 880 to 915 kg / m 3 Density in the range (ISO 1183) and MFR in the range of 0.001 to 1.0 g / 10min 2 (190°C, 2.16kg, ISO 1133); and Among them, multimodal linear low density polyethylene (mLLDPE) has 910 to 923 kg / m 3 Density in the range (ISO 1183), · MFR in the range of 0.1 to 1.2 g / 10 min 2 (190 °C, 2.16 kg, ISO 1133), and MFR in the range of 5.0 to 75.0 g / 10 min 21 (190°C, 21.6kg, ISO 1133), and MFR in the range of 35.0 to 60.0 21 / MFR 2 ratio; and (II) 1.0 to 50.0 wt% of a polyethylene recycled blend (PCR), based on the total weight of the composition, having (i) MFR in the range of 0.1 to 10.0 g / 10 min 5 (ISO 1133, 5.0 kg; 190 °C), and (ii) 950 to 970 kg / m 3 Density within the range (ISO1183), and (iii) a C2 fraction in an amount greater than 95.0 wt% as measured by NMR of the d2-tetrachloroethylene soluble fraction, and (iv) a homopolymer fraction (HPF) content in the range of 80.0 to 91.0 wt % based on the total weight of the PCR as determined by chemical composition analysis by cross fractionation chromatography (CFC), and (v) a copolymer fraction (CPF) content in the range of 9.0 to 20.0 wt% based on the total weight of PCR as determined by chemical composition analysis by cross fractionation chromatography (CFC), and (vi) optionally an iso-PP fraction (IPPF) content in the range of 0.0 to 2.0 wt% based on the total weight of the PCR as determined according to chemical composition analysis by cross fractionation chromatography (CFC), wherein the iso-PP fraction (IPPF) is defined as the polymer fraction eluting at a temperature of 104°C and above, wherein the homopolymer fraction (HPF), the copolymer fraction (CPF) and the iso-PP fraction (IPPF) add up to 100 wt%, and (vii) 0.01 to 2.00 wt% of inorganic residues (measured by TGA) relative to the total polyethylene recycled blend, and (viii) 10m by OCS counting instrument 2 OCS gels having a size of 100 to 299 microns measured in the range of 500 to 5000 counts / square meter; wherein (ix) CIELAB color space (L * a * b * ) is -L * 75.0 to 86.0; -a * -5.0 to 0.0; -b * 5.0 to less than 25.0 or (x) CIELAB color space (L * a * b * ) is -L * Above 86.0 to 97.0; -a * -5.0 to 0.0; -b * 0.0 to less than 5.

0.

2. The composition of claim 1, wherein in the metallocene-catalyzed multimodal linear low density polyethylene (mLLDPE), the ethylene-1-butene polymer component (A) consists of an ethylene-1-butene polymer fraction (A-1) and an ethylene-1-butene polymer fraction (A-2), The density (ISO 1183) of parts (A-1) and (A-2) is between 925 and 960 kg / m 3 Within the range and MFR 2 (190°C, 2.16kg, ISO 1133) in the range of 0.1 to 150g / 10min, and wherein the densities of the ethylene polymer fractions (A-1) and (A-2) may be the same or different and the MFR of the ethylene polymer fraction (A-2) is 2 (190°C, 2.16 kg, ISO 1133) equal to, preferably higher than, the MFR of the ethylene polymer part (A-1) 2 .

3. The composition according to claim 1 or 2, wherein in the metallocene-catalyzed multimodal linear low density polyethylene (mLLDPE), the melt flow rate (MFR) of the ethylene polymer component (A) 2 (at 190 °C, 2.16 kg, ISO 1133) is in the range of 8.0 to 80.0 g / 10 min, preferably 10.0 to 70.0 g / 10 min, more preferably 12.0 to 60.0 g / 10 min, and / or MFR of ethylene polymer component (B) 2 (190° C., 2.16 kg, ISO 1133) is in the range of 0.002 to 0.8 g / 10 min, preferably 0.003 to 0.5 g / 10 min, even more preferably 0.003 to 0.2 g / 10 min.

4. The composition according to claim 2 or 3, wherein in the metallocene-catalyzed multimodal linear low density polyethylene (mLLDPE), the MFR of part (A-2) is 2 MFR of part (A-1) 2 Ratio MFR 2 (A-2) / MFR 2 (A-1) is in the range of ≥1.0 to 100.0, preferably 1.5 to 50.0, more preferably 2.0 to 10.

0.

5. A composition according to any one of the preceding claims, wherein the metallocene-catalyzed multimodal linear low density polyethylene (mLLDPE) has an MFR of 2 (190°C, 2.16 kg, ISO 1133) is in the range of 0.2 to 1.0 g / 10 min, preferably 0.2 to 0.8 g / 10 min.

6. A composition according to any one of the preceding claims, wherein the density (ISO 1183) of the ethylene polymer component (A) in the metallocene-catalyzed multimodal linear low density polyethylene (mLLDPE) is in the range of 930 to 955 kg / m 3 , more preferably 932 to 952 kg / m 3 In the range of ethylene polymer component (B), the density (ISO 1183) is between 890 and 905 kg / m 3 The metallocene-catalyzed multimodal linear low-density polyethylene (mLLDPE) has a density (ISO 1183) of 912 to 922 kg / m 3 , preferably 914 to 922 kg / m 3 , more preferably 915 to 921 kg / m 3 within the range.

7. The composition according to any one of the preceding claims, wherein the polyethylene recycled blend (PCR) has one or both of the following properties: a) limonene content determined by using solid phase microextraction (HS-SPME-GC-MS) in an amount of 0.1 to 25 ppm, preferably 0.1 to 20 ppm b) a total amount of fatty acids consisting of the group of acetic acid, butyric acid, valeric acid and caproic acid of 10 to 500 ppm, preferably 10 to 300 ppm, determined by using solid phase microextraction (HS-SPME-GC-MS).

8. The composition according to any one of the preceding claims, wherein the polyethylene recycled blend (PCR) has an odor (VDA 270-B3) of 2.5 or less, preferably 2.0 or less.

9. The composition according to any one of the preceding claims, wherein the polyethylene recycled blend (PCR) has the following OCS gel count properties (for 10 m 2 One or more of the a) OCS gel with a size of 300 to 599 microns: 100 to 2500 counts / m2; b) OCS gel with a size of 600 to 1000 microns: 10 to 200 counts / m2; c) OCS gels with a size greater than 1000 μm: 1 to 40 counts / m2; All of these are counted by OCS instruments for 10m 2 The films were measured as described in the experimental section.

10. The composition according to any one of the preceding claims, wherein the polyethylene recycled blend (PCR) has a tensile modulus of at least 825 MPa, preferably at least 850 MPa, most preferably at least 910 MPa to 1100 MPa using injection molded specimens as described in EN ISO 1873-2 (dog bone shape, 4 mm thickness) (ISO 527-2, crosshead speed of 1 mm / min; 23°C).

11. The composition according to any one of the preceding claims, wherein the Large Amplitude Oscillatory Shear-Non-Linear Factor (LAOS-NLF) of the Polyethylene Recycled Blend (PCR) (190°C; 1000%) in G 1 ' is the first-order Fourier coefficient G 3 ' is the third-order Fourier coefficient In the range of 2.1 to 2.9, preferably 2.2 to 2.7, most preferably 2.3 to 2.

6.

12. The composition according to any one of the preceding claims, wherein the shear thinning factor (STF) of the polyethylene recycling blend (PCR) is It is higher than 46.0, preferably 48.0 to 60.

0.

13. A film comprising the composition according to any one of the preceding claims 1 to 12.

14. The film according to claim 13, wherein the film is characterized by a dart drop impact strength (DDI) determined according to ISO 7765-1:1988, method A on a 40 μm monolayer test blown film of at least 700 g and at most 1500 g, preferably 750 g to 1400 g, more preferably 800 g to 1300 g, and a tensile modulus in the machine direction (MD) and transverse direction (TD) (measured according to ISO 527-3 on a 40 μm monolayer test blown film) in the range of >250 MPa to 600 MPa, preferably 260 MPa to 550 MPa, more preferably 280 MPa to 500 MPa.

15. Use of a film according to any of the preceding claims 13 to 14 as packaging material, in particular for secondary packaging not requiring food approval or even for primary packaging of non-food products.

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