Multilayer article

Abstract

The present invention relates to a multilayer article comprising at least a specific oriented polyethylene-based film (OPEF) and a specific non-oriented polyethylene-based film (NOPEF). The invention further relates to a method for producing said article and to the use thereof as packaging material.

Description

[0001] The present invention relates to a multilayer article comprising at least a specific oriented polyethylene based film (OPEF) and a specific non-oriented polyethylene based film (NOPEF). Furthermore, the present invention relates to a method for producing said article and its use as a packaging material.

[0002] Polyethylene is widely used in various aspects of daily life, such as packaging, due to its excellent cost-performance ratio. Due to today's different needs, multilayer products with different types of materials are used, which on the one hand meet the needs, but the disadvantage is that these products are difficult to recycle. From the recycling point of view, a single material solution would be preferred. At the same time, the performance of the material should not be reduced.

[0003] Single material solutions are known in the prior art.

[0004] EP 0 575 465 A1 relates to a heat-sealable composition suitable for films and film structures, comprising: (a) 30 to 70% by weight of a low melting point polymer comprising a low melting point polymer having a density of 0.88 g / cm 3 Up to 0.915g / cm 3 , an ethylene copolymer having a melt index of 1.5 dg / min to 7.5 dg / min, a molecular weight distribution of not more than 3.5 and a component distribution permeability index of greater than 70%; and (b), different from (a), 70 to 30% by weight of a propylene-based polymer having 88 mol% to 100 mol% propylene and 12 mol% to 0 mol% of an α-olefin other than propylene.

[0005] WO 2012 / 061168 A1 relates to a sealant composition, a method for producing the same, an article made therefrom, and a method for forming such an article. The sealant composition according to the present invention comprises: (a) based on the total weight of the sealant composition, 70 to 99.5 weight percent of an ethylene / α-olefin interpolymer composition, wherein the ethylene / α-olefin interpolymer composition comprises an ethylene / α-olefin interpolymer, wherein the ethylene / α-olefin interpolymer has a comonomer distribution constant (CDC) of 15 to 250 and a density of 0.875 g / cm 3 Up to 0.963g / cm 3, a melt index (I2) of 0.2 g / 10 min to 20 g / 10 min, and a long chain branching frequency of 0.02 to 3 long chain branches (LCB) / 1000C; (b) 0.5 to 30 weight percent of a propylene / α-olefin interpolymer composition, wherein the propylene / α-olefin interpolymer composition comprises a propylene / α-olefin copolymer or a propylene / ethylene / butene terpolymer, wherein the propylene / α-olefin copolymer has a crystallinity of 1 weight percent to 30 weight percent, a heat of fusion of 2 J / g to 50 J / g, and a DSC melting point of 25°C to 110°C.

[0006] WO 2019 / 005930A1 relates to a laminated structure for flexible packaging, comprising a printed film comprising a vinyl polymer, a sealant film laminated to the printed film, wherein the sealant film comprises at least 3 layers and has a total thickness of 15 to 30 μm. The sealing film comprises an intermediate layer, an outer layer, and an inner layer disposed between the printed film and the intermediate layer. The inner layer comprises an ethylene interpolymer having a density of 0.910 g / cc to 0.925 g / cc and a melt index (I2) of 0.5 g / 10 min to 5 g / 10 min, and at least one of the inner layer, the intermediate layer, and the outer layer comprises a first composition comprising at least one ethylene-based polymer, wherein the first composition comprises a molecular weight comonomer distribution index (MWCDI) value greater than 0.9 and a melt index ratio (I10 / I2) satisfying the equation: I10I2≥7.0-log(I2).

[0007] Starting from this, it is an object of the present invention to provide a multilayer article which is not only easy to recycle but also has a good balance of mechanical, optical and sealing properties.

[0008] These objects have been solved by a multilayer article according to claim 1, comprising at least an oriented polyethylene based film (OPEF) and a non-oriented polyethylene based film (NOPEF), wherein the non-oriented polyethylene based film (NOPEF) comprises at least the following sublayers: i) a skin layer (SKL); ii) a core layer (CL); and iii) a sealant layer (SL); wherein the sealant layer comprises a metallocene-catalyzed multimodal polyethylene copolymer (P) consisting of 30.0 to 70.0 % by weight of an ethylene-1-butene polymer component (A) and 30.0 to 70.0 % by weight of an ethylene-1-hexene polymer component (B), wherein the ethylene-1-butene polymer component (A) has a molecular weight of 920 kg / m 3 Up to 950kg / m 3range (ASTM D792); MFR2 (190°C, 2.16 kg, ISO 1133) in the range of 2.0 g / 10 min to 200 g / 10 min; and 1-butene content in the range of 0.5 to 5.0 wt% based on ethylene-1-butene polymer component (A); and ethylene-1-hexene polymer component (B) has 880 kg / m 3 Up to 915kg / m 3 range of density (ASTM D792); MFR2 (190°C, 2.16kg, ISO1133) in the range of 0.01g / 10min to 1.5g / 10min; and 1-hexene content in the range of 15.0 to 25.0% by weight based on ethylene-1-hexene polymer compound (B); wherein the multimodal polyethylene copolymer (P) has a density in the range of 905kg / m 3 Up to 915kg / m 3 range (ASTM D792); MFR2 (190°C, 2.16kg, ISO 1133) in the range of 0.5g / 10min to less than 2.0g / 10min; and MFR 21 Ratio of MFR (190℃, 21.6kg, ISO 1133) to MFR2 (190℃, 2.16kg, ISO 1133), MFR 21 / MFR2, in the range of 22 to 70.

[0009] Advantageous embodiments of the multilayer article according to the invention are specified in dependent claims 2 to 13. The invention also relates to a method for producing a multilayer article according to claim 14. Claim 15 relates to the use of the article according to the invention as packaging material.

[0010] definition

[0011] Metallocene-catalyzed linear low density polyethylene is defined in the present invention as a linear low density polyethylene copolymer which is produced in the presence of a metallocene catalyst.

[0012] Ziegler-Natta catalyzed linear low density polyethylene is defined in the present invention as a linear low density polyethylene copolymer which is produced in the presence of a Ziegler-Natta catalyst.

[0013] For the purposes of the present invention, a metallocene-catalyzed linear low density polyethylene consisting of an ethylene-1-butene polymer component (A) and an ethylene-1-hexene polymer component (B) refers to a polymer produced in at least two-stage sequential polymerization process, wherein component (A) is first produced and then component (B) is produced in the presence of component (A) in a subsequent polymerization step to obtain a metallocene-catalyzed linear low density polyethylene, or vice versa, i.e. component (B) is first produced and then component (A) is produced in the presence of component (B) in a subsequent polymerization step to obtain a metallocene-catalyzed linear low density polyethylene.

[0014] In the context of multimodal metallocene-catalyzed linear low density polyethylene, the term "multimodal" herein refers to multimodality with respect to the melt flow rate (MFR) of at least ethylene polymer components (A) and (B), i.e. ethylene polymer components (A) and (B) have different MFR values. The multimodal metallocene-catalyzed linear low density polyethylene may have other multimodality between ethylene polymer components (A) and (B) with respect to one or more other properties such as density, comonomer type and / or comonomer content, as described below.

[0015] Low density polyethylene (LDPE) is defined in the present invention as a low density polyethylene copolymer, which is preferably produced in a high pressure process.

[0016] When 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 regarded as a preferred embodiment of the term "comprising of". If hereinafter a group is defined as comprising at least a certain number of embodiments, this should also be understood to disclose a group that preferably consists of only these embodiments.

[0017] Whenever the terms "including" or "having" are used, these terms are intended to be equivalent to "comprising" as defined above.

[0018] When referring to a singular noun, using an indefinite or definite article, for example "a", "an" or "the", this includes a plural of that noun unless something else is specifically stated.

[0019] Metallocene-catalyzed multimodal polyethylene copolymers (P)

[0020] The sealing layer of the multilayer article according to the present invention comprises a specific metallocene-catalyzed multimodal polyethylene copolymer (P). The other layers may also comprise said copolymer (P).

[0021] The metallocene-catalyzed multimodal polyethylene copolymer (P) is composed of (i) 30.0 to 70.0% by weight of an ethylene-1-butene polymer component (A) and (ii) 70.0 to 30.0% by weight of an ethylene-1-hexene polymer component (B). In a preferred embodiment of the present invention, the ethylene-1-butene polymer component (A) is composed of ethylene polymer parts (A-1) and (A-2).

[0022] In case the ethylene-1-butene polymer component (A) consists of the ethylene polymer fractions (A-1) and (A-2), the MFR2 of the ethylene polymer fractions (A-1) and (A-2) may be different from each other.

[0023] The MFR2 (190°C, 2.16 kg, ISO 1133) of the ethylene polymer portion (A-1) is preferably in the range of 1.0 g / 10 min to 200 g / 10 min or 3 g / 10 min to 300 g / 10 min, preferably 1.0 g / 10 min to 20.0 g / 10 min, more preferably 1.5 g / 10 min to 18.0 g / 10 min, still more preferably 2.0 g / 10 min to 16.0 g / 10 min, even more preferably 2.5 g / 10 min to 14.0 g / 10 min, such as 3.0 g / 10 min to 12.0 g / 10 min, and / or the density (ASTM D792) is 920 kg / m 3 Up to 960kg / m 3 In the range of 925kg / m 3 Up to 955kg / m 3 , more preferably 930kg / m 3 Up to 950kg / m 3 .

[0024] The MFR2 (190°C, 2.16 kg, ISO 1133) of the ethylene polymer portion (A-2) is in the range of 3.0 g / 10 min to 200 g / 10 min, preferably 3.0 g / 10 min to 40.0 g / 10 min, more preferably 3.2 g / 10 min to 30.0 g / 10 min, still more preferably 3.5 g / 10 min to 20.0 g / 10 min, most preferably 3.5 g / 10 min to 10.0 g / 10 min, and / or the density (ASTM D792) is 930 kg / m 3 Up to 950kg / m 3 In the range of 935kg / m 3 Up to 945kg / m 3 .

[0025] The MFR2 of the ethylene polymer components (A) and (B) are different from each other.

[0026] The MFR2 (190°C, 2.16 kg, ISO 1133) of the ethylene polymer component (A) is in the range of 2.0 g / 10min to 200 g / 10min, preferably 2.0 g / 10min to 40 g / 10min, more preferably 2.5 g / 10min to 30 g / 10min, still more preferably 3.0 g / 10min to 20 g / 10min, even more preferably 3.2 g / 10min to 10 g / 10min.

[0027] The MFR2 (190°C, 2.16 kg, ISO 1133) of the ethylene polymer component (B) is in the range of 0.01 g / 10min to 1.5 g / 10min, preferably 0.05 g / 10min to 1.5 g / 10min, more preferably 0.1 g / 10min to 1.2 g / 10g / 10min, even more preferably 0.2 g / 10min to 1.0 g / 10min.

[0028] The MFR2 (190°C, 2.16 kg, ISO 1133) of the multimodal copolymer (P) is in the range of 0.5 g / 10min to less than 2.0 g / 10min, preferably 0.8 g / 10min to 1.8 g / 10min, more preferably 1.0 g / 10min to 1.5 g / 10min.

[0029] MFR of the multimodal copolymer (P) 21 Ratio of MFR (190℃, 21.6kg, ISO 1133) to MFR2 (190℃, 2.16kg, ISO1133) 21 / MFR2 is in the range of 22 to 70, preferably 23 to 50, more preferably 25 to 40, still more preferably 28 to 35.

[0030] In an embodiment of the present invention, it is preferred that the ratio of the MFR2 (190°C, 2.16 kg, ISO 1133) of the ethylene-1-butene polymer component (A) to the MFR2 (190°C, 2.16 kg, ISO 1133) of the final multimodal copolymer (P) is at least 2.5 to 20.0, preferably 3.0 to 15.0, more preferably 3.5 to 10.0. Naturally, in addition to the multimodality with respect to the MFR2 of the ethylene polymer components (A) and (B) (i.e. the difference between them), the multimodal PE of the present invention may also be multimodal, e.g. with respect to one or both of the other two properties: multimodality with respect to the difference in the comonomer content present in the ethylene polymer components (A) and (B); and / or the difference in the density of the ethylene polymer components (A) and (B).

[0031] Preferably, the multimodal copolymer (P) is further multimodal with respect to the comonomer content of the ethylene polymer components (A) and (B).

[0032] The comonomer type of polymer fractions (A-1) and (A-2) is the same, so both fractions have 1-butene as a comonomer.

[0033] The comonomer content of components (A) and (B) can be measured, or, in the preferred case, one component is first produced and then the other component is produced in the presence of the first produced component in a so-called multi-stage process, then the comonomer content of the first produced component (e.g. component (A)) can be measured and the comonomer content of the other component (e.g. component (B)) can be calculated according to the following formula:

[0034] Comonomer content in component B (mol-%) = (comonomer content in final product (mol-%) - (weight fraction of component A * comonomer content in component A (mol-%)) / (weight fraction of component B). The total amount of 1-butene is preferably in the range of 0.1 to 2.5 wt%, preferably 0.1 to 1.0 wt%, more preferably 0.2 to 0.8 wt%, and more preferably 0.3 to 0.6 wt%, based on the multimodal polymer (P). The total amount of 1-hexene is preferably in the range of 2.0 to 20.0 wt%, more preferably 4.0 to 18.0 wt%, and more preferably 6.0 to 15.0 wt%, based on the multimodal polymer (P).

[0035] The total amount of 1-butene present in the ethylene-1-butene polymer component (A) is in the range of 0.5 to 5.0% by weight, preferably 0.8 to 4.0% by weight, more preferably 1.0 to 3.0% by weight, even more preferably 1.0 to 2.0% by weight, based on the ethylene-1-butene polymer component (A).

[0036] The total amount of 1-hexene present in the ethylene-1-hexene polymer component (B) is in the range of 15.0 to 25.0 wt%, preferably 16.0 to 22.0 wt%, more preferably 17.0 to 20.0 wt%, based on the ethylene-1-hexene polymer component (B).

[0037] Even more preferably, the multimodal polymer (P) of the present invention is further multimodal with respect to the difference in density between ethylene polymer component (A) and ethylene polymer component (B). Preferably, the density of ethylene polymer component (A) is different from, preferably higher than, the density of ethylene polymer component (B).

[0038] The density of the ethylene polymer component (A) is 920 kg / m 3 Up to 950kg / m 3In the range of 925kg / m 3 Up to 950kg / m 3 , more preferably 930kg / m 3 Up to 945kg / m 3 , and / or the density of the ethylene polymer component (B) is 880 kg / m 3 Up to 915kg / m 3 In the range of 885kg / m 3 Up to 905kg / m 3 , more preferably 888kg / m 3 Up to 900kg / m 3 .

[0039] The density of the polymer part (A-1) is 920 kg / m 3 Up to 960kg / m 3 In the range of 925kg / m 3 Up to 955kg / m 3 , more preferably 930kg / m 3 Up to 950kg / m 3 , for example 935kg / m 3 Up to 945kg / m 3 .

[0040] The density of the polymer part (A-2) is 930 kg / m 3 Up to 950kg / m 3 In the range of 935kg / m 3 Up to 945kg / m 3 .

[0041] The metallocene-catalyzed multimodal copolymer (P) is preferably a linear low density polyethylene (LLDPE). The density of the multimodal copolymer (P) is between 905 kg / m 3 Up to 915kg / m 3 In the range of 908.0kg / m 3 Up to 915kg / m 3 , more preferably 910.0kg / m 3 Up to 915.0kg / m 3 , and more preferably 911 kg / m 3 Up to 914kg / m 3 .

[0042] More preferably, the multimodal copolymer (P) is multimodal, i.e. there are differences, in at least MFR2, comonomer content and density of the ethylene polymer components (A) and (B), as defined above, below or in the claims, including any preferred ranges or embodiments of the polymer composition.

[0043] Furthermore, the ethylene-1-butene polymer component (A) is preferably characterized by an amount of isolated 1-butene comonomer units of > 95.0%, preferably at least 98.0%, more preferably 100%. The amount of isolated comonomer units is calculated according to formula (I):

[0044]

[0045] where X is the number of 1-butene branches per 1000 carbons (kCb).

[0046] In addition, the ethylene-1-hexene polymer component (B) preferably has an amount of isolated 1-hexene comonomer units according to formula (I), wherein X is the number of 1-hexene branches per 1000 carbons (kCb); and satisfies the formula (II) EXE%>-1.1875*C6(C6 in wt.-% of (B))+110.41(II)

[0047] Preferably, the ethylene-1-hexene polymer component (B) satisfies the following formula

[0048] EXE%>-1.1875*C6(as wt.-% of (B) C6)+111.41, more preferably EXE%>-1.1875*C6(as wt.-% of (B) C6)+112.41, even more preferably EXE%>-1.1875*C6(as wt.-% of (B) C6)+113.41.

[0049] The amount of isolated 1-hexene comonomer units of component (B) is preferably >92.0%, preferably at least 93.0%, more preferably at least 94.0%. A suitable upper limit is <100%, preferably 99.0%, more preferably 98.0%.

[0050] Within the scope of the present invention, the first and second ethylene polymer parts (A-1 and A-2) of the ethylene polymer component (A) are present in a weight ratio of 4:1 to up to 1:4, such as 3:1 to 1:3, or 2:1 to 1:2, or 1:1.

[0051] The ethylene polymer component (A) is present in an amount of 30.0 to 70.0 wt%, preferably 32.0 to 55.0 wt%, even more preferably 34.0 to 45.0 wt%, based on the multimodal copolymer (P).

[0052] Accordingly, the ethylene polymer component (B) is present in an amount of 70.0 to 30.0 wt%, preferably 68.0 to 45.0 wt%, more preferably 66.0 to 55.0 wt%, based on the multimodal copolymer (P).

[0053] The metallocene catalyzed multimodal copolymer (P) may be produced in a two stage process, preferably comprising a slurry reactor (loop reactor), wherein the slurry (loop) reactor is connected in series with 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 copolymer (P).

[0054] In case the ethylene component (A) of the multimodal copolymer (P) consists of ethylene polymer fractions (A-1) and (A-2), the multimodal copolymer (P) may be produced in a three-stage process, preferably comprising a first slurry reactor (loop reactor 1), wherein the first slurry loop reactor is connected in series with a further slurry reactor (loop reactor 2) such that the first ethylene polymer fraction (A-1) produced in the loop reactor 1 is fed to the loop reactor 2, wherein the second ethylene polymer fraction (A-2) is produced in the presence of the first fraction (A-1). The loop reactor 2 is thereby connected in series with a gas phase reactor (GPR) such that the first ethylene polymer fraction (A) leaving the second slurry reactor is fed to the GPR to produce a trimodal polyethylene copolymer. In this case, the reaction conditions in the two slurry reactors are selected such that products of different MFR and / or density are produced in the two slurry reactors.

[0055] This method is described in particular in WO 2016 / 198273 A1, WO 2021 / 009189 A1, WO 2021 / 009190 A1, WO 2021 / 009191 A1 and WO 2021 / 009192 A1. Full details of how to prepare suitable metallocene-catalyzed multimodal copolymers (P) can be found in these references. Metallocene-catalyzed multimodal copolymers (P) are produced by using a metallocene catalyst. The metallocene catalyst preferably comprises a metallocene complex and a cocatalyst. Metallocene compounds or complexes are also referred to herein as organometallic compounds (C).

[0056] 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.

[0057] 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 of 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 of the Elements (IUPAC 2007), as well as compounds of lanthanides or actinides.

[0058] In one embodiment, the organometallic compound (C) has the following formula (I):

[0059]

[0060] Wherein each X is independently a halogen atom, C 1-6 Alkyl, C 1-6 alkoxy, phenyl or benzyl;

[0061] Each Het is independently a monocyclic heteroaromatic group containing at least one heteroatom selected from O or S; L is -R'2Si-, wherein each R' is independently C 1-20 A hydrocarbon group or a C substituted alkoxy group having 1 to 10 carbon atoms 1-10 alkyl;

[0062] M is Ti, Zr or Hf;

[0063] Each R 1 Same or different, C 1-6 Alkyl or C 1-6 Alkoxy;

[0064] Each n is 1 to 2;

[0065] Each R 2 Same or different, C 1-6 Alkyl, C 1-6 Alkoxy or -Si(R)3 group;

[0066] Each R is C 1-10 Alkyl or optionally 1 to 3 C 1-6 Alkyl-substituted phenyl; and

[0067] Each p is from 0 to 1.

[0068] Preferably, the compound of formula (I) has the following structure:

[0069]

[0070] Wherein each X is independently a halogen atom, C 1-6 Alkyl, C 1-6 Alkoxy, phenyl or benzyl; L is Me2Si-;

[0071] Each R 1 Same or different, C 1-6 an alkyl group, such as methyl or tert-butyl;

[0072] Each n is 1 to 2;

[0073] R 2 is -Si(R)3 alkyl; each p is 1;

[0074] Each R is C 1-6 Alkyl or phenyl.

[0075] Highly preferred complexes of formula (I) are

[0076]

[0077] Most preferably, the complex dimethylsilanediylbis[2-(5-trimethylsilylfuran-2-yl)-4,5-dimethylcyclopentadien-1-yl]zirconium dichloride is used.

[0078] More preferably, the ethylene polymer components (A) and (B) of the multimodal copolymer (P) are produced using the same metallocene catalyst, ie are produced in the presence of the same metallocene catalyst.

[0079] To form the catalyst, a cocatalyst known in the art, also called an activator, is used. Cocatalysts containing Al or B are well known and can also be used here. Preferably, an aluminoxane (e.g. methylaluminoxane) or a boron-based cocatalyst (e.g. borates) is used.

[0080] In contrast to Ziegler Natta catalysis, polyethylene copolymers prepared using single-site catalysis 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 indicate the catalyst used. For example, Ziegler Natta catalysts do not contain Zr or Hf Group (IV) metals.

[0081] Multilayer products

[0082] The multilayer article according to the present invention comprises at least an oriented polyethylene base film (OPEF) and a non-oriented polyethylene base film (NOPEF), wherein the non-oriented polyethylene base film (NOPEF) comprises at least the following sublayers:

[0083] i) Surface layer (SKL);

[0084] ii) a core layer (CL); and

[0085] iii) a sealing layer (SL); wherein

[0086] The sealant layer comprises a metallocene-catalyzed multimodal polyethylene copolymer (P) consisting of:

[0087] 30.0 to 70.0% by weight of ethylene-1-butene polymer component (A), and

[0088] 30.0 to 70.0% by weight of the ethylene-1-hexene polymer component (B), wherein the ethylene-1-butene polymer component (A) has

[0089] At 920kg / m 3 Up to 950kg / m 3 Density within the range (ASTM D792);

[0090] an MFR2 (190° C., 2.16 kg, ISO 1133) in the range of 2.0 g / 10 min to 200 g / 10 min; and a 1-butene content in the range of 0.5 to 5.0% by weight based on the ethylene-1-butene polymer component (A); and an ethylene-1-hexene polymer component (B) having

[0091] At 880kg / m 3 Up to 915kg / m 3 Density within the range (ASTM D792);

[0092] an MFR2 (190° C., 2.16 kg, ISO 1133) in the range of 0.01 g / 10 min to 1.5 g / 10 min; and a 1-hexene content in the range of 15.0 to 25.0% by weight based on the ethylene-1-hexene polymer compound (B); wherein

[0093] The multimodal polyethylene copolymer (P) has

[0094] At 905kg / m 3 Up to 915kg / m 3 Density within the range (ASTM D792);

[0095] MFR2 (190°C, 2.16 kg, ISO 1133) in the range of 0.5 g / 10 min to less than 2.0 g / 10 min; and

[0096] MFR 21 Ratio of MFR (190℃, 21.6kg, ISO 1133) to MFR2 (190℃, 2.16kg, ISO 1133), MFR 21 / MFR2, in the range of 22 to 70.

[0097] A preferred embodiment of the present invention provides that the oriented polyethylene base film (OPEF) is produced according to the MDO (machine direction orientation) or BOPE process (biaxially oriented polyethylene), and preferably has a machine direction tensile modulus (ISO 527-3) in the range of 1000 to 3000 MPa. The manufacture of biaxially oriented films is well known (e.g., Chapters 2 and 3 in Biaxial stretching of film: principles and applications edited by Mark T. Demeuse, Woodhead Publishing, 2011). The manufacture of MDO films is also very mature. In general, the machine direction orientation of plastic films and sheets is achieved by heating the web and stretching it in the machine direction on a series of rollers. The device is generally referred to as a machine direction orientator (MDO). For details, see, for example, Multilayer Flexible Packaging (Second Edition), 2016, pages 147-152.

[0098] According to another preferred embodiment of the present invention, the thickness of the oriented polyethylene-based film (OPEF) is in the range of 10 to 100 μm; preferably in the range of 12 to 80 μm, more preferably in the range of 15 to 60 μm, still more preferably in the range of 20 to 40 μm, even more preferably in the range of 15 to 30 μm or 50 to 70 μm. In yet another preferred embodiment of the present invention, the thickness of the non-oriented polyethylene-based film (NOPEF) is in the range of 15 to 160 μm; preferably in the range of 30 to 120 μm, more preferably in the range of 50 to 70 μm.

[0099] According to another preferred embodiment of the present invention, the thickness of the skin layer (SKL) of the non-oriented polyethylene based film (NOPEF) is in the range of 5 to 30 μm; preferably in the range of 8 to 25 μm, more preferably in the range of 10 to 15 μm.

[0100] In another preferred embodiment of the present invention, the thickness of the core layer (CL) of the non-oriented polyethylene based film (NOPEF) is in the range of 10 to 100 μm; preferably in the range of 20 to 80 μm, more preferably in the range of 30 to 45 μm.

[0101] Yet another preferred embodiment of the present invention provides that the thickness of the sealing layer (SL) of the non-oriented polyethylene based film (NOPEF) is in the range of 1 to 30 μm; preferably in the range of 8 to 25 μm, more preferably in the range of 10 to 15 μm.

[0102] According to another preferred embodiment of the present invention, the thickness of the multilayer article is in the range of 25 to 260 μm, preferably in the range of 40 to 150 μm, more preferably in the range of 80 to 90 μm. It is further preferred that the multilayer article consists of a polyethylene-based polymer.

[0103] According to another preferred embodiment of the present invention, the non-oriented polyethylene based film (NOPEF) preferably consists of a skin layer (SKL), a core layer (CL) and a sealing layer (SL).

[0104] The skin layer (SKL) may comprise, based on the total weight of the skin layer (SKL), 70 to 100 wt%, more preferably 80 to 95 wt%, still more preferably 88 to 92 wt% of a multimodal metallocene-catalyzed linear low density polyethylene, preferably a bimodal ethylene / 1-butene / 1-hexene terpolymer, preferably having a molecular weight of 915 kg / m 3 Up to 930kg / m 3 , more preferably 916kg / m 3 Up to 925kg / m 3 The density (ASTM D792) in the range of 0.5 g / 10 min to 2 g / 10 min and the MFR2 (190° C., 2.16 kg, ISO 1133) in the range of 0.5 g / 10 min to 2 g / 10 min; and 0 to 30% by weight, preferably 5 to 20% by weight, more preferably 8 to 12% by weight of LDPE based on the total weight of the skin layer (SKL), which has a molecular weight of 910 kg / m 3 Up to 930kg / m 3 , preferably 920kg / m 3 Up to 925kg / m 3 The core layer (CL) preferably comprises, based on the total weight of the core layer (CL), 60 to 100 wt%, more preferably 70 to 99 wt%, still more preferably 75 to 85 wt% of a Ziegler-Natta catalyzed linear low density polyethylene, which is preferably a multimodal α-olefin terpolymer, preferably having a molecular weight of 920 kg / m 3 Up to 945kg / m 3 , more preferably 930kg / m 3 Up to 942kg / m 3 , and more preferably 928 kg / m 3 Up to 935kg / m 3The core layer (CL) has a density in the range of 0.5 g / 10 min to 2.5 g / 10 min, preferably a MFR2 in the range of 0.7 g / 10 min to 1.5 g / 10 min (190° C., 2.16 kg, ISO 1133); and based on the total weight of the core layer (CL), 0 to 40 wt%, preferably 1 to 30 wt%, more preferably 15 to 25 wt% of a multimodal metallocene-catalyzed linear low density polyethylene, preferably a bimodal ethylene / 1-butene / 1-hexene terpolymer, preferably having a molecular weight of 910 kg / m 3 Up to 930kg / m 3 , more preferably 916kg / m 3 Up to 925kg / m 3 The density is in the range of 0.5 g / 10 min to 2 g / 10 min (ASTM D792) and the MFR2 is in the range of 190°C, 2.16 kg, ISO 1133).

[0105] The sealing layer (SL) preferably comprises, based on the total weight of the sealing layer (SL), 60 to 100 wt% or 65 to 90 wt%, more preferably 75 to 85 wt% of a metallocene-catalyzed multimodal polyethylene copolymer (P) having a molecular weight of 910 kg / m 3 Up to 915kg / m 3 , preferably 911kg / m 3 Up to 914kg / m 3 The present invention relates to a polymer having a density in the range of 0.5 g / 10 min to 1.8 g / 10 min, preferably 1.0 g / 10 min to 1.5 g / 10 min, and a MFR2 (190° C., 2.16 kg, ISO 1133) in the range of 1.0 g / 10 min to 1.5 g / 10 min; and based on the total weight of the sealing layer (SL), 0 to 40% by weight or 10 to 35% by weight, preferably 15 to 25% by weight of a plastomer, preferably a copolymer of ethylene and 1-octene, preferably having a molecular weight of 860 kg / m 3 Up to 910kg / m 3 , preferably 895kg / m 3 Up to 905kg / m 3 The density is in the range of ASTM D792 and the MFR2 is in the range of 0.5 g / 10 min to 10 g / 10 min, preferably 1.0 g / 10 min to 1.5 g / 10 min.

[0106] A further preferred embodiment provides that the multilayer article is a laminate, preferably made of an oriented polyethylene base film (OPEF)

[0107] And non-oriented polyethylene film (NOPEF).

[0108] According to another preferred embodiment of the present invention, the multilayer article has a machine direction (MD) tensile modulus (ISO 527-3) in the range of 600 to 900 MPa, preferably 700 to 900 MPa, more preferably in the range of 750 to 820 MPa.

[0109] According to a further preferred embodiment of the invention, it is provided that the multilayer article has a tensile modulus in the transverse direction (TD) in the range from 800 to 1100 MPa, preferably in the range from 900 to 1000 MPa (ISO 527-3).

[0110] Yet another preferred embodiment provides that the multilayer article has a dart drop strength (ASTM D1709) in the range of 230 to 850 g, preferably 240 to 700 g, more preferably 240 to 600 g, still more preferably 240 to 400 g, even more preferably in the range of 250 to 320 g.

[0111] In another preferred embodiment according to the present invention, the multilayer article has a haze (ASTM D1003-00) in the range of 12% to 20%, preferably in the range of 15% to 18%.

[0112] According to a further preferred embodiment of the invention it is provided that the multilayer article has a sealing initiation temperature determined as described in the description in the range from 60 to 75° C., preferably in the range from 63 to 70° C.

[0113] According to a further preferred embodiment of the invention, the multilayer article has a protrusion (ASTM D5748) in the range of 150 to 300 N, preferably in the range of 159 to 200 N, more preferably in the range of 165 to 180 N.

[0114] The polymers used for the multilayer articles according to the invention may contain additives and fillers in the amounts customary 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).

[0115] It is to be understood in this context that any additives and / or fillers may optionally be added in the form of a so-called masterbatch comprising the respective additives and a carrier polymer. In this case, the carrier polymer is not included in the polymer component of the metallocene-catalyzed multimodal copolymer (P), but is included in the amount of the respective additive based on the total amount (100% by weight) of the polymer composition.

[0116] method

[0117] Another aspect of the invention relates to a method for producing a multilayer article.

[0118] Multilayer products can be obtained by laminating an oriented polyethylene base film (OPEF) to a non-oriented polyethylene base film (NOPEF). This can be achieved in any conventional laminating device using a conventional laminating method, such as adhesive lamination, including solvent-based and solvent-free adhesive lamination using any conventional commercially available adhesive. Alternatively, lamination can be carried out without any adhesive, such as sandwich lamination with or without molten webs, which can be pressed between substrates. This molten web can be any conventional molten web material based on polyethylene, such as LDPE. Lamination can also be carried out by extrusion coating technology. All these lamination methods are well known in the art and described in the literature.

[0119] use

[0120] Another aspect of the invention relates to the use of the multilayer article as packaging material, preferably for food and / or pharmaceutical products.

[0121] The invention will now be described with reference to the following non-limiting examples.

[0122] Experimental Section

[0123] A. Measurement Method

[0124] Unless otherwise defined, the following term definitions and determination methods apply to the above general description of the invention as well as the following examples.

[0125] Melt flow rate The melt flow rate (MFR) is determined according to ISO 1133 - Thermoplastics - Determination of melt mass-flow rate (MFR) and melt volume-flow rate (MVR) - Part 1: Standard method and is expressed in g / 10 min. The MFR is an indication of the fluidity of the polymer and therefore of the processability. The higher the melt flow rate, the lower the viscosity of the polymer. The MFR of polyethylene is determined at 190 °C and can be determined at different loads, such as 2.16 kg (MFR2), 5 kg (MFR5) or 21.6 kg (MFR 21 ).

[0126] Calculation of MFR2 of component B and part (A-2)

[0127] logA=x·logB+(1-x)·logC

[0128]

[0129] For component B:

[0130] B = MFR2 of component (A)

[0131] C = MFR2 of component (B)

[0132] A = Final MFR2 of the multimodal polyethylene copolymer (P) (blend)

[0133] X = weight fraction of component (A)

[0134] For part (A-2):

[0135] B = MFR2 of the first part (A-1)

[0136] C = MFR2 of the second part (A-2)

[0137] A = Final MFR2 of cyclic polymer (= component (A)) (mixture)

[0138] X = weight fraction of the first part (A-1).

[0139] density

[0140] The density of the polymers is measured according to ASTM D792 method B (density determined by balance at 23° C.) on compression molded specimens prepared according to EN ISO 1872-2 and is reported in kg / m.

[0141] DSC analysis, melting temperature (T m ) and crystallization temperature (T c )

[0142] Data were measured using a TAInstrument Q2000 Differential Scanning Calorimetry (DSC) on 5 to 7 mg samples. The DSC was run according to ISO 11357 / Part 3 / Method C2 in a heating / cooling / heating cycle with a scan rate of 10°C / min over a temperature range of -30°C to +225°C.

[0143] The crystallization temperature (T c ) and crystallization enthalpy (Hc), while the melting temperature (T m ) and melting enthalpy (H m ) is determined by the second heating step.

[0144] Haze

[0145] Haze was measured according to ASTM D1003-00 on films (non-oriented films, oriented films, and laminates) as described below.

[0146] Dart Drop Intensity (DDI): Impact resistance measured by the free-falling dart method

[0147] DDI was measured according to ISO 7765-1:1988 / Method A from films (non-oriented films and laminates) produced as shown below. This test method covers the determination of the energy to cause failure of a film under specified impact conditions of a free-falling dart from a specified height which would cause 50% of the test specimens to fail (Step Method A). Uniform increments of missile mass were used during the test and after each sample test, the missile weight was reduced or increased by uniform increments depending on the result observed for the sample (failure or no failure).

[0148] Standard conditions:

[0149] Conditioning time: >96 hours

[0150] Test temperature: 23℃

[0151] Dart head material: phenolic resin

[0152] Dart diameter: 38mm

[0153] Drop height: 660mm

[0154] result:

[0155] Impact failure weight - 50% [g]

[0156] Tensile modulus (TM)

[0157] Tensile modulus (MPa) was measured in accordance with ISO 527-3 in the machine direction (MD) and transverse direction (TD) on film samples (non-oriented films, oriented films, and laminates) prepared as described below using a crosshead speed of 1 mm / min.

[0158] Sealing start temperature (SIT); Sealing end temperature (SET), Sealing range The method determines the sealing temperature range (sealing range) of polyethylene films, in particular blown films, cast films or laminates. The sealing temperature range is the temperature range over which the film can be sealed according to the conditions given below.

[0159] The lower limit (heat seal initiation temperature (SIT)) is the sealing temperature at which a seal strength of ≥ 5 N is achieved. The upper limit (seal end temperature (SET)) is reached when the film adheres to the sealing device.

[0160] The measurements were performed according to a slightly modified ASTM F1921-12, where the test parameters sealing pressure, cooling time and test speed have been modified. The force / temperature curve was continued until thermal failure of the membrane.

[0161] The sealing range was determined on a J&B 4000 Universal Sealer using films (non-oriented films and laminates) produced as described below and having the following further parameters:

[0162] Conditioning time: >96 hours

[0163] Sample width: 25mm

[0164] Sealing pressure: 0.4N / mm 2 (PE)

[0165] Sealing time: 1 second

[0166] Delay time: 30 seconds

[0167] Sealing jaw size: 50x5mm

[0168] Sealing claw shape: flat

[0169] Sealing jaw coating: Niptef

[0170] Sealing temperature: ambient temperature to 240°C

[0171] Sealing temperature interval: 5°C

[0172] Starting temperature: 50℃

[0173] Clamp separation rate: 42mm / sec

[0174] Comonomer content - quantification of microstructure by NMR spectroscopy

[0175] Quantitative nuclear magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content of the polymers.

[0176] Quantification 13 C{ 1 H} NMR spectra were recorded in the molten state using a Bruker Advance III 500 NMR spectrometer at 500.13 MHz and 125.76 MHz, respectively. 1 H and 13 C. All spectra were obtained using 13 A C-optimized 7 mm magic angle spinning (MAS) probe was recorded at 150 °C, with nitrogen used for all pneumatics. Approximately 200 mg of material was loaded into a 7 mm outer diameter zirconium oxide MAS rotor and spun at 4 kHz. This setup was chosen primarily for the high sensitivity required for rapid identification and accurate quantification {klimke06, parkinson07, castignolles09}. Standard single pulse excitation was used, exploiting the NOE (nuclear Overhauser effect) with a short recovery delay time (3 s) {pollard04, klimke06}, and an RS-HEPT decoupling scheme {fillip05, griffin07} was employed. A total of 1024 (1k) transients were acquired for each spectrum.

[0177] Quantitative 13 C{ 1 H} NMR spectra were processed, integrated, and relevant quantitative properties determined from the integration. All chemical shifts were internally referenced to the bulk methylene signal (+) at 30.00 ppm.

[0178] The amount of ethylene was quantified using a methylene (+) site integration of 30.00 ppm (accounting for the number of reported sites per monomer):

[0179] E=I δ+ / 2

[0180] Correction for the presence of independent comonomers is made based on the amount of independent comonomer present: Etotal = E + (3*B + 2*H) / 2

[0181] wherein B and H are defined with respect to their respective comonomers. If there is a correction for the incorporation of continuous and non-continuous comonomers, it is done in a similar manner.

[0182] Characteristic signals corresponding to 1-butene incorporation were observed, and the comonomer fraction was calculated as the fraction of 1-butene in the polymer relative to all monomers in the polymer:

[0183] fBtotal=Btotal / (Etotal+Btotal+Htotal)

[0184] The amount of 1-butene isolated in the EEBEE sequence was quantified using a *B2 site integral of 39.8 ppm (accounting for the number of reported sites per comonomer):

[0185] B=I *B2

[0186] If present, the amount of 1-butene continuously incorporated into the EEBBEE sequence was quantified using a B2B2 site integral of 39.4 ppm (accounting for the number of reported sites per comonomer):

[0187] BB=2*IααB2B2

[0188] If present, the amount of non-reporting sites per comonomer:

[0189] HEH=2*I IββB4B4

[0190] No HHH sequence was observed. The total 1-hexene content was calculated from the sum of isolated, continuously and discontinuously incorporated 1-hexene:

[0191] Htotal=H+HH+HEH

[0192] The total mole fraction of 1-hexene in the polymer is then calculated:

[0193] fH=Htotal / (Etotal+Btotal+Htotal)

[0194] The mole percentage of comonomer incorporation is calculated from the mole fraction:

[0195] B[mol%]=100*fB

[0196] H[mol%]=100*fH

[0197] The weight percent of comonomer incorporation is calculated from the mole fraction:

[0198] B[wt.-%]=100*(fB*56.11) / ((fB*56.11)+(fH*84.16)+((1-(fB+fH))*28.05))

[0199] H[wt.-%]=100*(fH*84.16) / ((fB*56.11)+(fH*84.16)+((1-(fB+fH))*28.05))

[0200] References:

[0201] Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2006; 207:382.

[0202] Parkinson, M., Klimke, K., Spiess, HW, Wilhelm, M., Macromol. Chem. Phys. 2007; 208:2128.

[0203] Pollard,M.,Klimke,K.,Graf,R.,Spiess,HW,Wilhelm,M.,Sperber,O.,Piel,C.,Kaminsky,W.,Macromolecules 2004;37:813.

[0204] Filip,X.,Tripon,C.,Filip,C.,J.Mag.Resn.2005,176,239.

[0205] Griffin,JM,Tripon,C.,Samoson,A.,Filip,C.,and Brown,SP,Mag.Res.inChem.2007 45,S1,S198.

[0206] Castignolles,P.,Graf,R.,Parkinson,M.,Wilhelm,M.,Gaborieau,M.,Polymer50(2009)2373.

[0207] Busico,V.,Cipullo,R.,Prog.Polym.Sci.26(2001)443.

[0208] Busico,V.,Cipullo,R.,Monaco,G.,Vacatello,M.,Segre,AL,Macromoleucles30(1997)6251.

[0209] Zhou,Z.,Kuemmerle,R.,Qiu,X.,Redwine,D.,Cong,R.,Taha,A.,Baugh,D.Winniford,B.,J.Mag.Reson.187(2007)225.

[0210] Busico,V.,Carbonniere,P.,Cipullo,R.,Pellecchia,R.,Severn,J.,Talarico,G.,Macromol.Rapid Commun.2007,28,1128.

[0211] Resconi,L.,Cavallo,L.,Fait,A.,Pimontesi,F.,Chem.Rev.2000,100,1253.Outstanding

[0212] The films (laminates) produced as described below were subjected to protrusion puncture resistance testing according to ASTM D5748. The puncture resistance (N) is the maximum or highest force observed during the test, and the puncture resistance energy (J) is the energy used until the probe breaks the specimen, both of which are measured using a high-precision 500N load cell and a crosshead position sensor.

[0213] B. Materials used

[0214] HDPE

[0215] FB5600 is a bimodal high-density polyethylene (MFR2 (190℃ / 2.16kg): 0.70g / 10min, density: 960kg / m 3 , T m 132℃), can be used as Borouge FB5600 was commercially available.

[0216] LDPE

[0217] FT5236 is a low density polyethylene (MFR2 (190℃ / 2.16kg): 0.75g / 10min, density: 923kg / m 3 , T m 112°C, produced by Tubular Technology), commercially available as FT5236 from Borealis AG, and contains antiblocking agents, antioxidants and slip additives.

[0218] Multimodal metallocene-catalyzed linear low-density polyethylene

[0219] FK1820 is a bimodal ethylene / 1-butene / 1-hexene terpolymer (MFR2 (190°C / 2.16kg): 1.5g / 10min, density: 918kg / m 3 , T m 122℃, produced with metallocene catalysts), can be used as Anteo TM FK1820 is commercially available from Borouge and contains antioxidants and processing aids.

[0220] Ziegler-Natta catalyzed linear low density polyethylene

[0221] FX1001 is a multimodal α-olefin terpolymer (MFR5 (190℃ / 5kg): 0.9g / 10min, density: 931kg / m 3 , T m 127℃, produced with Ziegler-Natta catalyst), can be used as BorShape TM FX1001 is commercially available from Borealis AG and contains antioxidants.

[0222] FX1002 is a multimodal α-olefin terpolymer (MFR5 (190℃ / 5kg): 2.0g / 10min, density: 937kg / m 3 , T m 128℃, produced with Ziegler-Natta catalyst), can be used as BorShape TM FX1002 is commercially available from Borealis AG and contains antioxidants.

[0223] Plastic body

[0224] Queo0201 is a unimodal ethylene-based 1-octene plastomer (MFR2 (190°C / 2.16kg): 1.1g / 10min, density: 902kg / m 3 , T m 97℃, produced in a solution polymerization process using a metallocene catalyst), can be used as Queo TM 0201 is commercially available from Borealis AG and contains a processing stabilizer.

[0225] Slip MB can be used as CE-505-E is commercially available from A. Schulman and is a 5 wt% erucamide slip agent concentrate in polyethylene with an MFR2 of 20 g / 10 min.

[0226] Antiblock can be used as FSU-105-E is commercially available from A. Schulman and is a general purpose erucamide slip and antiblock concentrate in LDPE with an MFR2 of 13 g / 10 min. A metallocene-catalyzed multimodal polyethylene copolymer (P) was prepared as follows:

[0227] Catalyst preparation (CAT)

[0228] Silica loading:

[0229] 10 kg of silica (PQ Corporation ES757, calcined at 600° C.) was added from a feed drum and inerted in the reactor until an O2 level below 2 ppm was reached.

[0230] Preparation of MAO / tol / MC:

[0231] A 30% weight solution of MAO in toluene (14.1 kg) was added from a balance to another reactor, followed by the addition of toluene (4.0 kg) at 25°C (oil circulation temperature) with a stirring speed of 95 rpm. After the addition of toluene, the stirring speed was increased from 95 rpm to 200 rpm for 30 minutes. 477 g of racemic-dimethylsilanediylbis{2-(5-(trimethylsilyl)furan-2-yl)-4,5-dimethylcyclopentadiene-1-yl}zirconium dichloride metallocene was added from a metal cylinder, followed by a rinse with 4 kg of toluene (total toluene amount was 8.0 kg). The reactor stirring speed was changed to 95 rpm for MC feeding and returned to 200 rpm for a reaction time of 3 hours. After the reaction was completed, the MAO / tol / MC solution was transferred to the feed container.

[0232] Preparation of catalyst:

[0233] The reactor temperature was set to 10°C (oil circulation temperature) and the stirring speed was adjusted to 40 rpm during the addition of MAO / tol / MC. The MAO / tol / MC solution (22.2 kg) was added over 205 minutes, followed by stirring for 60 minutes (the oil circulation temperature was set to 25°C). After stirring, the "dry mixture" was stabilized at 25°C (oil circulation temperature) for 12 hours without stirring. The reactor was turned (back and forth) by 20° and stirred at a speed of 5 rpm for several rounds, once every hour.

[0234] After stabilization, the catalyst was dried at 60°C (oil circulation temperature) for 2 hours under a 2 kg / h nitrogen flow and then vacuum dried for 13 hours (under the same nitrogen flow with 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 thermogravimetric method. The target HC level was less than 2% (actual 1.3%).

[0235] polymerization:

[0236] The polymerization was carried out in a Borstar pilot plant with a 3-reactor set-up (Loop 1 - Loop 2 - GPR) and a prepolymerization loop reactor according to the conditions given in Table 1.

[0237] Table 1: Polymerization conditions.

[0238]

[0239]

[0240] The metallocene-catalyzed multimodal polyethylene copolymer (P) was mixed with 2400 ppm of Irganox B561 (commercially available from BASF) and 270 ppm of Dynamar FX 5922 (commercially available from 3M), compounded and extruded into pellets using a JSW extruder under a nitrogen atmosphere to give a SEI of 230 kWh / kg and a melt temperature of 250° C. The properties of (P) are summarized in Table 2 below.

[0241] Table 2: Properties of metallocene-catalyzed multimodal polyethylene copolymers (P).

[0242]

[0243]

[0244] C. Film and Laminate Manufacturing

[0245] A 5-layer MDO membrane (OPEF) was produced as follows.

[0246] The starting blown film was produced on an Alpine 7 semi-commercial line. The film formulation is shown in Table 3. The starting film had a thickness of 150 μm, a BUR of 1:2.5, and a melt temperature of 220°C. The film was stored at 23°C for 24 hours and then stretched on a pilot line in an Alpine MDO20. The stretch ratio was 1:6.0 and the stretching roll temperature was 122°C. The final film had a thickness of 25 μm, a haze of 7.7%, and a tensile modulus (MD) of 2514 MPa. In order to achieve a surface energy of at least 38 dynes, the laminated side was corona treated.

[0247] Table 3: 5-layer MDO membrane (OPEF).

[0248] layer Material (mass percentage content) Layer distribution (%) 1 FB5600(100) 15 2 FX1002(70)+FB5600(30) 10 3 FX1002(100) 50 4 FX1002(70)+FB5600(30) 10 5 FB5600(100) 15

[0249] In addition, three non-oriented films were produced as follows (see composition and properties in Table 4). The films were produced on an Alpine 7 semi-commercial production line with a BUR of 1:2.5 and a film thickness of 60 μm. The production line conditions were adjusted to ensure smooth production, such as film thickness distribution <5%. The film formulations and film properties are shown in Table 4. In order to achieve a surface energy of at least 38 dynes, the laminated side was corona treated.

[0250] Finally, laminates of the MDO film shown in Table 3 and the non-oriented film shown in Table 4 were produced. The skin layer was laminated to the MDO film. The lamination was performed on a laboratory scale on a solventless laminator, running at a speed of 150 m / min, with an adhesive content of 1.8 g / m2. The adhesive used was LA7825 and hardener LA6230 (both supplied by Henkel), mixed in a ratio of 2:1. The corona treatment intensity on the carrier web was 2.5 kW and on the auxiliary web was 1.5 kW.

[0251] D. Results

[0252] Table 4: Composition and properties of non-oriented films and laminates.

[0253]

[0254]

[0255] The mass percentages (wt.-%) are based on the total weight of the non-oriented film.

[0256] E. Discussion of Results

[0257] The laminates according to the invention (IE1 and IE2) have the same skin layers and the same core layer as the laminate according to the comparative example (CE1).The laminates according to IE1 and IE2 differ from the laminate according to CE1 by the polymer used in the sealing layer.

[0258] As can be seen from Table 4 above, the laminate according to the present invention not only shows better stiffness and toughness (indicated by tensile modulus, dart drop strength and stickout), but also shows better sealing performance (lower SIT) with comparable haze.

Claims

1. A multilayer article comprising at least an oriented polyethylene base film (OPEF) and a non-oriented polyethylene base film (NOPEF), wherein The non-oriented polyethylene-based film (NOPEF) comprises at least the following sublayers: i) Surface layer (SKL); ii) a core layer (CL); and iii) a sealing layer (SL); wherein The sealing layer comprises a metallocene-catalyzed multimodal polyethylene copolymer (P) consisting of: 30.0 to 70.0% by weight of ethylene-1-butene polymer component (A), and 30.0 to 70.0% by weight of ethylene-1-hexene polymer component (B), wherein The ethylene-1-butene polymer component (A) has ·920kg / m 3 Up to 950kg / m 3 Density within the range (ASTM D792); MFR2 (190°C, 2.16 kg, ISO 1133); and · a 1-butene content in the range of 0.5 to 5.0% by weight based on the ethylene-1-butene polymer component (A); and The ethylene-1-hexene polymer component (B) has ·880kg / m 3 Up to 915kg / m 3 Density within the range (ASTM D792); MFR2 (190°C, 2.16 kg, ISO 1133) in the range of 0.01 g / 10 min to 1.5 g / 10 min; and · a 1-hexene content in the range of 15.0 to 25.0% by weight based on the ethylene-1-hexene polymer compound (B); in The multimodal polyethylene copolymer (P) has ·At 905kg / m 3 Up to 915kg / m 3 Density within the range (ASTM D792); MFR2 (190°C, 2.16 kg, ISO 1133) in the range of 0.5 g / 10 min to less than 2.0 g / 10 min; and MFR 21 Ratio of MFR (190℃, 21.6kg, ISO 1133) to MFR2 (190℃, 2.16kg, ISO 1133), MFR 21 / MFR2, in the range of 22 to 70.

2. The multilayer product according to claim 1, characterized in that The oriented polyethylene based film (OPEF) is produced according to the MDO (machine direction orientation) or BOPE process (biaxially oriented polyethylene) and preferably has a machine direction tensile modulus (ISO 527-3) in the range of 1000 to 3000 MPa.

3. The multilayer product according to claim 1 or 2, characterized in that The thickness of the oriented polyethylene-based film (OPEF) is in the range of 10 to 100 μm; preferably in the range of 12 to 80 μm, more preferably 15 to 60 μm, still more preferably 20 to 40 μm, even more preferably in the range of 15 to 30 μm or 50 to 70 μm; and / or The thickness of the non-oriented polyethylene-based film (NOPEF) is in the range of 15 to 160 μm; preferably in the range of 30 to 120 μm, more preferably in the range of 50 to 70 μm; and / or The thickness of the skin layer (SKL) of the non-oriented polyethylene based film (NOPEF) is in the range of 5 to 30 μm; preferably in the range of 8 to 25 μm, more preferably in the range of 10 to 15 μm; and / or The thickness of the core layer (CL) of the non-oriented polyethylene based film (NOPEF) is in the range of 10 to 100 μm; preferably in the range of 20 to 80 μm, more preferably in the range of 30 to 45 μm; and / or The thickness of the sealing layer (SL) of the non-oriented polyethylene based film (NOPEF) is in the range of 1 to 30 μm; preferably in the range of 8 to 25 μm, more preferably in the range of 10 to 15 μm; and / or The thickness of the multilayer article is in the range of 25 to 260 μm; preferably in the range of 40 to 150 μm, more preferably in the range of 80 to 90 μm; and / or The multilayer article is composed of a polyethylene-based polymer.

4. The multilayer article according to any one of the preceding claims, characterized in that The non-oriented polyethylene-based film (NOPEF) preferably consists of a skin layer (SKL), a core layer (CL) and a sealing layer (SL); wherein The skin layer (SKL) preferably comprises Based on the total weight of the skin layer (SKL), 70 to 100% by weight, more preferably 80 to 95% by weight, still more preferably 88 to 92% by weight of a multimodal metallocene-catalyzed linear low density polyethylene, preferably a bimodal ethylene / 1-butene / 1-hexene terpolymer, preferably having a molecular weight of 915 kg / m 3 Up to 930kg / m 3 , more preferably 916kg / m 3 Up to 925kg / m 3 Density in the range of 1000 g / min to 2000 g / min (ASTM D792) and MFR2 in the range of 0.5 g / 10 min to 2 g / 10 min (190°C, 2.16 kg, ISO 1133); and Based on the total weight of the skin layer (SKL), 0 to 30% by weight, preferably 5 to 20% by weight, more preferably 8 to 12% by weight of a low density polyethylene having a molecular weight of 910 kg / m 3 Up to 930kg / m 3 , preferably 920kg / m 3 Up to 925kg / m 3 The density (ASTM D792) is in the range of 0.5 g / 10 min to 4 g / 10 min, preferably 1 g / 10 min to 2 g / 10 min or 0.5 g / 10 min to 1.0 g / 10 min.

5. The multilayer article according to any one of the preceding claims, characterized in that The non-oriented polyethylene-based film (NOPEF) preferably consists of a skin layer (SKL), a core layer (CL) and a sealing layer (SL); wherein The core layer (CL) preferably comprises Based on the total weight of the core layer (CL), 60 to 100 wt%, preferably 70 to 99 wt%, more preferably 75 to 85 wt% of a Ziegler-Natta catalyzed linear low density polyethylene, which is preferably a multimodal α-olefin terpolymer, preferably having a molecular weight of 920 kg / m 3 Up to 945kg / m 3 , more preferably 930kg / m 3 Up to 942kg / m 3 , and more preferably 928 kg / m 3 Up to 935kg / m 3 A density in the range of 100 to 200 g / min (ASTM D792) and an MFR2 in the range of 0.5 to 2.5 g / 10 min, preferably 0.7 to 1.5 g / 10 min; and Based on the total weight of the core layer (CL), 0 to 40 wt%, preferably 1 to 30 wt%, more preferably 15 to 25 wt% of a multimodal metallocene-catalyzed linear low density polyethylene, preferably a bimodal ethylene / 1-butene / 1-hexene terpolymer, preferably having a molecular weight of 910 kg / m 3 Up to 930kg / m 3 , more preferably 916kg / m 3 Up to 925kg / m 3 The density is in the range of 0.5 g / 10 min to 2 g / 10 min (ASTM D792) and the MFR2 is in the range of 190°C, 2.16 kg, ISO 1133).

6. The multilayer article according to any one of the preceding claims, characterized in that The non-oriented polyethylene-based film (NOPEF) preferably consists of a skin layer (SKL), a core layer (CL) and a sealing layer (SL); wherein The sealing layer (SL) preferably comprises Based on the total weight of the sealing layer (SL), 60 to 100 wt% or 65 to 90 wt%, preferably 75 to 85 wt% of the metallocene-catalyzed multimodal polyethylene copolymer (P) having a molecular weight of 910 kg / m 3 Up to 915kg / m 3 , preferably 911kg / m 3 Up to 914kg / m 3 A density in the range of 1.5 to 2.0 g / 10 min (ASTM D792) and an MFR2 in the range of 0.5 to 1.8 g / 10 min, preferably 1.0 to 1.5 g / 10 min; and Based on the total weight of the sealing layer (SL), 0 to 40% by weight or 10 to 35% by weight, preferably 15 to 25% by weight of a plastomer, preferably a copolymer of ethylene and 1-octene, preferably having a molecular weight of 860 kg / m 3 Up to 910kg / m 3 , preferably 895kg / m 3 Up to 905kg / m 3 The density is in the range of ASTM D792 and the MFR2 is in the range of 0.5 g / 10 min to 10 g / 10 min, preferably 1.0 g / 10 min to 1.5 g / 10 min.

7. The multilayer article according to any one of the preceding claims, characterized in that The multilayer article is a laminate, preferably consisting of the oriented polyethylene based film (OPEF) and the non-oriented polyethylene based film (NOPEF).

8. The multilayer article according to any one of the preceding claims, characterized in that The multimodal polyethylene copolymer (P) has in component (A) an amount of isolated 1-butene comonomer units of > 95%, wherein the amount of isolated 1-butene comonomer units is calculated according to formula (I) X is the number of 1-butene branches per 1000 carbons (kCb); and The amount of isolated 1-hexene comonomer units in component (B) according to formula (I), wherein X is the number of 1-hexene branches per 1000 carbons (kCb); satisfying formula (II) EXE%>-1.1875*C6(C6 in wt.-% (B))+110.41 (II).

9. The multilayer article according to any one of the preceding claims, characterized in that The component (A) of the metallocene-catalyzed multimodal polyethylene copolymer (P) consists of an ethylene polymer fraction (A-1) and an ethylene polymer fraction (A-2); wherein; The ethylene polymer portion (A-1) preferably has 920kg / m 3 Up to 960kg / m 3 , preferably 925kg / m 3 Up to 955kg / m 3 , more preferably 930kg / m 3 Up to 950kg / m 3 Density within the range (ASTM D792); and / or an MFR2 (190°C, 2.16 kg, ISO 1133) in the range of 1.0 g / 10min to 20.0 g / 10min or 3 g / 10min to 300 g / 10min, preferably 1.5 g / 10min to 18.0 g / 10min, more preferably 2.0 g / 10min to 16.0 g / 10min, even more preferably 2.5 g / 10min to 14.0 g / 10min, and / or The ethylene polymer portion (A-2) preferably has 930kg / m 3 Up to 950kg / m 3 , preferably 935kg / m 3 Up to 945kg / m 3 The density (ASTM D792) is in the range of 3.0 g / 10min to 40.0 g / 10min, preferably 3.2 g / 10min to 30.0 g / 10min, more preferably 3.5 g / 10min to 20.0 g / 10min, and most preferably 3.5 g / 10min to 10.0 g / 10min. MFR2 (190°C, 2.16 kg, ISO 1133) is in the range of 3.0 g / 10min to 40.0 g / 10min, preferably 3.2 g / 10min to 30.0 g / 10min, more preferably 3.5 g / 10min to 20.0 g / 10min, and most preferably 3.5 g / 10min to 10.0 g / 10min.

10. The multilayer article according to any one of the preceding claims, characterized in that The metallocene-catalyzed multimodal copolymer (P) has MFR 21 Ratio of MFR (190℃, 21.6kg, ISO 1133) to MFR2 (190℃, 2.16kg, ISO 1133) 21 / MFR2 is in the range of 23 to 50, preferably 25 to 40, more preferably 28 to 35; and / or the total amount of 1-butene is in the range of 0.1 to 2.5 wt.-%, preferably 0.1 to 1.0 wt.-%, more preferably 0.2 to 0.8 wt.-% and still more preferably 0.3 to 0.6 wt.-% based on the multimodal polymer (P); and / or The total amount of 1-hexene based on the multimodal polymer (P) is in the range of 2.0 to 20.0 wt.-%, preferably 4.0 to 18.0 wt.-%, and more preferably 6.0 to 15.0 wt.-%.

11. The multilayer article according to any one of the preceding claims, characterized in that The metallocene-catalyzed multimodal copolymer (P) is produced in the presence of a metallocene complex of formula (I): Wherein each X is independently a halogen atom, C 1-6 Alkyl, C 1-6 alkoxy, phenyl or benzyl; Each Het is independently a monocyclic heteroaromatic group containing at least one heteroatom selected from O or S; L is -R'2Si-, wherein each R' is independently C 1-20 A hydrocarbon group or a C substituted alkoxy group having 1 to 10 carbon atoms 1-10 alkyl; M is Ti, Zr or Hf; Each R1 is the same or different, for C 1-6 Alkyl or C 1-6 Alkoxy; Each n is 1 to 2; Each R2 is the same or different, and is C 1-6 Alkyl, C 1-6 Alkoxy or -Si(R)3 group; Each R is C 1-10 Alkyl or optionally 1 to 3 C 1-6 Alkyl-substituted phenyl; and Each p is from 0 to 1.

12. The multilayer article according to any one of the preceding claims, characterized in that The multilayer article has a machine direction tensile modulus (ISO 527-3) in the range of 600 to 900 MPa, preferably 700 to 900 MPa, more preferably 750 to 820 MPa; and / or a tensile modulus in the transverse direction in the range of 800 to 1100 MPa, preferably in the range of 900 to 1000 MPa (ISO 527-3); and / or • Dart drop strength (ASTM D1709) in the range of 230 to 850 g, preferably 240 to 750 g, more preferably 240 to 600 g, still more preferably 240 to 400 g, even more preferably in the range of 250 to 320 g.

13. The multilayer article according to any one of the preceding claims, characterized in that The multilayer article has A haze (ASTM D1003-00) in the range of 12% to 20%, preferably in the range of 15% to 18%; and / or Determining a sealing initiation temperature in the range of 60 to 75°C, preferably in the range of 63 to 70°C as described in the specification; and / or • Protrusion in the range of 150 to 300 N, preferably in the range of 159 to 200 N, more preferably in the range of 165 to 180 N (ASTM D5748).

14. A method of producing a multilayer article according to any one of the preceding claims.

15. Use of the multilayer article according to any one of claims 1 to 13 as packaging material, preferably for food and / or pharmaceutical products.

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