Biaxially oriented polyolefin film

Abstract

A biaxially oriented multilayer film having a core layer comprising a polyethylene-based composition, the core layer having a melt index (I2) in the range of 0.2 g / 10 min to 5.0 g / 10 min and a viscosity of 0.930 g / cm 3 ~0.956g / cm 3 and the portion between 4.0 and 5.0 log(Mw) (SCB logMw4~5 ) and an average short chain branching (SCB) level in the propylene-based composition. The biaxially oriented multilayer film also includes at least one additional layer comprising a propylene-based composition.

Description

[Technical Field]

[0001] The present invention relates to biaxially oriented multilayer polyolefin films comprising a polyethylene core, laminates comprising such films, and articles comprising such films and laminates. [Background technology]

[0002] Biaxially oriented polyethylene (BOPE) films have attracted much attention in the flexible packaging market because they are a very good candidate to replace oriented polyester or polyamide films in the development of sustainable and recyclable packaging. Various polyethylene resins have been developed and are commercially available for BOPE films, many of which have a viscosity of 0.930 g / cm. 3 The stiffness and heat resistance of BOPE films made from such resins are significantly lower than those of oriented polyester or oriented polyamide films. This has limited the current use of BOPE films in the flexible packaging industry. Given the multi-layer nature of flexible packaging and the compatibility between certain polyolefins, the inclusion of small amounts of heterogeneous polyolefins may be acceptable in recycling systems. For example, a polyethylene (PE)-based film containing a small amount of propylene-based polymers may still be recognized as mono-PE packaging. This opens up an opportunity to develop PE-rich biaxially oriented polyolefin films with improved stiffness, heat resistance, and balanced optical properties, which can meet the market need for more sustainable solutions in the packaging industry.

[0003] One relatively new material technology on the processing side is biaxially oriented polyethylene (BOPE) film, which is formed by cast extrusion and then oriented in the machine direction (MD) followed by transverse direction (TD) orientation using a tenter frame. Alternatively, these orientation steps may also be performed simultaneously. Due to the molecular structure, microstructure, and crystallization kinetics of polyethylene, it is often difficult to biaxially orient conventional polyethylene.

[0004] It would be desirable to have new polyethylene-based compositions that have good processability into biaxially oriented polyethylene films, and new biaxially oriented polyethylene films that have desirable and / or improved properties. Summary of the Invention

[0005] Typically, the stiffness and heat resistance of PE films are controlled by the density of the PE. Films made with higher density PE generally have higher stiffness. However, increasing the density of PE can reduce orientation stability and significantly narrow the operating window in biaxial orientation processes. As a result, it has been difficult to produce commercially acceptable BOPE films from higher density PE.

[0006] The present disclosure provides polyethylene-based compositions suitable for processing into biaxially oriented multilayer polyethylene polyolefin films, and biaxially oriented multilayer polyolefin films having desired and / or improved properties. Such polyethylene-based compositions, in some embodiments, can advantageously widen the operating window for stretching films to provide biaxially oriented polyolefin films. For example, widening the operating window for biaxial orientation can allow for higher density polyethylene orientation, which can result in improved film stiffness. Other advantages may include, but are not limited to, better film converting and printability, improved optical properties (e.g., higher clarity and lower haze), improved barrier performance of metallized biaxially oriented polyethylene films, and improved processability on larger and wider tenter frames.

[0007] Aspect 1 includes a biaxially oriented multilayer film, a core layer including a polyethylene-based composition, and the core layer has a total melt index (I2) of 0.2 g / 10 min to 5.0 g / 10 min and a melt index (I3) of 0.930 g / cm 3 ~0.956g / cm 3and the part between 4.0 and 5.0 log(Mw) (SCB logMw4~5 and at least one additional layer comprising a propylene-based composition.

[0008] Example 2 includes the biaxially oriented multilayer film of Example 1, wherein the propylene-based composition is selected from the group consisting of copolymers of propylene and other olefins, terpolymers of propylene and other olefins, and combinations thereof.

[0009] Aspect 3 includes the biaxially oriented multilayer film of any one of Aspects 1 or 2, wherein the propylene-based composition has a DSC melting point of 120°C to 150°C.

[0010] Example 4 includes the biaxially oriented multilayer film of any one of Examples 1-3, wherein the polyethylene-based composition is a blend including a first polyethylene-based component and a second polyethylene-based component.

[0011] In a fifth aspect, the first polyethylene-based component has a melt index (I2) of 0.1.0 g / 10 min to 1.5 g / 10 min and a viscosity of 0.965 g / cm 3 ~0.970g / cm 3 and the second polyethylene-based component is a high-density polyethylene (HDPE) having a melt index (I2) of 0.1 g / 10 min to 3.0 g / 10 min and a viscosity of 0.915 g / cm 3 ~0.930g / cm 3 The biaxially oriented multilayer film of embodiment 4, wherein the polyethylene is a linear low density polyethylene (LLDPE) having a density of

[0012] Example 6 includes the biaxially oriented multilayer film of any one of Examples 4 or 5, wherein the polyethylene-based composition further comprises a third polyethylene-based component.

[0013] In a seventh aspect, the third polyethylene-based component has a melt index (I2) of 0.1 g / 10 min to 0.5 g / 10 min and a viscosity of 0.955 g / cm 3 ~0.965g / cm 3 The biaxially oriented multilayer film of embodiment 6 is a high density polyethylene (HDPE) having a density of

[0014] In embodiment 8, the overall density of the core layer is 0.940 g / cm 3 ~0.955g / cm 3 The biaxially oriented multilayer film of any one of Aspects 1 to 7 includes the biaxially oriented multilayer film of any one of Aspects 1 to 7, wherein

[0015] Aspect 9 is a method for manufacturing a core layer having an average SCB greater than 4.5 SCB / 1000C. logMw4~5 The biaxially oriented multilayer film of any one of Aspects 1 to 8 includes the biaxially oriented multilayer film of any one of Aspects 1 to 8, having:

[0016] Example 10 includes the biaxially oriented multilayer film of any one of Examples 1-9, wherein the biaxially oriented multilayer film is oriented in the machine direction with a stretch ratio of 4:1 to 7:1 and in the transverse direction with a stretch ratio of 6:1 to 12:1.

[0017] Example 11 includes the biaxially oriented multilayer film of any one of Examples 1-10, wherein the core layer comprises greater than 70% of the total thickness of the biaxially oriented multilayer film.

[0018] Example 12 includes the biaxially oriented multilayer film of any one of Examples 1-11, wherein the core layer comprises greater than 90% of the total thickness of the biaxially oriented multilayer film.

[0019] Example 13 includes the biaxially oriented multilayer film of any one of Examples 1 to 12, wherein the biaxially oriented multilayer film has a longitudinal modulus of 500 MPa to 3500 MPa and a transverse modulus of 700 MPa to 4000 MPa.

[0020] Example 14 includes an article comprising the biaxially oriented multilayer film of any one of Examples 1-13, wherein the article is a flexible package, a pouch, a stand-up pouch, a pre-formed package, or a pre-formed pouch.

[0021] Example 15 includes a laminated article including the biaxially oriented multilayer film of any one of Examples 1-13.

[0022] These and other embodiments are described in more detail in the detailed description. DETAILED DESCRIPTION OF THE INVENTION

[0023] Unless otherwise stated to the contrary, implicit from context, or customary in the art, all parts and percentages are by weight, all temperatures are in degrees Celsius, and all test methods are current as of the filing date of this disclosure.

[0024] As used herein, the term "composition" refers to the mixture of materials that make up the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0025] "Polymer" means a polymeric compound prepared by polymerizing monomers, whether of the same or different types. Thus, the generic term polymer encompasses the term homopolymer, as defined below, and the term interpolymer, as defined below. Minor impurities (e.g., catalyst residues) may be incorporated into and / or within the polymer. The polymer may be a single polymer, a polymer blend, or a polymer mixture, including a mixture of polymers formed in situ during polymerization.

[0026] As used herein, the term "homopolymer" refers to a polymer prepared from only one type of monomer, with the understanding that trace amounts of impurities may be incorporated into the polymer structure.

[0027] As used herein, the term "interpolymer" refers to a polymer prepared by the polymerization of at least two different types of monomers. Thus, the general term interpolymer includes copolymers (used to refer to polymers prepared from two different types of monomers) and polymers prepared from two or more different types of monomers.

[0028] As used herein, the terms "olefin-based polymer" or "polyolefin" refer to a polymer that comprises, in polymerized form, a majority amount (based on the weight of the polymer) of an olefin monomer, e.g., ethylene or propylene, and may optionally include one or more comonomers.

[0029] As used herein, the term "ethylene / α-olefin interpolymer" refers to an interpolymer that, in polymerized form, contains a majority amount (greater than 50 mole %) of units derived from ethylene monomer, with the balance being derived from one or more α-olefins. Typical α-olefins used to form ethylene / α-olefin interpolymers are C3 to C6 10 It is an alkene.

[0030] As used herein, the term "ethylene / α-olefin copolymer" refers to a copolymer that contains, in polymerized form, a majority amount (greater than 50 mole %) of ethylene monomer and an α-olefin as the only two monomers.

[0031] As used herein, the term "α-olefin" refers to an alkene having a double bond in the primary or alpha (α) position.

[0032] "Polyethylene" or "ethylene-based polymer" shall mean a polymer containing a majority (greater than 50 mol%) of units derived from ethylene monomers. This includes polyethylene homopolymers or copolymers (meaning units derived from two or more comonomers). Common forms of polyethylene known in the art include low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (ULDPE), very low-density polyethylene (VLDPE), single-site catalyzed linear low-density polyethylene (m-LLDPE), including both linear and substantially linear low-density resins, ethylene-based plastomers (POP) and ethylene-based elastomers (POE), medium-density polyethylene (MDPE), and high-density polyethylene (HDPE). These polyethylene materials are generally well known in the art. However, the following discussion may be helpful in understanding the differences between some of these different polyethylene resins.

[0033] The term "LDPE," which may also be referred to as "high pressure ethylene polymer" or "highly branched polyethylene," is defined to mean that the polymer is partially or fully homopolymerized or copolymerized in an autoclave or tubular reactor at pressures above 14,500 psi (100 MPa) using a free radical initiator, such as peroxide (see, for example, U.S. Pat. No. 4,599,392, incorporated herein by reference). LDPE resins typically have a viscosity of 0.916 to 0.935 g / cm. 3 The density is in the range of

[0034] The term "LLDPE" includes both resins made using single-site catalysts, including, but not limited to, traditional Ziegler-Natta catalyst systems and chromium-based catalysts, as well as mono- or bis-cyclopentadienyl catalysts (typically referred to as metallocenes), constrained geometry catalysts, phosphinimine catalysts, and polyaryloxy ether catalysts (typically referred to as bisphenylphenoxy), and includes linear, substantially linear, or heterogeneous polyethylene copolymers or homopolymers. LLDPE contains less long chain branching than LDPE and includes substantially linear ethylene polymers, as further defined in U.S. Patent Nos. 5,272,236, 5,278,272, 5,582,923, and 5,733,155; homogeneously branched linear ethylene polymer compositions such as those in U.S. Patent No. 3,645,992; heterogeneously branched ethylene polymers such as those prepared according to the process disclosed in U.S. Patent No. 4,076,698; and / or blends thereof (such as those disclosed in U.S. Patent Nos. 3,914,342 or 5,854,045). LLDPE may be made via gas phase, solution phase, or slurry polymerization, or any combination thereof, using any type of reactor or reactor configuration known in the art.

[0035] The term "MDPE" refers to 0.926-0.935 g / cm 3 "MDPE" refers to polyethylene having a density of 1000 MPa or less. "MDPE" is typically produced using chromium or Ziegler-Natta catalysts, or using single-site catalysts including, but not limited to, substituted mono- or bis-cyclopentadienyl catalysts (typically referred to as metallocenes), constrained geometry catalysts, phosphinimine catalysts, and polyaryloxy ether catalysts (typically referred to as bisphenylphenoxy), and typically has a molecular weight distribution ("MWD") greater than 2.5.

[0036] The term "HDPE" refers to a polymer having a density of about 0.935 g / cm, typically prepared using a single-site catalyst, including, but not limited to, Ziegler-Natta, chromium, or substituted mono- or bis-cyclopentadienyl catalysts (typically referred to as metallocenes), constrained geometry catalysts, phosphinimine catalysts, and polyaryloxy ether catalysts (typically referred to as bisphenylphenoxy). 3 Super ~ maximum approx. 0.980g / cm 3 It refers to polyethylene having a density of

[0037] The term "ULDPE" refers to polymers with a yield of 0.855 to 0.912 g / cm, typically prepared using single-site catalysts, including, but not limited to, Ziegler-Natta catalysts, chromium catalysts, or substituted mono- or bis-cyclopentadienyl catalysts (typically referred to as metallocenes), constrained geometry catalysts, phosphinimine catalysts, and polyaryloxy ether catalysts (typically referred to as bisphenylphenoxy). 3 ULDPE refers to polyethylene having a density of 0.855 to 0.912 g / cm. Examples of ULDPE include, but are not limited to, polyethylene (ethylene-based) plastomers and polyethylene (ethylene-based) elastomers. Polyethylene (ethylene-based) elastomers and plastomers generally have a density of 0.855 to 0.912 g / cm. 3 It has a density of

[0038] "Blend," "polymer blend," and like terms refer to a composition of two or more polymers. Such blends may or may not be miscible. Such blends may or may not be phase separated. Such blends may or may not contain one or more domain configurations as determined from transmission electron spectroscopy, light scattering, X-ray scattering, and any other method known in the art. A blend is not a laminate, although one or more layers of a laminate may contain the blend. Such blends may be prepared as dry blends or may be formed in situ (e.g., in a reactor), as melt blends, or using other techniques known to those skilled in the art.

[0039] The terms "comprising," "including," "having," and their derivatives are not intended to exclude the presence of any additional component, step, or procedure, whether or not it is specifically disclosed. For the avoidance of doubt, all compositions claimed through the use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless otherwise stated to the contrary. In contrast, the term "consisting essentially of" excludes from the scope of any succeeding description any other component, step, or procedure, except those that are not essential to operability. The term "consisting of" excludes any component, step, or procedure not specifically delineated or listed.

[0040] The present disclosure generally relates to biaxially oriented multilayer polyolefin films having a polyethylene core. In some embodiments, such films are biaxially oriented using a tenter frame. Biaxially oriented multilayer polyethylene films utilize a core layer comprising a polyethylene-based composition. For example, by expanding the operating window for biaxial orientation, higher density polyethylene can be oriented, thereby improving film stiffness. In some embodiments, biaxially oriented multilayer polyethylene films can be used in packaging applications.

[0041] In an embodiment, the biaxially oriented multilayer polyethylene film has a melt index (I2) of 0.2 grams per 10 minutes (g / 10 min) to 5.0 g / 10 min, a viscosity of 0.930 grams per cubic centimeter (g / cm 3 ) to 0.956 g / cm 3 Density: More than 3.5SCB / 1000°C, logarithm of weight average molecular weight (SCB) of 4.0 to 5.0 logMw4~5 The core layer comprises a polyethylene-based composition comprising an average short chain branching (SCB) level in the portion having the polyethylene-based composition.

[0042] In some embodiments, the polyethylene core of the biaxially oriented multilayer film comprises at least 70% of the film thickness. In one or more embodiments, the biaxially oriented multilayer film comprises at least one skin layer, wherein the at least one skin layer comprises a propylene-based polymer having a differential scanning calorimetry (DSC) melting point of 120°C to 150°C.

[0043] In some embodiments, a biaxially oriented multilayer film according to any of the embodiments described herein is oriented in the machine direction with a stretch ratio of 4:1 to 7:1 and in the transverse direction with a stretch ratio of 6:1 to 12:1. In some embodiments, a biaxially oriented film is oriented in the machine direction with a stretch ratio of 5:1 to 6:1 and in the transverse direction with a stretch ratio of 8:1 to 10:1.

[0044] In embodiments, the polyethylene-based composition comprises a blend of a first polyethylene-based component and a second polyethylene-based component. In embodiments, the first polyethylene-based component may be HDPE having properties further described herein, and the second polyethylene-based component may be LLDPE having properties further described herein. In one or more embodiments, the polyethylene-based composition comprises a third polyethylene-based component. In embodiments, the third polyethylene-based component may be HDPE as further described herein.

[0045] In embodiments, the biaxially oriented polyethylene multilayer films disclosed herein may be used in packaging, such as food packaging, In embodiments, an article comprises any of the biaxially oriented multilayer films disclosed herein.

[0046] Core layer As described above, the biaxially oriented multilayer film disclosed herein includes a core layer comprising at least a polyethylene-based composition and having specific properties. In an embodiment, the core layer has a melt index (I2) of 0.2 g / 10 min to 5.0 g / 10 min, a melt index (I2) of 0.930 g / cm 3 ~0.956g / cm3 The density is greater than 3.5SCB / 1000C, and the part between 4.0 and 5.0 log(Mw) (SCB logMw4~5 ) have an average SCB level in

[0047] In an embodiment, the core layer has a melt index (I2) of 0.5 g / 10 min to 5.0 g / 10 min, for example, 1.0 g / 10 min to 5.0 g / 10 min, 1.5 g / 10 min to 5.0 g / 10 min, 2.0 g / 10 min to 5.0 g / 10 min, 2.5 g / 10 min to 5.0 g / 10 min, 3.0 g / 10 min to 5.0 g / 10 min, 3.5 g / 10 min to 5.0 g / 10 min, 4.0 g / 10 min to 5.0 g / 10 min, 4.5 g / 10 min to 5.0 g / 10 min, 0.2 g / 10 min to 4.5 g / 10 min, 0.5 g / 10 min to 4.5 g / 10 min, 1.0 g / 10 min to 4.5 g / 10 min, 1 .5g / 10 minutes~4.5g / 10 minutes, 2.0g / 10 minutes~4.5g / 10 minutes, 2.5g / 10 minutes~4.5g / 10 minutes, 3.0g / 10 minutes~ 4.5g / 10 minutes, 3.5g / 10 minutes~4.5g / 10 minutes, 4.0g / 10 minutes~4.5g / 10 minutes, 0.2g / 10 minutes~4.0g / 10 minutes, 0.5g / 10min~4.0g / 10min, 1.0g / 10min~4.0g / 10min, 1.5g / 10min~4.0g / 10min, 2.0g / 10min ~4.0g / 10min, 2.5g / 10min~4.0g / 10min, 3.0g / 10min~4.0g / 10min, 3.5g / 10min~4.0g / 10min , 0.2g / 10min~3.5g / 10min, 0.5g / 10min~3.5g / 10min, 1.0g / 10min~3.5g / 10min, 1.5g / 10 min~3.5g / 10min, 2.0g / 10min~3.5g / 10min, 2.5g / 10min~3.5g / 10min, 3.0g / 10min~3.5g / 10 min, 0.2g / 10min~3.0g / 10min, 0.5g / 10min~3.0g / 10min, 1.0g / 10min~3.0g / 10min, 1.5g / 1 0min~3.0g / 10min, 2.0g / 10min~3.0g / 10min, 2.5g / 10min~3.0g / 10min, 0.2g / 10min~2.5g / 1 0 minutes, 0.5g / 10 minutes~2.5g / 10 minutes, 1.0g / 10 minutes~2.5g / 10 minutes, 1.5g / 10 minutes~2.5g / 10 minutes, 2.0g / 10 minutes~2.5g / 10 minutes, 0.2g / 10 minutes~2.0g / 10 minutes, 0.5g / 10 minutes~2.0g / 10 minutes, 1.0g / 10 minutes~2.0g / 10 min, 1.5g / 10 min to 2.0g / 10 min, 0.2g / 10 min to 1.5g / 10 min, 0.5g / 10 min to 1.5g / 10 min, 1.0g / 10 min to 1.5g / 10 min, 0.2g / 10 min to 1.0g / 10 min, 0.5g / 10 min to 1.0g / 10 min, or 0.2g / 10 min to 0.5g / 10min.

[0048] In one or more embodiments, the core layer has a density of 0.935 g / cm 3 ~0.956g / cm 3 For example, 0.938 g / cm 3 ~0.956g / cm 3 , 0.940g / cm 3 ~0.956g / cm 3 , 0.942g / cm 3 ~0.956g / cm 3 , 0.945g / cm 3 ~0.956g / cm 3 , 0.948g / cm 3 ~0.956g / cm 3 , 0.950g / cm 3 ~0.956g / cm 3 , 0.952g / cm 3 ~0.956g / cm 3 , 0.935g / cm 3 ~0.952g / cm 3 , 0.938g / cm 3 ~0.952g / cm 3 , 0.940g / cm 3 ~0.952g / cm3, 0.942g / cm 3 ~0.952g / cm3, 0.945g / cm 3 ~0.952g / cm 3 , 0.948g / cm 3 ~0.952g / cm 3 , 0.950g / cm 3 ~0.952g / cm 3 , 0.935g / cm 3 ~0.950g / cm 3 , 0.938g / cm 3 ~0.950g / cm 3 , 0.940g / cm 3 ~0.950g / cm 3 , 0.942g / cm 3 ~0.950g / cm 3 , 0.945g / cm 3 ~0.950g / cm 3 , 0.948g / cm 3~0.950g / cm 3 , 0.935g / cm 3 ~0.948g / cm 3 , 0.938g / cm 3 ~0.948g / cm 3 , 0.940g / cm 3 ~0.948g / cm 3 , 0.942g / cm 3 ~0.948g / cm 3 , 0.945g / cm 3 ~0.948g / cm 3 , 0.935g / cm 3 ~0.945g / cm 3 , 0.938g / cm 3 ~0.945g / cm 3 , 0.940g / cm 3 ~0.945g / cm 3 , 0.942g / cm 3 ~0.945g / cm 3 , 0.935g / cm 3 ~0.942g / cm 3 , 0.938g / cm 3 ~0.942g / cm 3 , 0.940g / cm 3 ~0.942g / cm 3 , 0.935g / cm 3 ~0.940g / cm 3 , 0.938g / cm 3 ~0.940g / cm 3 or 0.935 g / cm 3 ~0.938g / cm 3 is.

[0049] In one or more embodiments, the core layer has an average SCB level (SCB) in the log(Mw) portion of 4.0 to 5.0. logMw4~5 ) and is greater than 3.5 SCB / 1000C, e.g., greater than 4.0 SCB / 1000C, greater than 4.5 SCB / 1000C, greater than 5.0 SCB / 1000C, greater than 5.5 SCB / 1000C, greater than 6.0 SCB / 1000C, greater than 6.5 SCB / 1000C, or greater than 7.0 SCB / 1000C. In one or more embodiments, the fraction between log(Mw) 4.0 and 5.0 (SCB logMw4~5The maximum average SCB level in a 1000C is 10.0 SCB / 1000C, which can be applied to any of the above values. logMw4~5 is measured according to the test procedures described herein below.

[0050] In one or more embodiments, the core layer has a DSC melting point (T m )

[0051] In some embodiments, the polyethylene-based composition in the core layer comprises a blend of two or more polyethylene-based components. It should be understood that when the polyethylene-based composition is a blend, the blending can be achieved by either in-reactor blending, melt blending, dry blending, or a combination of these blending methods.

[0052] In embodiments where the polyethylene-based composition in the core layer comprises a blend of two or more polyethylene-based components, the core layer comprises a first polyethylene-based component. In embodiments, the first polyethylene-based component is a high-density polyethylene having a melt index (I2) of 0.1 g / 10 min to 2.5 g / 10 min, e.g., 0.1 g / 10 min to 1.0 g / 10 min, 0.1 g / 10 min to 0.5 g / 10 min, 0.5 g / 10 min to 2.5 g / 10 min, 0.5 g / 10 min to 1.0 g / 10 min, 1.0 g / 10 min to 1.5 g / 10 min, or 1.5 g / 10 min to 2.5 g / 10 min. In embodiments, the first polyethylene-based component has a melt index (I2) of 0.955 g / cm 3 ~0.970g / cm 3 , 0.955g / cm 3 ~0.960g / cm 3 , 0.960g / cm 3 ~0.965g / cm 3 , or 0.965 g / cm 3~0.970g / cm 3 It has a density of

[0053] In one or more embodiments, the core layer of the biaxially oriented multilayer film comprises a polyethylene-based composition that is a blend of a first polyethylene-based component and a second polyethylene-based component. The second polyethylene-based component is, in embodiments, an LLDPE having a melt index (I2) at least 0.1 g / 10 min greater than the melt index (I2) of the first polyethylene-based component, such as at least 0.3 g / 10 min greater than the melt index (I2) of the first polyethylene-based component, at least 0.5 g / 10 min greater than the melt index (I2) of the first polyethylene-based component, or at least 0.7 g / 10 min greater than the melt index (I2) of the first polyethylene-based component. In embodiments, the melt index (I2) of the second polyethylene-based component is 10 g / 10 min or less. Thus, in an embodiment, the second polyethylene-based component has a melt index (I2) of 0.2 g / 10 min to 2.8 g / 10 min, for example, 0.2 g / 10 min to 1.3 g / 10 min, 0.2 g / 10 min to 0.8 g / 10 min, 0.6 g / 10 min to 2.8 g / 10 min, 0.6 g / 10 min to 1.3 g / 10 min, 1.1 g / 10 min to 1.8 g / 10 min, or 1.6 g / 10 min to 2.8 g / 10 min. In an embodiment, the second polyethylene-based component has a melt index (I2) of 0.2 g / 10 min to 10.0 g / 10 min, for example, 2.0 g / 10 min to 8.0 g / 10 min, or 4.0 g / 10 min to 6.0 g / 10 min. In an embodiment, the second polyethylene-based component has a density at least 0.005 g / cm 3 lower than that of the first polyethylene-based component. 3 has a density that is less than, for example, at least 0.01 g / cm 3 less than the density of the first polyethylene-based component; 3 and at least 0.02 g / cm less than the density of the first polyethylene-based component 3 and at least 0.03 g / cm less than the density of the first polyethylene-based component 3 and at least 0.04 g / cm less than the density of the first polyethylene-based component 3and at least 0.05 g / cm less than the density of the first polyethylene-based component 3 less than or at least 0.06 g / cm 3 less than the density of the first polyethylene-based component 3 In an embodiment, the density of the second polyethylene composition is less than 0.900 g / cm 3 The second polyethylene component has a viscosity of 0.900 g / cm 3 ~0.950g / cm 3 , 0.910g / cm 3 ~0.948g / cm 3 , or 0.920 g / cm 3 ~0.945g / cm 3 In some embodiments, the second polyethylene component can be INNate™ TF 80, commercially available from The Dow Chemical Company.

[0054] In one or more embodiments, the core layer of the biaxially oriented multilayer film comprises a polyethylene-based composition that is a blend comprising at least a second polyethylene-based component and a third polyethylene-based component. In an embodiment, the third polyethylene-based component is HDPE having a melt index (I2) of 0.1 g / 10 min to 0.5 g / 10 min, e.g., 0.3 g / 10 min to 0.5 g / 10 min, or 0.1 g / 10 min to 0.3 g / 10 min. In an embodiment, the third polyethylene-based component has a melt index (I2) of 0.955 g / cm 3 ~0.965g / cm 3 , 0.960g / cm 3 ~0.965g / cm 3 , or 0.955 g / cm 3 ~0.960g / cm 3 In embodiments, the third polyethylene component may be CONTINUUM™ DMDE-6620, available from The Dow Chemical Company.

[0055] In embodiments in which the polyethylene-based composition comprises a blend of a first polyethylene-based component and a second polyethylene-based component, the polyethylene-based composition comprises the first polyethylene-based component in an amount of 15% to 85% by weight of the polyethylene-based composition, e.g., 20% to 80% by weight, 25% to 75% by weight, 30% to 70% by weight, 35% to 65% by weight, or 40% to 50% by weight. Accordingly, in such embodiments, the polyethylene-based composition comprises the second polyethylene-based component in an amount of 15% to 85% by weight of the polyethylene-based composition, e.g., 20% to 80% by weight, 25% to 75% by weight, 30% to 70% by weight, 35% to 65% by weight, or 40% to 50% by weight.

[0056] In embodiments in which the polyethylene-based composition comprises a blend of a third polyethylene-based component and a second polyethylene-based component, the polyethylene-based composition comprises the third polyethylene-based component in an amount of 15% to 85% by weight of the polyethylene-based composition, e.g., 20% to 80% by weight, 25% to 75% by weight, 30% to 70% by weight, 35% to 65% by weight, or 40% to 50% by weight. Accordingly, in such embodiments, the polyethylene-based composition comprises the second polyethylene-based component in an amount of 15% to 85% by weight of the polyethylene-based composition, e.g., 20% to 80% by weight, 25% to 75% by weight, 30% to 70% by weight, 35% to 65% by weight, or 40% to 50% by weight.

[0057] Thus, in an embodiment, the polyethylene-based composition comprises the second polyethylene-based component in an amount of 15% to 85% by weight of the polyethylene-based composition, such as 20% to 80% by weight, 25% to 75% by weight, 30% to 70% by weight, 35% to 65% by weight, or 40% to 50% by weight.

[0058] In embodiments, the polyethylene-based composition may be a blend of a first polyethylene-based component and a second polyethylene-based component, a blend of a second polyethylene-based component and a third polyethylene-based component, or a blend of a first polyethylene-based component, a second polyethylene-based component, and a third polyethylene-based component.

[0059] It should be understood that in embodiments, the core layer can comprise, consist essentially of, or consist of the polyethylene-based compositions disclosed and described herein above. In other embodiments, the core layer may be a blend comprising, consisting essentially of, or consisting of the polyethylene-based compositions disclosed and described herein above and any number of additional polyethylene-based compositions. The number of polyethylene-based compositions used in combination in the core layer is not limited and, according to embodiments, may include two, three, four, or more polyethylene-based compositions.

[0060] Preparation of the first polyethylene-based component For embodiments in which the core layer comprises a first polyethylene-based component described herein, the following description provides information regarding polymerization and potential catalysts. Additional information regarding the preparation of the first polyethylene-based component can be found in the Examples section below.

[0061] polymerization In embodiments, the first polyethylene component can be made by a solution phase polymerization process. Generally, a solution phase polymerization process occurs in one or more well-mixed reactors, such as one or more isothermal loop reactors or one or more adiabatic reactors, at a temperature ranging from 115 to 250°C, e.g., 115 to 200°C, and at a pressure ranging from 300 to 1,000 psig, e.g., 400 to 750 psi. In some embodiments, in a dual reactor, the temperature of the first reactor is in the range of 115 to 190°C, e.g., 115 to 175°C, and the temperature of the second reactor is in the range of 150 to 250°C, e.g., 130 to 165°C. In other embodiments, in a single reactor, the reactor temperature is in the range of 115 to 250°C, e.g., 115 to 225°C.

[0062] The residence time in the solution phase polymerization process can be in the range of 2 to 30 minutes, for example, 10 to 20 minutes. Ethylene, solvent, hydrogen, one or more catalyst systems, optionally one or more cocatalysts, and optionally one or more comonomers are continuously fed into one or more reactors. An exemplary solvent includes, but is not limited to, isoparaffin. For example, such a solvent is commercially available from ExxonMobil Chemical Co. (Houston, Texas) under the name ISOPAR E. The resulting mixture of the polyethylene composition and solvent is then removed from the reactor, and the polyethylene composition is isolated. The solvent is typically recovered via a solvent recovery unit, i.e., a heat exchanger and a gas-liquid separator drum, and then recycled to the polymerization system.

[0063] In one embodiment, the polyethylene component can be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene is polymerized in the presence of one or more catalyst systems. In some embodiments, only ethylene is polymerized. In addition, one or more co-catalysts can be present. In another embodiment, the polyethylene composition can be produced by solution polymerization in a single reactor system, e.g., a single loop reactor system, where ethylene is polymerized in the presence of two catalyst systems. In some embodiments, only ethylene is polymerized.

[0064] catalyst system Specific embodiments of catalyst systems that can be used to produce the polyethylene compositions described herein are now described. It is understood that the catalyst systems of the present disclosure may be embodied in different forms and should not be construed as limited to the specific embodiments described in this disclosure. Rather, the embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0065] The term "independently selected" refers to 1 , R 2 , R 3 , R 4 , and R 5 and the R groups may be the same or different (e.g., R 1 , R 2 , R 3 , R 4 , and R 5 are all substituted alkyl, or R 1 and R 2 is a substituted alkyl, and R 3 The terms "a" and "an" are used herein to indicate that an R group is an alkyl group, and the R group may be an aryl group, etc. The use of the singular includes the use of the plural and vice versa (e.g., hexane solvent includes a plurality of hexanes). A named R group will generally have a structure recognized in the art as corresponding to the R group with that name. These definitions are intended to supplement and illustrate, not preclude, definitions known to those of skill in the art.

[0066] The term "procatalyst" refers to a compound that has catalytic activity when combined with an activator. The term "activator" refers to a compound that chemically reacts with a procatalyst to convert the procatalyst into a catalytically active catalyst. As used herein, the terms "cocatalyst" and "activator" are interchangeable terms.

[0067] When used to describe certain carbon atom-containing chemical groups, "(C x ~C y A parenthetical expression having the form "(C1-C )" means that the unsubstituted form of the chemical group has x to y carbon atoms, inclusive. For example, (C1-C 40 ) Alkyl is an alkyl group having 1 to 40 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups are R S The parenthesized "(C x ~C y )" for the chemical group R S The substituted form can be any group R S For example, "R S exactly one group R is phenyl (-C6H5) S (C1~C 40 A "(C ) alkyl" can contain from 7 to 46 carbon atoms. Therefore, the parenthesized "(C ) alkyl" is generally used. x ~C y )" is a group defined as one or more carbon atom-containing substituents R S When substituted by x and y, the minimum and maximum total number of carbon atoms in the chemical group is determined by the presence of all carbon atom-containing substituents R S It is determined by adding the total number of carbon atoms from

[0068] The term "substituted" means that at least one hydrogen atom (-H) bonded to a carbon or heteroatom of the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R SThe term "hypersubstituted" means that all hydrogen atoms (H) bonded to carbon atoms or heteroatoms of the corresponding unsubstituted compound or functional group are substituted with a substituent (e.g., R S The term "polysubstituted" means that at least two, but fewer than all, hydrogen atoms bonded to carbon atoms or heteroatoms of the corresponding unsubstituted compound or functional group are replaced by substituents.

[0069] The term "-H" means a hydrogen or hydrogen radical covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and mean the same thing unless otherwise specified.

[0070] "(C1~C 40 The term "(C1-C)hydrocarbyl" means a hydrocarbon radical of 1 to 40 carbon atoms. 40 The term "hydrocarbylene" means a hydrocarbon diradical of 1 to 40 carbon atoms, wherein each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (monocyclic and polycyclic, including fused and non-fused polycyclic, including bicyclic, 3 or more carbon atoms) or acyclic, unsubstituted or substituted with one or more R S has been replaced by

[0071] In this disclosure, (C1 to C 40 ) Hydrocarbyl is unsubstituted or substituted (C1-C 40 ) Alkyl, (C3-C 40 ) cycloalkyl, (C3-C 20 )Cycloalkyl-(C1-C 20 ) Alkylene, (C6-C 40 ) aryl, or (C6-C 20 )Aryl-(C1-C 20 In some embodiments, the aforementioned (C1-C) alkylene may be 40 Each of the hydrocarbyl groups has up to 20 carbon atoms (i.e., (C1-C 20) hydrocarbyl), in other embodiments, having up to 12 carbon atoms.

[0072] "(C1~C 40 ) alkyl" and "(C1-C 18 The term "alkyl" means a saturated straight or branched chain hydrocarbon radical of 1 to 40 carbon atoms or 1 to 18 carbon atoms, respectively, that is unsubstituted or substituted by one or more R-S. 40 Examples of alkyl are unsubstituted (C1-C 20 ) Alkyl, unsubstituted (C1-C 10 ) alkyl, unsubstituted (C1-C5) alkyl, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-nonyl, and 1-decyl. 40 Examples of substituted (C1-C 20 ) Alkyl, substituted (C1-C 10 ) alkyl, trifluoromethyl, and [C 45 ] alkyl. 45 The term "alkyl (with brackets)" means that there are up to 45 carbon atoms in the radical, including the substituents, e.g., one R that is (C1-C5) alkyl. S replaced by (C 27 ~C 40 Each (C1-C5)alkyl can be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl.

[0073] "(C6~C 40 The term "aryl" refers to an unsubstituted or substituted (one or more R) aryl group of 6 to 40 carbon atoms. Smeans a monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical, of which at least 6 to 14 carbon atoms are aromatic ring carbon atoms, and the monocyclic, bicyclic, or tricyclic radical contains 1, 2, or 3 rings, respectively, in which the single ring is aromatic and the two or three rings are independently fused or non-fused, and at least one of the two or three rings is aromatic. 40 Examples of aryl are unsubstituted (C-C 20 )Aryl, unsubstituted (C6-C 18 )aryl, 2-(C1-C5)alkyl-phenyl, 2,4-bis(C1-C5)alkyl-phenyl, phenyl, fluorenyl, tetrahydrofluorenyl, indacenyl, hexahydroindacenyl, indenyl, dihydroindenyl, naphthyl, tetrahydronaphthyl, and phenanthrene. 40 Examples of aryl are substituted (C1-C 20 ) Aryl, substituted (C6-C 18 )aryl, 2,4-bis[(C 20 ) alkyl]-phenyl, polyfluorophenyl, pentafluorophenyl, and fluoren-9-on-1-yl.

[0074] "(C3~C 40 The term "cycloalkyl" refers to a group that is unsubstituted or has one or more R S means a saturated cyclic hydrocarbon radical of 3 to 40 carbon atoms substituted with other cycloalkyl groups, such as (C x ~C y )cycloalkyl) has x to y carbon atoms and is unsubstituted or has one or more R S Unsubstituted (C3 to C 40 Examples of cycloalkyl include unsubstituted (C3-C 20 ) Cycloalkyl, unsubstituted (C3-C 10 ) cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl.40 Examples of cycloalkyl include substituted (C3-C 20 ) Cycloalkyl, substituted (C3-C 10 ) cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.

[0075] (C1~C 40 Examples of hydrocarbylenes include substituted or unsubstituted (C6-C 40 ) arylene, (C3-C 40 ) cycloalkylene, (C1-C 40 ) alkylene (e.g., (C1-C 20 ) alkylene). In some embodiments, the diradicals can be on the same carbon atom (e.g., —CH2—) or on adjacent carbon atoms (i.e., 1,2-diradicals), or separated by one, two, or more carbon atoms (e.g., 1,3-diradicals, 1,4-diradicals, etc.). Some diradicals include α,ω-diradicals. α,ω-diradicals are diradicals with the greatest carbon backbone spacing between the radical carbons. (C2-C 20 Some examples of alkylene α,ω-diradicals include ethane-1,2-diyl (i.e., -CHCH 2- ), propane-1,3-diyl (i.e., -CH2CH2CH2-), 2-methylpropane-1,3-diyl (i.e., -CH2CH(CH3)CH2-). (C6-C 50 Some examples of arylene α,ω-diradicals include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0076] "(C1~C 40) The term "alkylene" may be unsubstituted or may be substituted with one or more R S means a saturated straight or branched chain diradical of 1 to 40 carbon atoms (i.e., the radical is not on a ring atom) substituted with unsubstituted (C1-C 50 An example of an alkylene is an unsubstituted —CHCH 2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C * HCH3 and -(CH2)4C * Unsubstituted (C1-C, including (H)(CH3) 20 ) alkylene, wherein "C * " denotes a carbon atom from which a hydrogen atom has been removed to form a secondary or tertiary alkyl group. 50 Examples of alkylene are substituted (C1-C 20 ) alkylene, -CF 2- , -C(O)-, and -(CH2) 14 C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted normal-1,20-eicosylene). As mentioned above, the two R S are combined together (C1~C 18 ) alkylene, so that the substituted (C1-C 50 Examples of )alkylene also include 1,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and 2,3-bis(methylene)bicyclo[2.2.2]octane.

[0077] "(C3~C 40 The term "cycloalkylene" may be unsubstituted or may contain one or more R S means a cyclic diradical (i.e., the radicals are on ring atoms) of 3 to 40 carbon atoms substituted with

[0078] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of heteroatoms include O, S, S(O), S(O), Si(R C )2, P(R P ), N(R N ), -N=C(R C )2, -Ge(R C ) 2- , or -Si(R C )-, and each R C , each R N , and each RP is unsubstituted (C1 to C 18 ) hydrocarbyl or -H. The term "heterohydrocarbon" refers to a molecule or molecular backbone in which one or more carbon atoms are replaced with a heteroatom. 1~ C 40 The term "(C1-C)heterohydrocarbyl" means a heterohydrocarbon radical of 1 to 40 carbon atoms. 40 The term "heterohydrocarbylene" means a heterohydrocarbon diradical of 1 to 40 carbon atoms, each heterohydrocarbon having one or more heteroatoms. The heterohydrocarbyl radical can be present on a carbon atom or a heteroatom, and the heterohydrocarbyl diradical can be present on (1) one or two carbon atoms, (2) one or two heteroatoms, or (3) one carbon atom and one heteroatom. Each (C1 to C 50 ) heterohydrocarbyl and (C1-C 50 ) heterohydrocarbylene is unsubstituted or (one or more R S and may be aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0079] (C1~C 40 ) Heterohydrocarbyl is unsubstituted or substituted (C1-C 40 ) heteroalkyl, (C1-C 40 ) hydrocarbyl-O-, (C1-C 40 ) hydrocarbyl-S-, (C1-C 40 ) hydrocarbyl-S(O)-, (C1-C 40 ) hydrocarbyl-S(O)2-, (C1-C 40 ) Hydrocarbyl-Si(R C )2-, (C1~C 40 ) Hydrocarbyl N(R N )-, (C1~C 40 ) hydrocarbyl-P(R P )-, (C2~C 40 ) heterocycloalkyl, (C2-C 19 )Heterocycloalkyl-(C1-C 20) alkylene, (C3-C 20 )Cycloalkyl-(C1-C 19 ) heteroalkylene, (C2-C 19 )Heterocycloalkyl-(C1-C 20 ) heteroalkylene, (C1-C 40 ) heteroaryl, (C1-C 19 )Heteroaryl-(C1-C 20 ) Alkylene, (C6-C 20 ) aryl-(C 1~ C 19 ) heteroalkylene, or (C1-C 19 )Heteroaryl-(C1-C 20 ) heteroalkylene.

[0080] "(C4~C 40 The term "heteroaryl" refers to an unsubstituted or substituted (one or more R) heteroaryl group of 4 to 40 total carbon atoms and 1 to 10 heteroatoms. S (according to the formula:), monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radicals, where the monocyclic, bicyclic, or tricyclic radicals contain 1, 2, or 3 rings, respectively, which are independently fused or unfused, and at least one of the 2 or 3 rings is a heteroaromatic ring. Other heteroaryl groups (e.g., generally (C4-C 12 ) heteroaryl, etc. x ~C y ) heteroaryl) has x to y carbon atoms (e.g., 4 to 12 carbon atoms) and is unsubstituted or has one or more R SThe monocyclic heteroaromatic hydrocarbon radical is defined in the same manner as being substituted with . The monocyclic heteroaromatic hydrocarbon radical is a 5-membered or 6-membered ring. The 5-membered ring has 5 minus h carbon atoms, where h is the number of heteroatoms and may be 1, 2, or 3, and each heteroatom may be O, S, N, or P. Examples of 5-membered heteroaromatic hydrocarbon radicals include pyrrol-1-yl, pyrrol-2-yl, furan-3-yl, thiophen-2-yl, pyrazol-1-yl, isoxazol-2-yl, isothiazol-5-yl, imidazol-2-yl, oxazol-4-yl, thiazol-2-yl, 1,2,4-triazol-1-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, tetrazol-1-yl, tetrazol-2-yl, and tetrazol-5-yl. A 6-membered ring has 6 minus h carbon atoms, where h is the number of heteroatoms, which may be 1 or 2, and the heteroatoms may be N or P. Examples of 6-membered heteroaromatic hydrocarbon radicals include pyridin-2-yl, pyrimidin-2-yl, and pyrazin-2-yl. Bicyclic heteroaromatic hydrocarbon radicals may be fused 5,6- or 6,6-ring systems. Examples of fused 5,6-ring bicyclic heteroaromatic hydrocarbon radicals are indol-1-yl and benzimidazol-1-yl. Examples of fused 6,6-ring bicyclic heteroaromatic hydrocarbon radicals are quinolin-2-yl and isoquinolin-1-yl. Tricyclic heteroaromatic hydrocarbon radicals may be fused 5,6,5-, 5,6,6-, 6,5,6-, or 6,6,6-ring systems. An example of a fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of a fused 5,6,6-ring system is 1H-benzo[f]indol-1-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,6,6-ring system is acridine-9-yl.

[0081] The heteroalkyl group may be any of (C1-C 50) or fewer carbon atoms and one or more heteroatoms. Similarly, heteroalkylene may be a saturated straight or branched chain diradical containing 1 to 50 carbon atoms and one or more heteroatoms. Heteroatoms as defined above include Si(R C )3, Ge(R C )3, Si(R C )2, Ge(R C )2, P(R P )2, P(R P ), N(R N )2, N(R N ), N, O, OR C , S, S.R. C , S(O), and S(O)2, each of the heteroalkyl and heteroalkylene groups being unsubstituted or containing one or more R S is replaced by

[0082] Unsubstituted (C2~C 40 Examples of heterocycloalkyl include unsubstituted (C-C 20 ) Heterocycloalkyl, unsubstituted (C2-C 10 ) heterocycloalkyl, aziridin-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl, tetrahydrothiophene-S,S-dioxid-2-yl, morpholin-4-yl, 1,4-dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl, and 2-aza-cyclodecyl.

[0083] The term "halogen atom" or "halogen" refers to a radical of a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I). The term "halide" refers to the anionic form of a halogen atom, such as fluoride (F-), chloride (Cl-), bromide (Br-), or iodide (I-).

[0084] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds. A saturated chemical group is one or more substituents R S When substituted by, one or more double and / or triple bonds may optionally be substituted by a substituent R S The term "unsaturated" refers to the presence of one or more carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds, provided that the substituents R, if present, are not present in the group. S It is meant to exclude any double bonds that may be present in, or, if present, in, a (hetero)aromatic ring.

[0085] According to some embodiments, the catalyst system for producing the polyethylene composition comprises a metal-ligand complex according to formula (I):

[0086] [ka]

[0087] In formula (I), M is a metal selected from titanium, zirconium, or hafnium, the metal being in a +2, +3, or +4 formal oxidation state; n is 0, 1, or 2; when n is 1, X is a monodentate or bidentate ligand; when n is 2, each X is a monodentate ligand and is the same or different; the metal-ligand complex is overall charge neutral; and each Z is independently —O—, —S—, —N(R N )-, or -P(R P )-, and L is selected from (C1 to C 40 ) hydrocarbylene or (C1-C 40 ) heterohydrocarbylene, (C1-C 40 The hydrocarbylene has a linker skeleton of 1 to 10 carbon atoms that connects the two Z groups in formula (I) to which L is attached, or 40) Heterohydrocarbylene has a moiety containing a linker skeleton of 1 atom to 10 atoms connecting the two Z groups in formula (I), and (C1-C 40 Each of the 1 to 10 atoms of the 1 to 10 atom linker backbone of the heterohydrocarbylene is independently a carbon atom or a heteroatom, and each heteroatom is independently O, S, S(O), S(O), Si(R C )2, Ge(R C )2, P(R C ), or N(R C ) and independently, each R C is (C1~C 30 ) hydrocarbyl or (C1-C 30 ) heterohydrocarbyl, and R 1 and R 8 are independently -H, (C1 to C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R N )2NC(O)-, halogen, and a radical having formula (II), formula (III), or formula (IV).

[0088] [ka] In formulas (II), (III), and (IV), R 31~35 , R 41~48 , or R 51~59 Each of (C1 to C 40 ) hydrocarbyl, (C1-C 40) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -N=CHR C , -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R N )2NC(O)—, halogen, or —H, with the proviso that R 1 or R 8 At least one of is a radical having formula (II), formula (III), or formula (IV).

[0089] In formula (I), R 2~4 , R 5~7 , and R 9~16 Each of (C1 to C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -N=CHR C , -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2NC(O)-, halogen, and -H.

[0090] In some embodiments, the polyethylene composition is formed using a first catalyst according to formula (I) in a first reactor and a different catalyst according to formula (I) in a second reactor.

[0091] In one exemplary embodiment in which a dual loop reactor is used, the procatalyst used in the first loop is zirconium,[[2,2''-[[bis[1-methylethyl]germylene]bis(methyleneoxy-κO)]bis[3'',5,5''-tris(1,1-dimethylethyl)-5'-octyl[1,1':3',1''-terphenyl]-2'-olato-κO]](2-)]dimethyl-, which has the chemical formula C 86 H 128 F2GeO4Zr, and having the following structure (V):

[0092] [ka] In such embodiments, the procatalyst used in the second loop is zirconium, [[2,2'''-[1,3-propanediylbis(oxy-κO)]bis[3-[2,7-bis(1,1-dimethylethyl)-9H-carbazol-9-yl]]-5'-(dimethyloctylsilyl)-3'-methyl-5-(1,1,3,3-tetramethylbutyl)[1,1]-biphenyl]-2-olato-κO]](2-)]dimethyl, and has the chemical formula C 107 H 154 N2O4Si2Zr and has the following structure:

[0093] [ka]

[0094] cocatalyst component Catalyst systems containing the metal-ligand complexes of formula (I) can be catalytically activated by any technique known in the art for activating metal-based catalysts for olefin polymerization reactions. For example, systems containing the metal-ligand complexes of formula (I) can be catalytically activated by contacting the complex with or combining the complex with an activating cocatalyst. Activating cocatalysts suitable for use herein include alkylaluminums, polymeric or oligomeric alumoxanes (also known as aluminoxanes), neutral Lewis acids, and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions). A suitable activation technique is bulk electrolysis. Combinations of one or more of the foregoing activating cocatalysts and techniques are also contemplated. The term "alkylaluminum" refers to monoalkylaluminum dihydrides or dihalides, dialkylaluminum hydrides or halides, or trialkylaluminums. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, triisobutylaluminum modified methylalumoxane, and isobutylalumoxane.

[0095] Lewis acid activators (co-catalysts) include those having 1 to 3 (C1 to C2) groups, as described herein. 20 In one embodiment, the Group 13 metal compound includes a tri((C1-C) hydrocarbyl substituent. 20 )hydrocarbyl)-substituted-aluminum or tri((C1-C 20 In other embodiments, the Group 13 metal compound is a tri(hydrocarbyl)-substituted aluminum, tri((C1-C 20 )hydrocarbyl)-boron compounds, tri((C1-C 10 ) alkyl) aluminum, tri((C6-C 18)aryl)boron compounds and their halogenated (including perhalogenated) derivatives. In further embodiments, the Group 13 metal compound is tris(fluoro-substituted phenyl)borane, tris(pentafluorophenyl)borane. In some embodiments, the activating cocatalyst is tris((C1-C 20 ) hydrocarbyl borate (e.g., trityl tetrafluoroborate) or tri((C 20 )hydrocarbyl)ammonium tetra((C1-C 20 )hydrocarbyl)borane (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borane). As used herein, the term "ammonium" refers to a ((C1-C 20 ) Hydrocarbyl) 4N + , ((C1~C 20 )hydrocarbyl)3N(H) + , ((C1~C 20 )hydrocarbyl)2N(H)2 + , (C1~C 20 ) Hydrocarbyl N(H)3 + , or N(H)4 + Each of the nitrogen cations (C1 to C 20 ) When two or more hydrocarbyls are present, they may be the same or different.

[0096] As a combination of neutral Lewis acid activators (cocatalysts), tri((C1-C4) alkyl)aluminum and tri((C6-C 18(aryl)boron compounds, particularly tris(pentafluorophenyl)borane. Other embodiments include mixtures of such neutral Lewis acid mixtures with polymeric or oligomeric alumoxanes, and combinations of a single neutral Lewis acid, particularly tris(pentafluorophenyl)borane, with polymeric or oligomeric alumoxanes. The molar ratio of (metal-ligand complex):(tris(pentafluorophenyl)borane):(alumoxane) [e.g., Group 4 metal-ligand complex):(tris(pentafluorophenyl)borane):(alumoxane)] is from 1:1:1 to 1:10:30, and in other embodiments, from 1:1:1.5 to 1:5:10.

[0097] Catalyst systems comprising the metal-ligand complexes of formula (I) can be activated to form active catalyst compositions by combination with one or more cocatalysts, such as cation-forming cocatalysts, strong Lewis acids, or combinations thereof. Suitable activating cocatalysts include polymeric or oligomeric aluminoxanes, particularly methylaluminoxane, as well as inert, compatible, non-coordinating, ion-forming compounds. Examples of suitable cocatalysts include modified methylaluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate (1 - ) amines, and combinations thereof.

[0098] In some embodiments, one or more of the aforementioned activating cocatalysts are used in combination with one another. Particularly preferred combinations are mixtures of tri((C1-C4)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane, or ammonium borate with an oligomeric or polymeric alumoxane compound. The ratio of the total number of moles of one or more metal-ligand complexes of Formula (I) to the total number of moles of one or more activating cocatalysts is 1:10,000 to 100:1. In some embodiments, this ratio is at least 1:5000; in some other embodiments, it is at least 1:1000 and not more than 10:1; and in some other embodiments, it is not more than 1:1. When alumoxane is used alone as the activating cocatalyst, it is preferred that the number of moles of alumoxane used be at least 100 times the number of moles of the metal-ligand complex of Formula (I). When tris(pentafluorophenyl)borane is used alone as the activating cocatalyst, in some other embodiments, the number of moles of tris(pentafluorophenyl)borane used relative to the total number of moles of one or more metal-ligand complexes of Formula (I) is from 0.5:1 to 10:1, from 1:1 to 6:1, or from 1:1 to 5:1. The remaining activating cocatalyst is generally used in a molar amount approximately equal to the total molar amount of one or more metal-ligand complexes of Formula (I).

[0099] Biaxially Oriented Multilayer Film The biaxially oriented polyethylene films of the present disclosure are multilayer films. As previously indicated, such films include a core layer comprising the polyethylene-based composition described herein.

[0100] The amount of polyethylene-based composition used in the core layer of embodiments can vary depending on numerous factors, including, for example, the other layers in the film, the desired properties of the film, the end use of the film, etc. As disclosed above, in embodiments, the core layer consists of or consists essentially of the polyethylene-based composition. In embodiments where the core layer comprises a blend of compositions, the core layer may comprise the polyethylene-based composition disclosed and described herein in an amount of from 30 weight percent (wt%) to 70 wt% of the core layer, e.g., 35 wt% to 70 wt%, 40 wt% to 70 wt%, 45 wt% to 70 wt%, 50 wt% to 70 wt%, 55 wt% to 70 wt%, 60 wt% to 70 wt%, 65 wt% to 70 wt%, 30 wt% to 65 wt%, 35 wt% to 65 wt%, 40 wt% to 65 wt%, 45 wt% to 65 wt%, 50 wt% to 65 wt%, 55 wt% to 65 wt%, 60% by weight to 65% by weight, 30% by weight to 60% by weight, 35% by weight to 60% by weight, 40% by weight to 60% by weight, 45% by weight to 60% by weight, 50% by weight to 60% by weight, 55% by weight to 60% by weight, 30% by weight to 55% by weight, 35% by weight to 55% by weight, 40% by weight to 55% by weight, 45% by weight to 55% by weight, 50% by weight to 55% by weight, 30% by weight to 50% by weight, 35% by weight to 50% by weight, 40% by weight to 50% by weight, 45% by weight to 50% by weight, 30% by weight to 45% by weight, 35% by weight to 45% by weight, 40% by weight to 45% by weight, or 30% by weight to 35% by weight.

[0101] The number of layers in a film can vary depending on numerous factors, including, for example, the desired properties of the film, the desired thickness of the film, the content of other layers in the film, the end use of the film, the equipment available to manufacture the film, etc. For example, a multilayer film can further include other layers typically included in multilayer films depending on the application, including, for example, sealant layers, barrier layers, tie layers, structural layers, etc. A multilayer blown or cast film can be composed of up to 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11 layers in various embodiments.

[0102] Layers other than the core, also referred to herein as skin layers, within the multilayer films of embodiments of the present disclosure can comprise a propylene-based polymer. In embodiments, the propylene-based polymer can be a copolymer of propylene and another olefin (e.g., ethylene, butane, etc.). According to embodiments, the propylene-based polymer can also be a terpolymer of propylene and another olefin, such as ethylene, butane, etc.

[0103] In embodiments, one or more skin layers comprise a propylene-based composition. By using a propylene-based composition in the skin layers in combination with the core layer described above, the biaxially oriented multilayer film has similar stiffness and melting properties to propylene-based films, allowing it to be used in conventional propylene processing lines. However, the biaxially oriented multilayer films of the embodiments disclosed herein may be more easily recycled than films containing significantly more propylene. Furthermore, too much propylene in the film can cause haze and clarity problems in the multilayer film. In embodiments, the skin layers are preferably measured using a DSC T of 120°C to 150°C, e.g., 120°C to 150°C, 130°C to 150°C, 140°C to 150°C, 100°C to 140°C, 120°C to 140°C, 130°C to 140°C, 100°C to 130°C, 120°C to 130°C, or 100°C to 120°C. m In an embodiment, the propylene-based composition may be Sanren F800E manufactured by Sinopec.

[0104] The skin layer, in embodiments, may be a blend of the propylene-based composition with another composition, such as an ethylene-based composition, polymethyl methacrylate (PMMA), polystyrene, etc. In embodiments in which the skin layer is a blend of the propylene-based composition with another composition, the skin layer comprises the propylene-based composition in an amount greater than 40 wt%, e.g., greater than 45 wt%, greater than 50 wt%, greater than 55 wt%, greater than 60 wt%, greater than 65 wt%, greater than 70 wt%, greater than 75 wt%, greater than 80 wt%, greater than 85 wt%, greater than 90 wt%, or greater than 95 wt%.

[0105] The thickness of the biaxially oriented multilayer film according to the embodiment is mainly from the core layer. In the embodiment, the core layer is more than 70% of the thickness of the biaxially oriented multilayer film, for example, more than 75% of the thickness of the biaxially oriented multilayer film, more than 80% of the thickness of the biaxially oriented multilayer film, more than 85% of the thickness of the biaxially oriented multilayer film, or more than 90% of the thickness of the biaxially oriented multilayer film. In the embodiment, the core layer is more than 70% but less than 95% of the thickness of the biaxially oriented multilayer film, for example, more than 75% but less than 95% of the thickness of the biaxially oriented multilayer film, more than 80% but less than 95% of the thickness of the biaxially oriented multilayer film, more than 85% but less than 95% of the thickness of the biaxially oriented multilayer film, or more than 90% but less than 95% of the thickness of the biaxially oriented multilayer film.

[0106] In an embodiment, a biaxially oriented multilayer film according to an embodiment includes at least one skin layer, wherein the at least one skin layer comprises less than 30% of the thickness of the biaxially oriented multilayer film, e.g., less than 25% of the thickness of the biaxially oriented multilayer film, less than 20% of the thickness of the biaxially oriented multilayer film, less than 15% of the thickness of the biaxially oriented multilayer film, less than 10% of the thickness of the biaxially oriented multilayer film, or less than 5% of the thickness of the biaxially oriented multilayer film.

[0107] In an embodiment, the biaxially oriented multilayer film comprises a core layer comprising the polyethylene-based composition disclosed and described herein and at least one skin layer comprising the propylene-based composition.

[0108] In one or more embodiments, a biaxially oriented multilayer film includes a core layer comprising a polyethylene-based composition and two skin layers, each comprising a propylene-based polymer. The polyethylene-based composition, in embodiments, comprises, consists essentially of, or consists of a blend of a first polyethylene-based component and a second polyethylene-based component. In embodiments, the polyethylene-based composition comprises, consists essentially of, or consists of a blend of a first polyethylene-based component, a second polyethylene-based component, and a third polyethylene-based component.

[0109] It should be understood that any of the foregoing layers within the film may, in some embodiments, further comprise one or more additives as would be known to one of ordinary skill in the art, such as, for example, antioxidants, UV stabilizers, heat stabilizers, slip agents, antiblocking agents, pigments or colorants, processing aids, crosslinking catalysts, flame retardants, fillers, and blowing agents.

[0110] By being polyethylene-based, the biaxially oriented multilayer films of the present invention, according to embodiments disclosed herein, can be incorporated into articles that are primarily, if not substantially or entirely, composed of polyethylene to provide more readily recyclable films and articles. For example, films that comprise primarily polyethylene have improved recyclability profiles in addition to other benefits that the use of such polymers may offer. For example, in some embodiments, the multilayer film is composed entirely of ethylene-based polymers, other than additives.

[0111] In embodiments, the biaxially oriented multilayer film comprises at least 65% by weight of the polyethylene-based component, e.g., at least 70% by weight of the polyethylene-based component, at least 75% by weight of the polyethylene-based component, at least 80% by weight of the polyethylene-based component, at least 85% by weight of the polyethylene-based component, at least 90% by weight of the polyethylene-based component, or at least 95% by weight of the polyethylene-based component.

[0112] Multilayer films can have a variety of thicknesses before orientation, depending, for example, on the number of layers, the intended use of the film, and other factors. In some embodiments, such multilayer films have a thickness of 250 to 3200 microns (typically, 500 to 1920 microns) before orientation.

[0113] Prior to orientation, the polyethylene film can be formed using techniques known to those skilled in the art based on the teachings herein. For example, the film can be a blown film or a cast film. For example, in the case of a multilayer film, for layers that can be coextruded, such layers can be coextruded as a blown film or a cast film using techniques known to those skilled in the art and based on the teachings herein.

[0114] In some embodiments in which the film is bilayer oriented, the polyethylene film is biaxially oriented using a tenter frame sequential biaxial orientation process. Such techniques are generally known to those skilled in the art. Generally, in a tenter frame sequential biaxial orientation process, a tenter frame is incorporated as part of a multilayer coextrusion line. After extrusion from a flat die, the film is cooled on a chill roll and immersed in a water bath filled with room temperature water. The cast film is then passed over a series of rollers with different rotation speeds to achieve stretching in the machine direction. The MD stretching segment of the production line has several pairs of rollers, all of which are oil heated. The pairs of rollers operate sequentially as preheating rollers, stretching rollers, and relaxation and annealing rollers. The temperature of each pair of rollers is controlled separately. After stretching in the machine direction, the film web passes through a tenter frame hot air oven with heating zones to achieve stretching in the transverse direction. The first several zones are for preheating, followed by a stretching zone and then a final zone for relaxation and annealing.

[0115] In an embodiment, biaxial orientation is performed sequentially in two different stretching chambers at a predetermined temperature. Machine direction orientation (MDO) is performed in the first chamber. Immediately thereafter, the machine direction oriented sample is sent to the second chamber for transverse direction orientation (TDO). In the MDO process, the sheet is first heated to the desired temperature (T MDO ) by hot air with forced convection, and then stretched 5x in the machine direction at a stretch rate of 500 percent per second (% / s). In the TDO process, the sample is brought to the desired temperature (T) by circulating air in a second chamber before undergoing 8x transverse orientation at a stretch rate of 250% / s. TDO ) for 30 seconds.

[0116] Suitable T for TDO orientation investigation MDO is a fixed T about 2°C higher than the DSC Tm of the core layer. TDO Various T with 2°C intervals MDO The appropriate T MDO is defined as the lowest MDO temperature at which stable sequential stretching can be achieved. For example, the T of a structure having a core layer with a DSC Tm of about 131°C is MDO is a fixed T at 133 °C. TDO Various T combined with MDO The lowest T that can result in stable sequential biaxial orientation is MDO is the appropriate T for investigating the TDO operating window. MDO is.

[0117] In embodiments, the biaxially oriented multilayer film has a TDO operating window that is greater than 5°C, greater than 7°C, greater than 10°C, greater than 12°C, greater than 14°C, or greater than 15°C. In one or more embodiments, the biaxially oriented multilayer film has a TDO operating window of 5°C to 20°C, for example, 7°C to 20°C, 10°C to 20°C, 12°C to 20°C, 14°C to 20°C, 15°C to 20°C, 17°C to 20°C, 5°C to 17°C, 7°C to 17°C, 10°C to 17°C, 12°C to 17°C, 14°C to 17°C, 15°C to 17°C, 5°C to 15°C, 7°C to 15°C, 10°C to 15°C, 12°C to 15°C, 14°C to 15°C, 5°C to 14°C, 7°C to 14°C, 10°C to 14°C, 12°C to 14°C, 5°C to 12°C, 7°C to 12°C, 10°C to 12°C, 5°C to 10°C, 7°C to 10°C, or 5°C to 7°C.

[0118] In some embodiments, after orientation, the biaxially oriented film has a thickness of 5 to 50 microns, hi some embodiments, the biaxially oriented film has a thickness of 15 to 40 microns.

[0119] In an embodiment, the biaxially oriented multilayer film has an average machine direction (MD) modulus of 500 megapascals (MPa) to 3500 MPa, for example, 600 MPa to 3000 MPa, 700 MPa to 2500 MPa, 800 MPa to 2000 MPa, or 900 MPa to 1500 MPa. In an embodiment, the biaxially oriented multilayer film has an average transverse direction (TD) modulus of 700 MPa to 4000 MPa, for example, 1000 MPa to 3500 MPa, 1250 MPa to 3000 MPa, 1500 MPa to 2500 MPa, or 1750 MPa to 2000 MPa.

[0120] In some embodiments, depending on, for example, the end use application, the oriented polyethylene film may be corona treated, plasma treated, or printed using techniques known to those skilled in the art. In some embodiments, the oriented multilayer film may be surface coated with aluminum, silicon oxide, aluminum oxide, or other metals known to those skilled in the art based on the teachings herein.

[0121] In embodiments, the BOPE films disclosed and described herein may be laminated with other layers. Lamination can be done by any suitable and known lamination process, such as adhesive lamination or extrusion lamination.

[0122] Goods Embodiments of the present disclosure also relate to articles, such as packaging, formed from or incorporating biaxially oriented multilayer films as disclosed herein.

[0123] Examples of such articles may include flexible packaging, pouches, stand-alone pouches, and pre-made packages or pouches. In some embodiments, the oriented multilayer polyethylene films or laminates of the present invention may be used in food packaging. Examples of foods that may be included in such packaging include meat, cheese, cereal, nuts, juice, sauce, etc. Such packaging may be formed using techniques known to those skilled in the art based on the teachings herein and on the particular application of the packaging (e.g., type of food, amount of food, etc.).

[0124] Test Method Unless otherwise indicated herein, the following analytical methods are used in describing embodiments of the present invention.

[0125] Melt Index Melt index I2 (or I2) and I 10 (or I10) were measured according to ASTM D-1238 (Method B) at 190° C. and 2.16 kg and 10 kg loads, respectively. The values ​​are reported in g / 10 min.

[0126] density Density was measured according to ASTM D792.

[0127] DSC melting point DSC melting point (DSC T m) were measured on a TA instruments Q2000 series differential scanning calorimeter under a nitrogen atmosphere at heating and cooling rates of 10°C / min. Three cycles were performed: the first from ambient temperature to 250°C, the second from 250°C to 0°C, and the third from 0°C to 280°C. The endothermic (melting) peaks in the third cycle were analyzed using the Integrate Peak Signal Horizontal method in TA Universal Analysis software to obtain the DSC Tm for each sample.

[0128] Gel Permeation Chromatography (GPC) Molecular weights (Mw, Mz, Mn, etc.) were measured using GPC unless otherwise indicated.

[0129] The chromatography system consisted of a PolymerChar (Valencia, Spain) GPC-IR high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The autosampler oven compartment was set to 160 °C, and the column compartment was set to 150 °C. The columns used were four Agilent "Mixed A" 30 cm, 20 micron linear mixed-bed columns. The chromatography solvent used was 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was nitrogen sparged. The injection volume used was 200 microliters, and the flow rate was 1.0 milliliters / minute.

[0130] The GPC column set was calibrated using 21 narrow molecular weight distribution polystyrene standards ranging from 580 to 8,400,000 molecular weights, arranged in six "cocktail" mixtures with at least 10-fold spacing between individual molecular weights. Standards were purchased from Agilent Technologies. Polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights above 1,000,000 and 0.05 grams in 50 milliliters of solvent for molecular weights below 1,000,000. The polystyrene standards were dissolved at 80°C for 30 minutes with gentle agitation. The peak molecular weights of the polystyrene standards were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)): M ポリエチレン =A×(M ポリスチレン ) B (Formula 1) where M is the molecular weight, A has a value of 0.4315, and B is equal to 1.0.

[0131] A fifth-order polynomial was used to fit each polyethylene-equivalent calibration point. A small adjustment (approximately 0.375 to 0.445) was made to A to correct for column resolution and band-broadening effects for a linear homopolymer polyethylene standard obtained at 120,000 MW.

[0132] Total plate counts for the GPC column set were performed using decane (prepared at 0.04 g in 50 milliliters of TCB and dissolved for 20 minutes with gentle stirring). Plate counts (Equation 2) and symmetry (Equation 3) were measured with a 200 microliter injection according to the following equations:

[0133]

number

[0134]

number

[0135] Samples were prepared in a semi-automated fashion using PolymerChar's "Instrument Control" software, with a target sample weight of 2 mg / ml, and solvent (containing 200 ppm BHT) was added via a PolymerChar high-temperature autosampler to a pre-nitrogen-sparged, septum-capped vial. Samples were dissolved at 160°C for 2 hours under "slow" shaking.

[0136] Mn (GPC) , Mw (GPC) , and Mz (GPC) The calculation was based on GPC results using the internal IR5 detector (measurement channel) of a PolymerChar GPC-IR chromatograph according to Equations 4-6 using PolymerChar GPCOne™ software, baseline-subtracted IR chromatograms at each equally spaced data collection point (i), and polyethylene equivalent molecular weights obtained from a narrow standard calibration curve for point (i) of Equation 1.

[0137]

number

[0138] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by a PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (Flow Rate (Apparent)) for each sample by RV-matching the respective decane peak in the sample (RV (FM Sample)) with that of the decane peak in the narrow standard calibration (RV (FM Calibrated)). Any change in the time of the decane marker peak is then assumed to be related to a linear shift in flow rate (Flow Rate (Effective)) throughout the run. To facilitate the highest accuracy in the RV measurement of the flow rate marker peaks, a least-squares fitting routine is used to fit the peaks of the flow rate marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation is then used to solve for the true peak position. After calibrating the system based on the flow rate marker peaks, the effective flow rate (relative to the narrow standard calibration) is calculated as shown in Equation 7. Processing of the flow rate marker peaks was performed via PolymerChar GPCOne™ software. An acceptable flow correction is such that the effective flow rate should be within ±1% of the apparent flow rate. Flow rate (effective) = Flow rate (apparent) * (RV (FM calibrated) / RV (FM sample)) (Equation 7).

[0139] Branch Measurement SCB logMw4~5The compositions of polymer resins and blends were examined using gel permeation chromatography (GPC). The GPC system consisted of a 150 °C high-temperature chromatograph equipped with a Polymer Char IR-5 infrared detector, a two-angle light scattering detector (Agilent 1260), and a Polymer Char differential viscometer. Four Agilent PL Mixed A columns (7.5 × 300 mm) were placed in series before the IR-5 detector in the detector oven. 1,2,4-Trichlorobenzene (TCB, HPLC grade) and 2,5-di-tert-butyl-4-methylphenol (BHT) (e.g., commercially available from Sigma-Aldrich) were obtained. 800 milligrams of BHT were added to 4 liters of TCB. Here, the TCB containing BHT will be referred to simply as "TCB." Sample preparation was performed using an autosampler at 2 mg / mL with shaking at 160 °C for 3 hours. The injection volume is 200 mL. The GPC temperature is 150° C. and the flow rate is 1 mL / min. The GPC is calibrated using a series of narrow molecular weight (Mw) polystyrene standards.

[0140] Calibration of the GPC column set is performed using 21 narrow molecular weight distribution polystyrene standards ranging in molecular weight from 580 to 9,835,000, arranged in six "cocktail" mixtures with at least 10-year intervals between individual molecular weights. A fifth-order polynomial is used to fit each polyethylene-equivalent calibration point. The polystyrene standard peak molecular weights are converted to polyethylene molecular weights using Equation 1A.

[0141] Composition is measured along with MWD using an IR-5 infrared detector. The composition detector is calibrated using a series of copolymer standards with varying levels of comonomer. The weight percent comonomer levels of these samples are calculated using the C 13The composition-related signals are obtained by NMR. For each standard, composition-related signals are collected and labeled "measurement," "methylene" (CH2), and "methyl" (CH3). The "measurement" signal is used as the concentration signal when performing molecular weight calibration, and the ratio of the "methyl" and "methylene" signals is used for composition calculation. A plot of the weight percent comonomer from NMR versus these ratios is made for a series of standards. Linear regression of the data provides a good fit of the data set. The weight percent comonomer data can be converted to short-chain branches per 1000 total carbons (SCB / 1000C).

[0142] Mw is the weight average molecular weight. logMw is the logarithm of the weight average molecular weight. logMw is the weight fraction of the part at a particular logMw. logMw is the short chain branching per 1000 carbons of a moiety at a particular logMw. (SCB / 1000C) logMw4~5 is calculated by the following formula:

[0143]

number

[0144] Biaxially Oriented Biaxial orientation is carried out sequentially in two different stretching chambers at a predetermined temperature. A sheet sample is cut into a size of 10 x 10 cm along the MD and TD directions and mounted on a stretching frame with five clips positioned on each of the four sides. The clips are pneumatically actuated to clamp the edges of the sample, and then the stretching frame is transferred into the first chamber. Machine direction orientation (MDO) is carried out in the first chamber. Immediately thereafter, the machine direction oriented sample is sent to the second chamber for transverse direction orientation (TDO). In the MDO process, the sample sheet is first heated to a desired temperature (T MDO ) by hot air with forced convection, and then stretched 5 times in the machine direction at a stretch rate of 500% / s. In the TDO process, the sample is brought to the desired temperature (T) by circulating air in a second chamber before undergoing 8 times transverse orientation at a stretch rate of 250% / s.TDO ) for 30 seconds. The stretched film samples were then removed from the stretching frame and allowed to age for at least one week before being tested for film properties as described below in this section.

[0145] Suitable T for TDO orientation investigation MDO is a fixed T about 2°C higher than the DSC Tm of each core layer. TDO In combination with various T MDO The appropriate T MDO is defined as the lowest MDO temperature at which stable sequential stretching can be achieved. For example, screening of a structure with a core layer having a DSC Tm of about 131°C is performed using a fixed T of 133°C. TDO Various T MDO The lowest T that can result in stable sequential biaxial orientation is MDO is the appropriate T for investigating the TDO orientation window. MDO is.

[0146] Hayes Haze is measured according to ASTM D1003 using a BYK Gardner Haze-gard.

[0147] transparency Clarity is measured according to ASTM D1746.

[0148] Tensile modulus Tensile modulus (including machine direction (MD) modulus and transverse direction (TD) modulus) is measured according to the 2% secant modulus in ASTM D882.

[0149] Some embodiments of the present invention are described in detail in the following examples. [Example]

[0150] Materials for Examples and Comparative Examples The materials used to form the films of the examples and comparative examples are listed below.

[0151] The "first polyethylene-based component" has a melt index (I2) of 1.1 g / 10 min and a viscosity of 0.9668 g / cm 3 The high density polyethylene according to embodiments disclosed herein is used for the core layer in the examples, having a density of 1000 MPa. A method for making the first polyethylene-based component is provided below.

[0152] The "second polyethylene-based component" has a melt index (I2) of 1.7 g / 10 min and a viscosity of 0.927 g / cm 3 The preferred polyethylene is INNATE™ TF80, a linear low density polyethylene from The Dow Chemical Company, having a density of 1000 MPa, and is used in the core layer of the examples.

[0153] The "third polyethylene component" is CONTINUUM™ DMDE-6620 NT 7, a high density polyethylene manufactured by The Dow Chemical Company, with a melt index (I2) of 0.3 g / 10 min and a density of 0.960 g / cm 3 and is used in the core layer of some embodiments.

[0154] Exceed XP 6026 ("XP6026") is a linear low-density polyethylene manufactured by Exxon Mobil with a melt index (I2) of 0.2 g / 10 min and a density of 0.916 g / cm 3 and is used in the comparative core.

[0155] Evolue SP 3022 ("SP3022") has a melt index (I2) of 1.7 g / 10 min and a 3 and is used in the core layer of the comparative example.

[0156] CONTINUUM™ DMDC-1270 NT 7 (“DMDC-1270”) is a high density polyethylene manufactured by The Dow Chemical Company with a melt index (I2) of 2.5 g / 10 min and a melt strength of 0.955 g / cm 3 and is used in the core layer of the comparative example.

[0157] Exxon HTA108 ("HTA-108") is a high-density polyethylene from ExxonMobil Corporation with a melt index (I2) of 0.7 g / 10 min and a melt strength of 0.961 g / cm 3 and is used in the core layer of the comparative example.

[0158] The skin layers of the examples and comparative examples are made from Sanren F800E propylene random copolymer supplied by Sinopec, which has a DSC Tm of 142.6°C.

[0159] Method for Making a First Polyethylene-Based Composition The first polyethylene-based component used in the examples is prepared according to the following process and based on the reaction conditions reported in Table 1.

[0160] All raw materials (ethylene monomer) and process solvents (high-purity narrow-boiling-range isoparaffinic solvent, Isopar-E) were purified with molecular sieves before being introduced into the reaction environment. Hydrogen was supplied under pressure as a high-purity grade with no further purification. The reactor monomer feed stream was pressurized above the reaction pressure via a mechanical compressor. The solvent feed was pressurized above the reaction pressure via a pump. Individual catalyst components were manually batch diluted with purified solvent to specific component concentrations and pressurized above the reaction pressure. All reaction feed streams were measured with mass flow meters and independently controlled by a computerized automated valve control system.

[0161] The continuous solution polymerization reactor consisted of two liquid-filled, non-adiabatic, isothermal circulating loop reactors similar to continuous stirred tank reactors (CSTRs) with heat removal. Independent control of all fresh solvent, monomer, hydrogen, and catalyst component feeds to each reactor was possible. The entire fresh feed stream (solvent, monomer, and hydrogen) to each reactor was temperature controlled by passing the feed streams through heat exchangers. The entire fresh feed to each polymerization reactor was injected into the reactor at two locations per reactor, with approximately equal reactor volume between each injection location. The unused feed to the first reactor was typically controlled so that each injector received half of the total fresh feed mass flow rate. The fresh feed to the second reactor in series was typically controlled to maintain half of the total ethylene mass flow rate near each injector; since unreacted ethylene from the first reactor entered the second reactor adjacent to the low-pressure fresh feed, this injector usually had less than half of the total fresh feed mass flow rate to the second reactor.

[0162] The catalyst / cocatalyst components for each reactor were injected into the polymerization reactor through specially designed injection stingers. Each catalyst / cocatalyst component was injected separately into the same relative position within the reactor without prior contact time. The primary catalyst components were computer-controlled to maintain the monomer conversion of each reactor at a specific target value. The cocatalyst components were fed to the primary catalyst components based on a specific calculated molar ratio.

[0163] The catalyst used in the first reactor was zirconium, [[2,2''-[[bis[1-methylethyl]germylene]bis(methyleneoxy-κO)]bis[3',5,5'-tris(1,1-dimethylethyl)-5'-octyl[1,1':3',1'-terphenyl]-2'-olato-κO]](2-)]dimethyl-, which has the chemical formula C 86 H 128 F2GeO4Zr, and having the following structure ("Catalyst 1"):

[0164]

number

[0165] The catalyst used in the second reactor was zirconium, [[2,2''-[1,3-propanediylbis(oxy-κO)]bis[3-[2,7-bis(1,1-dimethylethyl)-9H-carbazol-9-yl]]-5'-(dimethyloctylsilyl)-3'-methyl-5-(1,1,3,3-tetramethylbutyl)[1,1]-biphenyl]-2-olato-κO]](2-)]dimethyl, and has the chemical formula C 107 H 154 N2O4Si2Zr and having the following structure ("Catalyst 2"):

[0166]

number

[0167] Immediately after each reactor feed injection point, the feed stream was mixed with the contents of the circulation polymerization reactor using a static mixing element. The contents of each reactor were continuously circulated through a heat exchanger, which served to remove the majority of the heat of reaction, with the coolant side temperature serving to maintain an isothermal reaction environment at the specified reactor temperature. Circulation around each reactor loop was provided by a pump.

[0168] The effluent from the first polymerization reactor (containing solvent, monomer, hydrogen, catalyst components, and molten polymer) exited the first reactor loop, passed through a control valve (responsible for maintaining the pressure of the first reactor at a specific target value), and was injected into a second polymerization reactor of similar design. The final effluent from the second polymerization reactor entered a zone where the effluent was deactivated by adding and reacting with a suitable reagent (water). At this same reactor exit location, other additives were added for polymer stabilization. This final effluent stream passed through another set of static mixing elements to facilitate catalyst deactivation and additive dispersion.

[0169] Following catalyst deactivation and additive addition, the reactor effluent entered a devolatilization system where the polymer was removed from the non-polymer stream. The isolated polymer melt was pelletized and collected. The non-polymer stream passed through various equipment that separated most of the ethylene removed from the system. Most of the solvent was recycled to the reactor after passing through a purification system. A small amount of solvent was purged from the process. The first polyethylene component was stabilized with a small (ppm) amount of stabilizer.

[0170] The polymerization conditions for the first polyethylene component are reported in Table 1. As seen in Table 1, Cocatalyst 1 (bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)amine); and Cocatalyst 2 (modified methylaluminoxane (MMAO)) were used as cocatalysts for Catalyst 1 and Catalyst 2, respectively.

[0171] [Table 1]

[0172] Multilayer film formation Core layer compounds were prepared by melt blending according to the formulations listed in Table 1. The core layer compounds were produced in a Coperion ZSK40 twin-screw extruder. The screw speed was 250 rpm and the feed rate was controlled at 50 kg / h. The temperatures of the different zones are listed in Table 2. All materials were fed through the main feed throat. A vacuum was used in zone 11 to remove volatiles. Underwater pelletization was used to produce pellets. The core layer compound pellets were then used for characterization and cast into sheets.

[0173] [Table 2]

[0174] The second polyethylene-based component is a state-of-the-art PE used for biaxial orientation and was used in the Core-1 and Core-2 formulations for orientation properties. The first polyethylene-based component is an HDPE used in high-stiffness applications, which, when blended with the second polyethylene-based component, provided the Core-1 and Core-2 formulations with the desired high density and short chain distribution. The third polyethylene-based component is a very low-MI HDPE, which provided the Core-2 formulation with a higher molecular weight. HTA-108 is a conventional HDPE, and SP3022 is a comparative PE for biaxial orientation disclosed in WO2019156733, which were combined to create the Core-3 formulation. DMDC-1270 is a high-MI HDPE that allows the Core-4 formulation to have a lower average short-chain branching level in the log(MW) range between 4.0 and 5.0. XP6026 is a low-MI LLDPE that provided the Core-4 formulation with the desired density.

[0175] [Table 3]

[0176] The properties of the core layer formulation were analyzed according to the test methods introduced in the previous section and are listed in Table 3.

[0177] [Table 4]

[0178] Six different three-layer coextruded sheets were made on a laboratory-scale multilayer cast sheet line supplied by POTOP by following a typical cast sheet process at a melt temperature of approximately 200°C. Except for CE-5, which had a single-layer structure, the remaining sheets shared the same skin components and similar total thickness (approximately 700 μm), but had different core layer components and layer ratios. Detailed structural information is listed in Table 4, with "E" indicating an example according to the embodiment and "CE" indicating a comparative example. Layer ratios are in percentage of thickness.

[0179] [Table 5]

[0180] Biaxial orientation of multilayer films The biaxial orientation properties of each multilayer coextruded sheet were then evaluated in a Xia Furnace IV laboratory stretcher supplied by Brueckner according to the method described in the previous section. MDO was found at 129 °C for E-1, E-2, CE-1, and CE-2, as defined by the above protocol. For CE-3, the appropriate T MDO The optimal TDO temperature for the CE-4 structure was found to be 125°C. Although it shares the same core layer as E-1, alignment of the CE-4 structure was not successful at E-1's best MDO temperature (129°C). The CE-4 MDO was operated at 131°C, and combined with a higher TDO temperature, continuous biaxial alignment was successful. Considering the difference in layer ratio of CE-4, alignment performance evaluation was performed at an MDO temperature of 131°C, as this is the lowest MDO temperature at which good alignment can be obtained. The MDO of CE-5 was similar to that of E-1 because they share the same core layer components. MDO The best T MDO Detailed T in TDO The window is summarized in Table 5. In Table 5, three repeat orientation attempts were performed at each MDO / TDO temperature combination to ensure stable orientation performance. Successful orientation was defined by good stretching (no film break or slipping off the clips) in all three attempts. If a poor stretching (film break or slipping off the clips) occurred, it was classified as a failure.

[0181] [Table 6] F: Failure, at least one orientation attempt failed S: Success, all orientation attempts were successful N: No orientation test was performed

[0182] In biaxial orientation tests, E-1 and E-2 exhibited significantly wider stable operating windows compared to CE-1, CE-2, CE-3, and CE-5.

[0183] Typically, films oriented at lower temperatures within the orientation window have better optical properties and higher stiffness. As a result, film samples made near the lower end of the orientation window were selected for optical and modulus testing according to the methods described above. The results are summarized in Table 6. CE-5 cannot be successfully oriented under any conditions, so film data is not available.

[0184] [Table 7]

[0185] E-1 and E-2 were found to provide the best combination of desired optical properties (high clarity and low haze) and high stiffness (high modulus). CE-1 exhibited good haze and fairly good stiffness, but poor clarity. CE-2's clarity, haze, and TD modulus were all inferior to E-1 and E-2. CE-3 provided both poorer optical properties and lower stiffness compared to E-1 and E-2. CE-4's haze and stiffness were inferior and undesirable compared to E-1 and E-2. The present application provides, for example, the following inventions. [1] A biaxially oriented multilayer film, A core layer comprising a polyethylene-based composition, the core layer comprising: Total melt index (I) ranging from 0.2g / 10min to 5.0g / 10min 2 )and, 0.930g / cm 3 ~0.956g / cm 3 and the overall density is The part between log(Mw) 4.0 and 5.0 (SCB logMw4~5 a core layer having an average short chain branching level of more than 3.5 SCB / 1000C and less than 10.0 SCB / 1000C; and at least one additional layer, wherein the at least one additional layer comprises a propylene-based composition. [2] The propylene-based composition Copolymers of propylene with other olefins, Terpolymers of propylene with other olefins, and The biaxially oriented multilayer film according to [1] above, wherein the biaxially oriented multilayer film is selected from the group consisting of: [3] The biaxially oriented multilayer film according to any one of the above [1] or [2], wherein the propylene-based composition has a DSC melting point of 120°C to 150°C. [4] The biaxially oriented multilayer film according to any one of [1] to [3] above, wherein the polyethylene composition is a blend containing a first polyethylene component and a second polyethylene component. [5] The first polyethylene component has a melt index (I) of 1.0 g / 10 min to 1.5 g / 10 min. 2 ), and 0.965 g / cm 3 ~0.970g / cm 3 and high density polyethylene (HDPE) having a density of The second polyethylene component has a melt index (I) of 0.1 g / 10 min to 3.0 g / 10 min. 2 ), and 0.915 g / cm 3 ~0.930g / cm 3 The biaxially oriented multilayer film according to [4] above, wherein the film is a linear low-density polyethylene (LLDPE) having a density of [6] The biaxially oriented multilayer film according to any one of [4] or [5] above, wherein the polyethylene composition further comprises a third polyethylene component. [7] The third polyethylene component has a melt index (I) of 0.1 g / 10 min to 0.5 g / 10 min. 2 ) and 0.955g / cm 3 ~0.965g / cm 3 [6] The biaxially oriented multilayer film according to the above [6], wherein the biaxially oriented multilayer film is made of high density polyethylene (HDPE) having a density of [8] The overall density of the core layer is 0.940 g / cm 3 ~0.955g / cm 3 The biaxially oriented multilayer film according to any one of the above [1] to [7], [9] The core layer has an average SCB exceeding 4.5 SCB / 1000C. logMw4~5 The biaxially oriented multilayer film according to any one of the above [1] to [8], having:

[10] The biaxially oriented multilayer film is oriented in the machine direction at a draw ratio of 4:1 to 7:1; The biaxially oriented multilayer film according to any one of the above [1] to [9], which is oriented in the transverse direction at a draw ratio of 6:1 to 12:1.

[11] The biaxially oriented multilayer film according to any one of the above [1] to

[10] , wherein the core layer constitutes more than 70% of the total thickness of the biaxially oriented multilayer film.

[12] The biaxially oriented multilayer film according to any one of [1] to

[11] above, wherein the core layer constitutes more than 90% of the total thickness of the biaxially oriented multilayer film.

[13] The biaxially oriented multilayer film according to any one of [1] to

[12] above, wherein the biaxially oriented multilayer film has a longitudinal modulus of elasticity of 500 MPa to 3500 MPa and a transverse modulus of elasticity of 700 MPa to 4000 MPa.

[14] An article comprising the biaxially oriented multilayer film according to any one of [1] to

[13] above, wherein the article is a flexible package, a pouch, a stand-up pouch, a pre-made package, or a pre-made pouch.

[15] A laminated product comprising the biaxially oriented multilayer film according to any one of [1] to

[13] above.

Claims

1. A biaxially oriented multilayer film, A core layer comprising a polyethylene-based composition, the core layer comprising: A total melt index (I) of 0.2 g / 10 min to 5.0 g / 10 min ２ ) (according to ASTM D-1238 (Method B) at 190°C and 2.16 kg load) 0.930 g / cm ３ ~0.956g / cm ３ and the overall density is The portion with log(Mw) between 4.0 and 5.0 (SCB ｌｏｇＭｗ４～５ an average short chain branching level greater than 3.5 SCB / 1000C and less than 10.0 SCB / 1000C; two skin layers comprising a propylene-based composition, each skin layer comprising less than 10% of the thickness of the film; Including, the polyethylene-based composition is a blend comprising a first polyethylene-based component and a second polyethylene-based component; the first polyethylene-based component is a high density polyethylene (HDPE) having a melt index (I 2 ) (according to ASTM D-1238 (Method B) at 190° C. and 2.16 kg load) of 0.1 g / 10 min to 1.5 g / 10 min, and a density of 0.955 g / cm 3 to 0.970 g / cm 3 ; the second polyethylene-based component is a linear low-density polyethylene (LLDPE) having a melt index (I 2 ) (according to ASTM D-1238 (Method B) at 190° C. and 2.16 kg load) of 0.1 g / 10 min to 3.0 g / 10 min, and a density of 0.915 g / cm 3 to 0.930 g / cm 3 ; Biaxially oriented multilayer film.

2. The propylene-based composition is Copolymers of propylene with other olefins, Terpolymers of propylene with other olefins, and 10. The biaxially oriented multilayer film of claim 1, wherein the biaxially oriented multilayer film is selected from the group consisting of:

3. 3. The biaxially oriented multilayer film according to claim 1, wherein the propylene-based composition has a DSC melting point of 120°C to 150°C.

4. The first polyethylene-based component has a viscosity of 0.965 g / cm ３ ~0.970g / cm ３ 2. The biaxially oriented multilayer film of claim 1, wherein the film is a high density polyethylene (HDPE) having a density of

5. 5. The biaxially oriented multilayer film of claim 1, wherein the polyethylene-based composition further comprises a third polyethylene-based component.

6. The third polyethylene-based component has a melt index (I ２ ) (according to ASTM D-1238 (Method B) at 190°C and a load of 2.16 kg) and 0.955 g / cm ３ ~0.965g / cm ３ 6. The biaxially oriented multilayer film of claim 5, wherein the film is a high density polyethylene (HDPE) having a density of

7. The overall density of the core layer is 0.940 g / cm ３ ~0.955g / cm ３ The biaxially oriented multilayer film according to any one of claims 1 to 6,

8. The core layer has an average SCB greater than 4.5 SCB / 1000C. ｌｏｇＭｗ４～５ The biaxially oriented multilayer film according to any one of claims 1 to 7, having

9. the biaxially oriented multilayer film is oriented in the machine direction at a draw ratio of 4:1 to 7:1; The biaxially oriented multilayer film of any one of claims 1 to 8, which is oriented in the transverse direction at a draw ratio of from 6:1 to 12:

1.

10. The biaxially oriented multilayer film of any one of claims 1 to 9, wherein the core layer comprises more than 70% of the total thickness of the biaxially oriented multilayer film.

11. The biaxially oriented multilayer film of any one of claims 1 to 10, wherein the core layer comprises more than 90% of the total thickness of the biaxially oriented multilayer film.

12. 12. The biaxially oriented multilayer film according to any one of claims 1 to 11, wherein the biaxially oriented multilayer film has a longitudinal modulus of 500 MPa to 3500 MPa and a transverse modulus of 700 MPa to 4000 MPa.

13. An article comprising the biaxially oriented multilayer film of any one of claims 1 to 12, which is a flexible package, a pouch, a stand-up pouch, a pre-made package, or a pre-made pouch.

14. A laminated product comprising the biaxially oriented multilayer film according to any one of claims 1 to 12.

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