Polyethylene film

Abstract

Provided is a biaxially oriented shrink film comprising a metallocene linear low density polyethylene having a density in the range of from 0.900 g / cm3 to 0.940 g / cm3 a. melt index (I2) in the range of from 0.1 g / 10 min to 5.0 g / 10 min, a melt index ratio (MIR) in the range of from 20 to 38, a molecular weight distribution (MWD) in the range of from 2.0 to 4.5, and a broad orthogonal comonomer distribution. In some embodiments, the shrink film provides adequate shrink force at a temperature less than 160°C.

Description

POLYETHYLENE FILM CROSS-REFRENCE TO RELATED APPLICATION

[0001] This application claims the benefit of U.S. Provisional Application 63 / 502,865, filed May 17, 2023, entitled “Polyethylene Film”, the entirety of which is incorporated by reference herein. FIELD OF THE INVENTION

[0002] This disclosure relates to co-extruded structures for collation shrink films and blends of polyethylene used therefor. BACKGROUND OF THE INVENTION

[0003] Collation shrink (CS) concerns the bundling of items together using heat shrinkable film. Collation shrink is used for a very wide variety of applications and notably for the secondary packaging of food or drinks. Examples include metal cans and plastic bottles.

[0004] Typically, films are applied at room temperature and placed under a heat source to shrink. Suitable performance characteristics on a shrink packaging line include sufficient stiffness allowing the film to be correctly wrapped around the items being packaged and sufficient dimensional shrinkage to ensure a snug fit. Films appropriate for use as collation shrink must have a high thermal shrink force to ensure a tight fit and high tensile strength to withstand handling and abuse during transportation.

[0005] CS film is widely used in beverage industry. For a conventional CS film, the shrink tunnel operation temperature is normally from 180°C-220°C, and even for thin CS film (e.g., 30µm), the shrink tunnel temperature is higher than 150°C. There is a need to provide a low temperature shrink CS film solution to, among other things, save energy, improve packaging efficiency, and minimize the temperature impact to the content inside the packaged containers.

[0006] References of potential interest in this regard include US Patent Nos. 7,422,786; 9,126,269; 9,902,822; 10,273,029; and 11,441,023; as well as in US patent publication No US2022 / 0259417. SUMMARY OF THE INVENTION

[0007] The present disclosure provides for a biaxially oriented film having at least a first outer layer, a second outer layer, and a core layer disposed between the first outer layer and the second outer layer, the core layer comprising a first polymer composition. The first polymer compositioncomprises at least 50 wt% of a first metallocene linear low density polyethylene (mLLDPE). The first mLLDPE comprises from 80 wt% to 99 wt% ethylene derived units and 1 wt% to 20 wt% units derived from one or more C3 to C20 ^-olefins, based on the weight of the first mLLDPE, and has: i) a density in the range of from 0.900 g / cm3to 0.940 g / cm3; or equal to 40%;a range g / 10 min; and iv) a broad orthogonal comonomer distribution.

[0008] The first outer layer comprises a second polymer composition, and the second outer layer comprises a third polymer composition. The second and third polymer compositions are the same or different. The second and third polymer compositions each independently comprises: a) a narrow-CD mLLDPE, having a CDBI greater than or equal to 50% and a melt index (I2) greater than or equal to 1.2 dg / min.; b) a long chain branched (LCB) mLLDPE, having a CDBI greater than or equal to 60% and a melt index (I2) less than 1.2 dg / min.; c)d) a combination thereof.

[0009] In some embodiments, the first polymer composition further comprises: a) a narrow-CD mLLDPE, having a CDBI greater than or equal to 50% and a melt index (I2) greater than or equal to 1.2 dg / min.; b) a long chain branched (LCB) mLLDPE, having a CDBI greater than or equal to 60% and a melt index (I2) less than 1.2 dg / min.; c) a high density polyethylene (HDPE); or d) a combination thereof.

[0010] In some embodiments, the biaxial orientation comprises a machine direction (MD) orientation stretch ratio in a range of from 2.0:1 to 7.5:1 and a transverse direction (TD) orientation stretch ratio in a range of from 6.5:1 to 11.5:1.

[0011] In some embodiments, the film has a shrink temperature in the range of from 120°C to 170°C.

[0012] The present disclosure further discloses a process for collation shrink packaging, the process comprising arranging two or more items adjacent to one another in one or more rows of two or more items to form a collated bundle, wherein a cartesian coordinate system is defined bya first horizontal axis parallel to the one or more rows, a second horizontal axis perpendicular to the one or more rows, and a vertical axis. The process further comprises wrapping the collated bundle in a multilayer film, as disclosed herein, at a temperature in the range of from 10°C to 40°C to form a wrapped bundle, wherein: i) the multilayer film forms a tube encasing the collated bundle items; ii) the tube as a first opening at one end of the bundle and a second opening at the opposite end of the bundle; and iii) the tube is oriented such that the central axis of the tube is parallel to the first horizontal axis, the second horizontal axis, or the vertical axis. The process further comprises heating the wrapped bundle to a temperature sufficient to shrink the tube to conform to the outermost surfaces of the collated bundle to form a shrink wrapped bundle.

[0013] In some embodiments of the process, the wrapping of the collated bundle is performed such that the machine direction of the film is perpendicular to the central axis of the tube.

[0014] The foregoing has outlined rather broadly the features and technical advantages of the present invention in order that the detailed description of the invention that follows may be better understood. Additional features and advantages of the invention will be described hereinafter, which form the subject matter of the claims of the invention. It should be appreciated by those skilled in the art that the conception and specific embodiments disclosed may be readily utilized as a basis for modifying processes for carrying out the same purposes of the present invention. It should also be realized by those skilled in the art that such equivalent constructions do not depart from the spirit and scope of the invention as set forth in the appended claims. The novel features which are believed to be characteristic of the invention, both as to its structure and method of manufacture, together with further objects and advantages will be better understood from the following description. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] FIG.1 is an overlaid graph of shrink force versus time for comparison of inventive and comparative films in accordance with embodiments and / or techniques disclosed herein.

[0016] While the disclosed process and system are susceptible to various modifications and alternative forms, the drawing illustrates a specific embodiment herein described in detail by way of example. It should be understood, however, that the description herein of a specific embodiment is not intended to limit the invention to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.DETAILED DESCRIPTION OF THE INVENTION

[0017] Illustrative embodiments of the subject matter claimed below will now be disclosed. In the interest of clarity, some features of some actual implementations may not be described in this specification. It will be appreciated that in the development of any such actual embodiments, numerous implementation-specific decisions must be made to achieve the developer’s specific goals, such as compliance with system-related and business-related constraints, which will vary from one implementation to another. Moreover, it will be appreciated that such a development effort, even if complex and time-consuming, would be a routine undertaking for those of ordinary skill in the art having the benefit of this disclosure.

[0018] The words and phrases used herein should be understood and interpreted to have a meaning consistent with the understanding of those words and phrases by those skilled in the relevant art. No special definition of a term or phrase, i.e., a definition that is different from the ordinary and customary meaning as understood by those skilled in the art, is intended to be implied by consistent usage of the term or phrase herein. To the extent that a term or phrase is intended to have a special meaning, i.e., a meaning other than the broadest meaning understood by skilled artisans, such a special or clarifying definition will be expressly set forth in the specification in a definitional manner that provides the special or clarifying definition for the term or phrase.

[0019] For example, the following discussion contains a non-exhaustive list of definitions of several specific terms used in this disclosure (other terms may be defined or clarified in a definitional manner elsewhere herein). These definitions are intended to clarify the meanings of the terms used herein. It is believed that the terms are used in a manner consistent with their ordinary meaning, but the definitions are nonetheless specified here for clarity. Definitions

[0020] “Central axis” with respect to a tube, as used herein, refers to the axis in a cartesian coordinate system that is parallel to the wall of the tube and passes through the centroid or geometric center of the shape defined by the intersection of the tube and a plane perpendicular to the central axis of the tube.

[0021] “Free of” a component, as used herein, refers to a composition substantially devoid of the component, or comprising the component in an amount of less than about 0.01 wt %, by weight of the total composition.

[0022] “HDPE,” as used herein, means ethylene homopolymers and ethylene copolymers produced in a gas phase and / or slurry phase polymerization and having a density in the range of 0.940 g / cm3to 0.970 g / cm3.

[0023] “LCB-mLLDPE,” as used herein, means a metallocene catalyzed LLDPE having a melt index ratio (MIR) of greater than or equal to 20.

[0024] “LDPE” or “low density polyethylene” as used herein, means ethylene homopolymers and / or ethylene copolymers produced in a high pressure free radical polymerization and having a density in the range of 0.910 g / cm3to 0.940 g / cm3.

[0025] “LLDPE” or “linear low density polyethylene” as used herein, means ethylene copolymers produced in a suspension, solution, slurry, or gas phase polymerization process and having a density in the range of 0.910 g / cm3to 0.940 g / cm3. LLDPEs can be produced with conventional Ziegler-Natta catalysts, vanadium catalysts, with metallocene catalysts, and / or with inhaving a composition distribution breadth index (CDBI) of greater than or equal to 50%.

[0027] “Polyethylene,” as used herein, means an ethylene homopolymer or a copolymer comprising at least 79 wt.% ethylene. The terms “polyethylene polymer,” “polyethylene,” “ethylene polymer,” “ethylene copolymer,” and “ethylene-based polymer” have the same meaning as polyethylene copolymer, except where otherwise indicated (e.g. where a polyethylene homopolymer is referred to, this means a polymer formed from ethylene monomer without comonomer units, e.g., 100 wt% ethylene-derived units).

[0028] “Stretch ratio,” as used herein, means the ratio of the length of a section of film after stretching to the length of that section of film before stretching. For example, a film having a length of 10 cm stretched in the machine direction (MD) to a length of 40 cm would have a MD stretch ratio or MD orientation ratio of 4:1.

[0029] It is noted that in this disclosure and particularly in the claims and / or paragraphs, terms such as “comprises”, “comprised”, “comprising” and the like can have the meaning attributed to it in U.S. patent law; e.g., they can mean “includes”, “included”, “including”, and the like; and that terms such as “consisting essentially of” and “consists essentially of” have the meaning ascribedto them in U.S. patent law, e.g., they allow for elements not explicitly recited, but exclude elements that are found in the prior art or that affect a basic or novel characteristic of the disclosure. Multilayer film

[0030] A multilayer film useful in collation shrink applications as disclosed herein comprises 70 orequal to 1.2 dg / min.; b) a long chain branched (LCB) mLLDPE, having a CDBI greater than or equal to 60% and a melt index (I2) less than 1.2 dg / min.; c) a high density polyethylene (HDPE); or d) a combination thereof.

[0032] In some embodiments, the narrow-CD mLLDPE is present in the first polymer composition in an amount less than or equal to 50 wt%, less than or equal to 40 wt%, less than or equal to 30 wt%, less than or equal to 20 wt%, or less than or equal to 10 wt%, based on the total weight of the first polymer composition.

[0033] In some embodiments, the LCB mLLDPE is present in the first polymer composition in an amount less than or equal to 50 wt%, less than or equal to 40 wt%, less than or equal to 30 wt%, less than or equal to 20 wt%, or less than or equal to 10 wt%, based on the total weight of the first polymer composition.

[0034] In some embodiments, the HDPE is present in the first polymer composition in an amount less than or equal to 50 wt%, less than or equal to 40 wt%, less than or equal to 30 wt%, less than or equal to 20 wt%, or less than or equal to 10 wt%, based on the total weight of the first polymer composition.

[0035] In some embodiments, the first polymer composition comprises the first mLLDPE in an amount in the range of from to 50 wt% to 95 wt%, from to 60 wt% to 90 wt%, from to 70 wt% to 85 wt%, or from to 75 wt% to 80 wt%, and HDPE in an amount in the range of from to 5 wt% to 50 wt%, from to 10 wt% to 40 wt%, from to 15 wt% to 30 wt%, or from to 20 wt% to 25 wt%, based on the total weight of the first polymer composition.

[0036] The first mLLDPE is a narrow MWD BOCD-mLLDPE, as defined herein, comprising from 80 wt% to 99 wt% ethylene derived units and 1 wt% to 20 wt% units derived from one or more C3 to C20 ^-olefins, based on the weight of the first mLLDPE, and having: a) the first mLLDPE comprises from 80 wt% to 99 wt% ethylene derived units and 1 wt% to 20 wt% units derived from one or more C3 to C20 ^-olefins, based on the weight of the first mLLDPE, and has: i) a density in the range of from 0.900 g / cm3to 0.940 g / cm3; ii) a composition distribution breadth index (CDBI) less than or equal to 40%; iii) a melt index (I2) in the range of from 0.1 g / 10 min to 5.0 g / 10 min; and iv) a broad orthogonal comonomer distribution. The first outer layer comprises a second polymer composition, and the second outer layer comprises a third polymer composition, wherein the second and third polymer compositions are the same or different. Each of the second and third polymer compositions independently comprise: i) a narrow-CD mLLDPE, having a CDBI greater than or equal to 50% and a melt index (I2) greater than or equal to 1.2 dg / min.; ii) a long chain branched (LCB) mLLDPE, having a CDBI greater than or equal to 60% and a melt index (I2) less than 1.2 dg / min.; iii) a high density polyethylene (HDPE); or iv) a combination thereof.

[0038] In some embodiments, the narrow-CD mLLDPE is present in the first outer layer and / or the second outer layer in an amount greater than or equal to 50 wt%, greater than or equal to 60 wt%, greater than or equal to 70 wt%, greater than or equal to 80 wt%, or greater than or equal to 90 wt%, based on the total weight of the relevant layer.

[0039] In some embodiments, the LCB mLLDPE is present in the first outer layer and / or the second outer layer in an amount greater than or equal to 50 wt%, greater than or equal to 60 wt%, greater than or equal to 70 wt%, greater than or equal to 80 wt%, or greater than or equal to 90 wt%, based on the total weight of the relevant layer.

[0040] In some embodiments, the HDPE is present in the first outer layer and / or the second outer layer in an amount greater than or equal to 50 wt%, greater than or equal to 60 wt%, greater than or equal to 70 wt%, greater than or equal to 80 wt%, or greater than or equal to 90 wt%, based on the total weight of the relevant layer.

[0041] In some embodiments, the first polymer composition comprises the first mLLDPE in an amount in the range of from to 50 wt% to 95 wt%, from to 60 wt% to 90 wt%, from to 70 wt% to 85 wt%, or from to 75 wt% to 80 wt%, and HDPE in an amount in the range of from to 5 wt% to 50 wt%, from to 10 wt% to 40 wt%, from to 15 wt% to 30 wt%, or from to 20 wt% to 25 wt%, based on the total weight of the first polymer composition.

[0042] In some embodiments, the first outer layer and / or the second outer layer comprise 100 wt% of the narrow-CD mLLDPE, based on the polymeric portion of the relevant layer excluding additives.

[0043] In some embodiments, the multilayer film is free of low density polyethylene (LDPE). LDPE is added to conventional CS films to help improve TD shrinkage, believed to result form long-chain branching present in LDPE. However, TD shrinkage of conventional CS film comprising LDPE and produced in a blown film process is typically limited to about 20-25%. In contrast, some embodiments of the BOPE CS films disclose herein have TD shrinkage of greater than or equal to 50%. Furthermore, addition of LDPE negatively impacts certain mechanical properties, such as, but not limited to, dart impact strength. BOPE CS films disclosed herein comprising less or no LDPE provide better dart impact strength relative to conventional CS films. As used herein, LDPE, as distinct from LLDPE (linear low density polyethylene), refers to low- density polyethylene that has a substantial degree of long chain branching (LCB) and is well known in the art to be produced from, e.g., free radical polymerization of ethylene monomers, often in autoclave or tubular reactors, as opposed to the catalyzed LLDPE polymerized from ethylene monomers and ^-olefin comonomers, and having substantial degrees of short-chain branching (SCB) (typically attributed to incorporation of said comonomer into the polymer chains), with minor amounts or substantially no LCB. First mLLDPE

[0044] The first mLLDPE is a narrow MWD BOCD-mLLDPE. In some embodiments, the Narrow MWD BOCD-mLLDPE is produced using a substituted bulky ligand hafnium transition metal metallocene-type catalyst compound and substituted versions thereof, as disclosed in one ornarrow MWD with a broad orthogonal comonomer distribution (BOCD), which may be referred to herein as Narrow MWD BOCD-mLLDPEs.

[0045] As mentioned above, a suitable mLLDPE can have a narrow molecular weight distribution (MWD) with broad orthogonal composition distribution (BOCD). The molecular weight distribution (MWD) or (Mw / Mn) can range from about 2.0 to about 4.5, from about 2.2 to about 4.5, from about 3.0 to about 4.0, or from about 2.5 to about 4.0. The weight average molecular weight (Mw) can range from about 15,000 to about 400,000 g / mol, from about 20,000 to about 250,000 g / mol, from about 20,000 to about 200,000 g / mol, from about 25,000 to about 150,000 g / mol, from about 150,000 to about 400,000 g / mol, from about 200,000 to about 400,000 g / mol, or from about 250,000 to about 350,000 g / mol. The z-average molecular weight (Mz) to weight average molecular weight (Mw) ratio can be greater than about 1.5, or greater than about 1.7, or greater than about 2.0. In some embodiments, this ratio is from about 1.7 to about 3.5, from about 2.0 to about 3.0, or from about 2.2 to about 3.0.

[0046] The term “orthogonal comonomer distribution” is used herein to mean across the molecular weight range of the polymer, comonomer contents for the various polymer fractions are not substantially uniform and a higher molecular weight fraction thereof generally has a higher comonomer content than that of a lower molecular weight fraction. The term “substantially uniform comonomer distribution” is used herein to mean that comonomer content of the polymer fractions across the molecular weight range of the ethylene-based polymer vary by < 10.0 wt%. In some embodiments, a substantially uniform comonomer distribution may refer to < 8.0 wt%, < 5.0 wt%, or < 2.0 wt%. Both a substantially uniform and an orthogonal comonomer distribution may be determined using fractionation techniques such as gel permeation chromatography- differential viscometry (GPC-DV), temperature rising elution fraction-differential viscometry (TREF-DV) or cross-fractionation techniques.

[0047] The broadness of the composition distribution of the polymer may be characterized by T75−T25. TREF is measured using an analytical size TREF instrument (Polymerchar, Spain), with a column of the following dimensions: inner diameter (ID) 7.8 mm, outer diameter (OD) 9.53 mm, and column length of 150 mm. The column may be filled with steel beads. 0.5 mL of a 4 mg / ml polymer solution in orthodichlorobenzene (ODCB) containing 2 g BHT / 4 L were charge onto the column and cooled from 140°C to −15°C at a constant cooling rate of 1.0°C / min Subsequently, ODCB may be pumped through the column at a flow rate of 1.0 ml / min, and the column temperature may be increased at a constant heating rate of 2°C / min to elute the polymer. The polymer concentration in the eluted liquid may then be detected by means of measuring the absorption at a wavenumber of 2941 cm−1 using an infrared detector. The concentration of theethylene-^-olefin copolymer in the eluted liquid may be calculated from the absorption and plotted as a function of temperature. As used herein, T75−T25 values refer to where T25 is the temperature in degrees Celsius at which 25% of the eluted polymer is obtained and T75 is the temperature in degrees Celsius at which 75% of the eluted polymer is obtained via a TREF analysis.

[0048] By “broad orthogonal comonomer distribution” or BOCD, it is meant that a substantially higher degree of short chain branching is present on longer molecular-weight polymer chains than on shorter molecular-weight polymer chains within the copolymer. Suitable narrow-MWD mLLDPEs with BOCD can have a T75−T25 value from 5 to 10, alternatively, a T75−T25 value from 5.5 to 10, and alternatively, a T75−T25 value from 5.5 to 8, alternatively, a T75−T25value from 6 to 10, and alternatively, a T75−T25value from 6 to 8, where T25is the temperature in degrees Celsius at which 25% of the eluted polymer is obtained and T75is the temperature in degrees Celsius at which 75% of the eluted polymer is obtained via temperature rising elution fractionation (TREF).

[0049] These mLLDPEs can have a CDBI of less than about 40%, or less than about 35%, or less than about 30%, or less than about 25%. The CDBI can also range from a low of about 15%, 20%, or 25% to a high of about 30%, 35%, or 40%, and it is further noted that composition distribution is such that higher molecular weight chains of these mLLDPEs have greater wt% of comonomer than lower molecular weight chains of the mLLDPEs. CDBI is defined as the weight percent of the copolymer molecules having a comonomer content within + / -50% of the median comonomer mol% value, as described at pp. 18-19 of WO 1993 / 003093 in conjunction with FIG. 17 therein. This means that for a copolymer having median comonomer mol% value (Cmed) of 8mol% comonomer on a polymer chain, CDBI is the wt% of copolymer chains having comonomer mol% that is between (0.5 x Cmed) and (1.5 x Cmed). In this example, CDBI is the wt% of copolymer chains having comonomer mol% between (0.5 x 8) and (1.5 x 8), or comonomer content between 4 mol% and 12 mol%. WO 1993 / 003093 also describes the process for determining the weight fraction of polymer vs. composition curve (i.e., the composition distribution curve) using chromatography and C13 NMR, and determining the median comonomer composition Cmed therefrom, with reference to Figures 16 and 17 of that publication. See also Wild, et al., J. Poly. Sci., Poly. Phys. Ed., vol. 20, p. 441 (1982) and U.S. Patent No. 5,008,204, which are also incorporated herein by reference. Thus, a higher value of CDBI indicates a narrow composition distribution (meaning that comonomer is distributed relatively evenly across polymer chains of different molecular weight).

[0050] These mLLDPEs can have 70.0 wt% to 100.0 wt% of units derived from ethylene. The lower limit on the range of ethylene content may be from 70.0 wt %, 75.0 wt%, 80.0 wt%, 85.0 wt%, 90.0 wt%, 92.0 wt%, 94.0 wt%, 95.0 wt%, 96.0 wt%, 97.0 wt%, 98.0 wt%, or 99.0 wt% based on the wt% of polymer units derived from ethylene. These mLLDPEs can also have an upper ethylene limit of 80.0 wt%, 85.0 wt%, 90.0 wt%, 92.0 wt%, 94.0 wt%, 95.0 wt%, 96.0 wt%, 97.0 wt%, 98.0 wt%, 99.0 wt%, 99.5 wt%, or 100.0 wt%, based on polymer units derived from ethylene. Less than 30.0 wt% of polymer units can be derived from a C3- C20olefin, preferably, an alpha-olefin, e.g., hexene or octene. The lower limit on the range of C3-C20 olefin-content can be 25.0 wt%, 20.0 wt%, 15.0 wt%, 10.0 wt%, 8.0 wt%, 6.0 wt%, 5.0 wt%, 4.0 wt%, 3.0 wt%, 2.0 wt%, 1.0 wt%, or 0.5 wt%, based on polymer units derived from the C3-C20olefin. The upper limit on the range of C3-C20olefin-content can be 20.0 wt%, 15.0 wt%, 10.0 wt%, 8.0 wt%, 6.0 wt%, 5.0 wt%, 4.0 wt%, 3.0 wt%, 2.0 wt%, or 1.0 wt%, based on polymer units derived from the C3 to C20 olefin.

[0051] These mLLDPEs can have a density in accordance with ASTM D-4703 and ASTM D- 1505 / ISO 1183 of from about 0.900 g / cm3to about 0.940 g / cm3, from about 0.910 g / cm3to about 0.935 g / cm3, from about 0.900 g / cm3to about 0.930 g / cm3, from about 0.900 g / cm3to about 0.925 g / cm3, from about 0.900 g / cm3to about 0.923 g / cm3, from about 0.900 g / cm3to about 0.920 g / cm3, from about 0.912 g / cm3to about 0.919 g / cm3, from about 0.912 g / cm3to about 0.918 g / cm3, from about 0.914 g / cm3to about 0.918 g / cm3, or from about 0.915 g / cm3to about 0.918 g / cm3.

[0052] These mLLDPEs can have a melt index (MI) or (I2.16) as measured by ASTM D-1238- E (190°C / 2.16 kg) of about 0.1 g / 10 min to about 5.0 g / 10 min, about 0.1 g / 10 min to about 3.0 g / 10 min, about 0.1 g / 10 min to about 2.0 g / 10 min, about 0.1 g / 10 min to about 1.2 g / 10 min, about 0.2 g / 10 min to about 1.5 g / 10 min, about 0.2 g / 10 min to about 1.1 g / 10 min, about 0.3 g / 10 min to about 1.0 g / 10 min, about 0.4 g / 10 min to about 1.0 g / 10 min, about 0.5 g / 10 min to about 1.0 g / 10 min, about 0.6 g / 10 min to about 1.0 g / 10 min, about 0.7 g / 10 min to about 1.0 g / 10 min, or about 0.75 g / 10 min to about 0.95 g / 10 min.

[0053] These mLLDPEs can have a melt index ratio (MIR) (I21.6 / I2.16) (as defined below) of from about 20 to about 38, from about 22 to about 35, from about 20 to about 32, from about 25 to about 32 or from about 28 to about 31.

[0054] These mLLDPEs can also have at least a first peak and a second peak in a comonomer distribution analysis, wherein the first peak has a maximum at a log(Mw) value of from 4.0 to 5.4, or from 4.3 to 5.0, or from 4.5 to 4.7; and a TREF elution temperature of from 70.0°C to 100.0°C,or from 80.0°C to 95.0°C, or from 85.0°C to 90.0°C. The second peak in the comonomer distribution analysis has a maximum at a log(Mw) value of 5.0 to 6.0, 5.3 to 5.7, or 5.4 to 5.6; and a TREF elution temperature of 40.0°C to 60.0°C, 45.0°C to 60.0°C, or 48.0°C to 54.0°C.

[0055] In any of the embodiments described above, a suitable mLLDPE can have a narrow MWD with broad orthogonal composition distribution with one or more of the following properties: a melt index (MI) (190°C / 2.16 kg) of from about 0.1 g / 10 min to about 5.0 g / 10 min; a melt index ratio (MIR) of from about 25 to about 32; a Mwof from about 20,000 to about 200,000 g / mol; a Mw / Mn of from about 2.0 to about 4.5; and a density of from about 0.900 g / cm3to about 0.940 g / cm3. These narrow MWD BOCD-mLLDPEs may be referred to as a “second mLLDPE” in recycled resin compositions of the present disclosure.

[0056] Commercially available examples of such second mLLDPEs having the foregoing unique combination of properties include Exceed XP™ resins from ExxonMobil Chemical Company. Narrow-CD mLLDPE

[0057] Narrow-CD mLLDPE can be produced using an unbridged bis-cyclopentadienyl Group 4 and substituted versions thereof. Such catalysts produce polyethylene grades having a narrow composition distribution (i.e., a move uniform distribution of comonomer among polymer chains) and are referred to herein as narrow-CD mLLDPE.

[0058] A narrow-CD mLLDPE can, for example, include a flat composition distribution metallocene-catalyzed LLDPE (mLLDPE) that is a copolymer of 80 to 99.9 wt% ethylene-derived units, with the balance of units derived from one or more C3to C12^-olefin comonomer (and in particular one or more of butene, hexene, octene; preferably one of those; and more preferably hexene). The wt% is based on total mass of ethylene-derived units plus comonomer-derived units in the polyethylene. Such polyethylenes are referred to as “flat composition distribution” in recognition that comonomer is incorporated in relatively equal amounts (by wt%) in shorter vs. longer molecular-weight chains within the polymer. These also may be referred to as “narrow- CD” or “narrow-composition-distribution” polyethylenes; or, equivalently, high-CDBI mLLDPEs. Composition distribution refers to the distribution of comonomer among polymer chains of different length (different molecular weight), and CDBI refers to Composition Distribution Breadth Index, which is defined as above.

[0059] The narrow-CD polyethylene may have CDBI of at least 50%, more preferably at least 60%, such as within the range from 50 to 90%, or 60 to 80%.

[0060] A narrow-CD polyethylene may more particularly have ethylene-derived content within the range from a low of any one of 80, 85, 86, 87, 87.5, 88, 90, 91, 92, 93, 94 or 95 wt% to a high of any one of 88, 90, 93, 94, 95, 96, 97, 98, 99, or 99.9 wt%; with ranges from any foregoing low to any foregoing high contemplated, provided the high end is greater than the low end (e.g., 85 to 95 wt%, such as 86 to 92 wt% ethylene-derived units; or 94 to 99 wt% ethylene-derived units). The balance is comprised of the C3 to C12 ^-olefin comonomer-derived units (e.g., hexene).

[0061] The narrow-CD mLLDPE can provide reduced softening point relative to formation processes, and furthermore provide excellent sealing, optical, and mechanical properties to a film made therefrom. The narrow-CD mLLDPE preferably also has one or more, preferably all, of the following further properties: • Peak melting temperature within the range from 105°C to 120°C, preferably 110°C or 111°C to 115°C or 116°C. Peak melting temperature, also referred to herein by the shorthand “melting point” is determined by using a differential scanning calorimeter (DSC). DSC measurements can be carried out with a TA DSC8000 instrument under N2atmosphere with a heating / cooling rate of 10 K / min. The samples are heated from −50 to 300°C., held for 5 minutes in order to remove the previous thermal history, then cooled down to −50°C, and then heated again to 300°C. • Vicat softening temperature (ASTM D1525) within the range from softening point within the range from 70°C to 130°C, preferably 90°C to 110°C, such as from a low of any one of 70, 75, 80, 85, 90, 95, 96, 97, 98, 99, or 100°C to a high of any one of 100, 101, 102, 103, 104, 105, 110, 115, 120, 125, or 130°C (with ranges from any foregoing low to any foregoing high contemplated, provided the high is greater than the low, e.g., 90°C to 110°C or 97°C to 103°C). • Melt index (MI, also referred to as I2 or I2.16 in recognition of the 2.16 kg loading used in the test) within the range from 0.1 to 5.0 g / 10 min (ASTM D1238, 190°C, 2.16 kg load), such as from a low of any one of 0.1, 0.2, 0.3, 0.4, 0.5, 0.7, or 0.8 g / 10 min to a high of any one of 1.0, 1.1, 1.2, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, or 5.0 g / 10 min; with ranges from any foregoing low end to any foregoing high end also contemplated. • Long chain branching index (LCB Index, also referred to herein as g^visor g^ index) greater than 0.95, preferably greater than or equal to 0.96 or 0.97.

[0062] The narrow-CD mLLDPE can also have one or more, preferably all, of the following:• Weight average molecular weight (Mw) within the range from 45,000 to 120,000 g / mol, such as from 50,000 to 115,000 g / mol or 60,000 to 110,000 g / mol (with ranges from any foregoing low end to any foregoing high end also contemplated, e.g., 45,000 to 110,000 g / mol); • Number average molecular weight (Mn) within the range from 20,000 to 55,000 g / mol, such as within the range from 25,000; 30,000; 35,000; or 40,000 to a high of 30,000; 35,000; 40,000; 45,000; 50,000; or 55,000 g / mol, with ranges from any foregoing low end to any foregoing high end also contemplated (provided the high end is greater than the low end), e.g., from 35,000 to 55,000 g / mol; • Molecular weight distribution (MWD) within the range from 1.5 or 2.0 to 3.5 or 4; and • Density (ASTM D1505) within the range from 0.905 to 0.940 g / cm3, such as within the range from a low end of any one of 0.905, 0.910, 0.911, 0.912, or 0.915 g / cm3to a high end of any one of 0.913, 0.914, 0.915, 0.920, 0.925, 0.926, 0.928, 0.930, 0.935, or 0.940 g / cm3, with ranges from any foregoing low end to any foregoing high end contemplated (provided the high end is greater than the low end), e.g., 0.910 to 0.915 g / cm3.

[0063] Examples of suitable polyethylenes for the narrow-CD mLLDPE include Exceed™ performance polyethylenes available from ExxonMobil Chemical Company, as well as other commercially available mLLDPEs such as Evolue™ SP1510, available from Prime Polymer Co., Ltd. LCB-mLLDPE

[0064] An LCB-mLLDPE can be produced using a bridged bis-cyclopentadienyl Group 4 and substituted versions thereof, as disclosed in one or more of U.S. Pat. No.6,255,426 and 6,476,171, the contents of which are fully incorporated by reference herein. Such Type 2 catalysts produce polyethylene grades having some long-chain branching (as compared to the highly linear structure of most mLLDPEs), and are referred to herein as “LCB-mLLDPE.”considered long-chain-branched as compared to other linear low-density polyethylenes, and in particular as compared to other metallocene LLDPEs; whereas their total long-chain branching will still be less than LDPEs with very high degrees of long-chain branching.) This small amount of LCB can be evidenced through, e.g., a high melt index ratio (MIR) and / or particular rheology characteristics as shown through data obtained by small angle oscillatory shear (SAOS) experiments (for instance, ratio of ^0.01 / ^100, the complex viscosity recorded at shear rates of 0.01 and 100 rad / s, respectively).

[0066] Yet another useful parameter illustrating presence of some LCB can be seen in the melt index ratio. Melt index ratio (MIR) is the ratio of high load melt index (HLMI, ASTM D1238 at 190 °C, 21.6 kg) to melt index (MI2, ASTM D1238 at 190°C, 2.16 kg).

[0067] Accordingly, LCB-mLLDPEs useful for the present compositions can have one or more of the following properties (which can be useful indicia of moderate LCB): • MIR within the range from a low of any one of 20, 25, 26, 27, 28, 29, 30, or 31 to a high of any one of 40, 35, 34, 33, 32, 31, or 30 with ranges from any of the foregoing lows to any of the foregoing highs contemplated herein (e.g., 27 to 33, such as 28 to 32, or 29 to 31). • Complex shear viscosity (^*) @ 0.01 rad / sec and 190º C in the range of 5,000 to 12,000 Pa·s; or from a low of any one of 5,000; 6,000; 7,000; 8,000; 9,000; 10,000; or 11,000 Pa·s, to a high of any one of 12,000; 11,000; 10,000; 9,000; 8,000; 7,000; or 6,000 Pa·s, with ranges from any low end to any high end contemplated (e.g., 6,000 to 8,000 Pa·s). • Complex shear viscosity (^*) @ 100 rad / sec and 190º C within the range from 900 to 2000 Pa·s; such as from a low end of any one of 900; 1,000; 1,100; or 1,200 Pa·s to a high end of any one of 1,200; 1,300; 1,400; 1,500; or 2,000 Pa·s, with ranges from any foregoing low to any foregoing high also contemplated (e.g., 1,100 to 1,300 Pa·s). • Shear thinning ratio (^* @ 0.01 / 100) less than 15, or in the range of 3 to 15, or 4 to 12, or 5 to 10, or 5.5 to 8. • An inflection point in a Van Gurp Palmen plot of phase angle vs. complex modulus (Pa) of the LCB-mLLDPE.

[0068] Finally, yet another indicator of LCB can be seen in the LCB index (g' or alternatively g'vis), which for LCB-mLLDPE could be less than 1, such as within the range from 0.9 to 0.99 or 0.94 to 0.98, although still substantially higher than g' for heavily-LCB polyethylene, such as LDPE made using free radical polymerization.

[0069] Suitable mLLDPEs with the aforementioned moderate LCB are preferably copolymers of 80, 85, 88, 90, 92, 93, 94, or 95 to 6, 97, 98, or 99 wt% ethylene-derived units, with the balance derived from one or more C3to C12^-olefins (and in particular one or more of butene, hexene, octene; preferably one of those; and more preferably hexene). The wt% is based on total mass of ethylene-derived units plus comonomer-derived units in the polyethylene.

[0070] Suitable LCB mLLDPEs can also have a CDBI greater than or equal to 60%, preferably greater than or equal to 70%, such as within the range from a low of any one of 60, 70, or 75% toa high of 80, 85, 90, 95, or 99%, with ranges from any foregoing low end to any foregoing high end contemplated. Composition Distribution Breadth Index (CDBI) is defined as the weight percentage of the copolymer molecules having a comonomer content within 50% of the median total molar comonomer content. The CDBI of a copolymer is readily determined utilizing well known techniques for isolating individual fractions of a sample of the copolymer. One such technique is Temperature Rising Elution Fraction (TREF), as described in Wild, et al., J. Poly. Sci., Poly. Phys. Ed., Vol. 20, p. 441 (1982) and U.S. Patent No. 5,008,204, which are fully incorporated herein by reference.

[0071] Suitable LCB mLLDPEs can also have a MWD (Mw / Mn) within the range of 2.5 to 5.5, such as within the range of 3 or 3.5 to 4.5 or 5.

[0072] Suitable LCB mLLDPEs can further have a Melt Index (I2, determined per ASTM D1238 at 190°C, 2.16 kg load) within the range of 0.1 to 3.0 g / 10 min, or can range from a low of any one of 0.1, 0.15, 0.2, or 0.22 to a high of any one of 0.30, 0.40, 0.50, 0.60, 0.70, 0.80, 0.90, 1.0, 1.5, 2.0, 2.2, 2.5, 2.7, or 3.0 g / 10 min; with ranges from any foregoing low end to any foregoing high end also contemplated (provided the high end is greater than the low end), e.g., from 0.1 to 2.5 g / 10 min; 0.15 to 1.0 g / 10 min; or 0.2 to 0.50 g / 10 min.

[0073] High load melt index (HLMI, or I21, determined per ASTM D1238 at 190°C, 21.6 kg load) can be within the range from 10 to 75 g / 10 min, such as from 12 to 70 g / 10 min.

[0074] Density of the LCB-mLLDPE can be within the range from 0.900 to 0.940 g / cm3, such as from a low of any one of 0.905, 0.910, 0.920, or 0.925 g / cm3to a high of any one of 0.930, 0.932, 0.933, 0.934, 0.935, or 0.940 g / cm3, with ranges from any forgoing low to any foregoing high contemplated herein (e.g., 0.910 to 0.935 g / cm3).

[0075] These LCB-mLLDPEs can be referred to as a “first mLLDPE” in compositions described herein. Some particular examples of such first mLLDPEs having the foregoing unique combination of properties include certain Enable™ and Exceed™ XP brand polyethylenes from ExxonMobil Chemical Company, such as Exceed™ XP 6026, Enable™ 2010, Enable™ 2703, Enable™ 3505, Enable™ 4002, and Enable™ 4009 performance polyethylenes. Other commercial examples include Dow Innate™ ST70, Dow Agility™ 2001, Dow Elite™ 5940, Dowlex™ 2038.68G, Dow Elite™ AT 6401, Dow Attane™ 4701G, Marlex™ TR130, and Nova Surpass™ 117 / 116.Additives

[0076] The polymer composition herein comprising COC and polyethylene may be used in combination with the following additives and other components. - First Antioxidant

[0077] The first antioxidant comprises one or more antioxidants. They include, but are not limited to, hindered phenols, for example, octadecyl-3-(3,5-di-tert.butyl-4-hydroxyphenyl)- propionate (CAS 002082-79-3) commercially available as Irganox™ 1076, pentaerythritol tetrakis (3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (CAS 6683-19-8) commercially available as Irganox™ 1010; and combinations thereof.

[0078] They may be combined with one or more polymers in range from 100 to 4000 parts by weight of the first antioxidant, based on one million parts of the polymer or polymer composition; alternatively, from 250 to 3000 parts by weight of the first antioxidant, based on one million parts of the polymer or polymer composition, alternatively, from 500 to 2500 parts by weight of the first antioxidant, based on one million parts of the polymer or polymer composition, alternatively, from 750 to 2500 parts by weight of the first antioxidant, based on one million parts of the polymer or polymer composition, alternatively, from 750 to 2000 parts by weight of the first antioxidant, based on one million parts of the polymer or polymer composition, and alternatively, from 1000 to 2000 parts by weight of the first antioxidant, based on one million parts of the polymer or polymer composition. - Second Antioxidant

[0079] The second antioxidant comprises one or more antioxidants. They include, but are not limited to, liquid phosphites, such as C2-C7, preferably C2-C4, and alkyl aryl phosphites mixed structures. Non-limiting examples include mono-amylphenyl phosphites, di-amylphenyl phosphites, dimethylpropyl phosphites, 2-methylbutanyl phosphites, and combinations thereof. In several embodiments of the invention, the second antioxidant may also be represented by the formula [4-(2-methylbutan-2-yl)phenyl]x[2,4-bis(2-methylbutan-2-yl)phenyl]3-x, phosphate, wherein x=0, 1, 2, 3, or combinations thereof.

[0080] Such antioxidants and their use with polyolefin polymers have been described in U.S. Patent Application Nos. 2005 / 0113494; 2007 / 0021537; 2009 / 0326112; 2013 / 0190434; 2013 / 225738; 2014 / 0045981, and U.S. Pat. Nos. 5,254,709; 6,444,836; 7,888,414; 7,947,769; 8,008,383; 8,048,946; 8,188,170; and 8,258,214. An example of a commercially available liquid phosphite is sold under the tradename WESTON™ 705 (Addivant, Danbury, Conn.).

[0081] The second antioxidant may be combined with one or more polymers in the range from 100 to 4000 parts by weight of the second antioxidant, based on one million parts of the polymer or polymer composition; alternatively, from 250 to 3000 parts by weight of the second antioxidant, based on one million parts of the polymer or polymer composition, alternatively, from 300 to 2000 parts by weight of the second antioxidant, based on one million parts of the polymer or polymer composition, alternatively, from 400 to 1450 parts by weight of the second antioxidant, based on one million parts of the polymer or polymer composition, alternatively, from 425 to 1650 parts by weight of the second antioxidant, based on one million parts of the polymer or polymer composition, and alternatively, from 1 to 450 parts by weight of the second antioxidant, based on one million parts of the polymer or polymer composition.

[0082] The polymers and / or compositions comprising the first antioxidant and / or the second antioxidant described above may be used in combination with the following neutralizing agents, additional additives and other components. - Neutralizing Agents

[0083] One or more neutralizing agents (also called catalyst deactivators) include, but are not limited to, calcium stearate, zinc stearate, calcium oxide, synthetic hydrotalcite, such as DHT4A, and combinations thereof. - Additional Additives and Other Components

[0084] Additional additives and other components include, but are limited to, fillers (especially, silica, glass fibers, talc, etc.) colorants or dyes, pigments, color enhancers, whitening agents, cavitation agents, anti-slip agents, antiblock agents (such as Polybatch™ F15 antiblock, commercially available from A. Schulman in Ohio), lubricants, plasticizers, processing aids, antistatic agents, antifogging agents, nucleating agents, stabilizers, mold release agents, and other antioxidants (for example, hindered amines and phosphates). Nucleating agents include, for example, sodium benzoate and talc. Slip agents include, for example, oleamide and erucamide.

[0085] In a class of embodiments, the one or more layers or the films may comprise one or more of fillers, pigments, slip additives / agents, colorants or dyes, color enhancers, whitening agents, cavitation agents, lubricants, plasticizers, processing aids, antifogging agents, nucleating agents, stabilizers, mold release agents, or antioxidants.

[0086] In some embodiments, the first outer layer and / or the second outer layer comprise an antiblock agent (such as Polybatch™ F15) in an amount in the range of from 0.1, 0.2, 0.3, 0.4, or 0.5 wt% to 2.0, 2.5, 3.0, 3.5, or 4.0 wt%, based on the weight of the relevant layer.Films and Methods of Making Them

[0087] The polymer compositions comprising mLLDPE and HDPE as described above may be formed into monolayer or multilayer films. As used herein a “film” or “multilayered film” is a material that has an average thickness of less than or equal to 250 µm and may include one or more substances such as polymers, fillers, additives, oils, etc. In some embodiments, the film or multilayered film is continuous within its measurable width and length, typically is flexible, and preferably has a thickness within a range from 2, 10, 20, 40, or 45 ^m to 50, 100, 150, 200, or 250 µm.

[0088] In some embodiments of the multilayer film comprising at least a first outer layer, a second outer layer, and a core layer disposed between the first outer layer and the second outer layer, the thickness of the core layer is in the range of from 25%, 35%, 45%, or 55% to 75%, 80%, 85%, or 90% of the total thickness of the multilayer film.

[0089] In some embodiments, the core layer of the films is sandwiched between two polyethylene skin layers. In some embodiments, at least a core layer is sandwiched between two to six layers comprising LLDPE. Some configurations include a skin / core / skin, and skin / sub- skin / core / sub-skin / core layer arrangements. In some embodiments, each skin layer independently comprises at least 50 wt% linear low density polyethylene by weight of each skin layer. In any embodiment, the multilayered film further comprises a sub-skin layer sandwiched between a core layer(s) and each skin layer. In some embodiments, each sub-skin layer independently comprises at least 50 wt% linear low density polyethylene by weight of each skin layer. In embodiments where there are two or more core layers, they are preferably adjacent to one another, but may have a layer of LLDPE therebetween.

[0090] It is contemplated that other materials can be incorporated into a film layer, or that a film layer itself may comprise or consist essentially of another material in any embodiment herein. Suitable materials include ethylene vinyl acetate, ethylene-based ionomers, polypropylene, propylene-based elastomers, ethylene-based plastomers, ethylene-propylene rubbers, styrenic block copolymers, styrenic polymers, cellulosic polymers, and combinations thereof.

[0091] In some embodiments, the films of the current invention are subjected to a post-quench biaxial orientation process. As is well known in the art, orientation may be achieved by reheating an extruded, quenched and unoriented polymeric film in an oven or heated zone that raises the temperature of the polymeric material above its glass transition temperature. The material is then stretched in at least one direction to orient, or align, the polymer chains within the film. The filmis then annealed and subsequently cooled thereby allowing crystals to reform so that the stretch and orientation is maintained.

[0092] Orientation in the direction of extrusion is known as machine direction (MD) orientation. Orientation perpendicular to the direction of extrusion is known as transverse direction (TD) orientation. Either sequential or simultaneous orientation processes may be utilized depending upon the desired film features. Sequential orientation may be accomplished by stretching or pulling a film first in the MD followed by TD orientation. A simultaneous orientation process means the film is stretched in both the machine direction and the transverse direction in a single step utilizing a series of motors rather than clips, for example as with the LISIM® process. Tenter orientation processes may also be used in the biaxial orientation of the films of the current invention. In some embodiments of present invention, a double-bubble orientation process may be used.

[0093] In some embodiments, machine direction orientation stretch ratios for the films disclosed herein are greater than or equal to 2.0:1, greater than or equal to 2.5:1, greater than or equal to 3.0:1, or greater than or equal to 3.5:1. In some embodiments, machine direction orientation stretch ratios for the films disclosed herein are less than or equal to 7.5:1, less than or equal to 7.0:1, less than or equal to 6.5:1, or greater than or equal to 6.0:1.

[0094] In some embodiments, transverse direction orientation ratios for the films disclosed herein are greater than or equal to 6.5:1, greater than or equal to 7.0:1, greater than or equal to 7.5:1, or greater than or equal to 8.0:1. In some embodiments, transverse direction orientation ratios for the films disclosed herein are less than or equal to 11.5:1, less than or equal to 11.0:1, less than or equal to 10.5:1, or greater than or equal to 10.0:1.

[0095] A biaxial orientation ratio is the product of the machine direction orientation ratio and the transverse direction orientation ratio of the film. In some embodiments, the film has a biaxial orientation ratio ranging from about 20:1 to about 60:1, subsequent to a post-quench biaxial orientation process.

[0096] In some embodiments, the biaxial oriented films disclosed herein have a machine direction (MD) shrinking force in a range of from 700 mN to 1,400 mN, from 750 mN to 1,350 mN, from 800 mN to 1,300 mN, or from 850 mN to 1,250 mN.

[0097] In some embodiments, the biaxial oriented films disclosed herein have a normalized machine direction (MD) shrinking force in a range of from 23.3 mN / µm to 46.7 mN / µm, from25.0 mN / µm to 45.0 mN / µm, from 26.7 mN / µm to 43.3 mN / µm, or from 28.3 mN / µm to 41.7 mN / µm.

[0098] In some embodiments, the biaxial oriented films disclosed herein have a transverse direction (TD) shrinking force in a range of from 700 mN to 1,400 mN, from 750 mN to 1,350 mN, from 800 mN to 1,300 mN, or from 850 mN to 1,250 mN.

[0099] In some embodiments, the biaxial oriented films disclosed herein have a normalized transverse direction (TD) shrinking force in a range of from 23.3 mN / µm to 46.7 mN / µm, from 25.0 mN / µm to 45.0 mN / µm, from 26.7 mN / µm to 43.3 mN / µm, or from 28.3 mN / µm to 41.7 mN / µm.

[0100] In some embodiments, the biaxial oriented films disclosed herein have a shrink temperature in the range of from 120°C to 170°C, from 130°C to 165°C, from 140°C to 160°C, or from 145°C to 155°C. Shrink wrap process

[0101] In some embodiments, a process for collation shrink packaging comprises arranging two or more items adjacent to one another in one or more rows of two or more items to form a collated bundle. The collated bundle defines a cartesian coordinate system having a first horizontal axis parallel to the one or more rows, a second horizontal axis perpendicular to the one or more rows, and a vertical axis. The process further comprises wrapping the collated bundle in a multilayer film, as described herein, at a temperature in the range of from 10°C to 40°C to form a wrapped bundle, wherein: i) the multilayer film forms a tube encasing the collated bundle items; ii) the tube as a first opening at one end of the bundle and a second opening at the opposite end of the bundle; and iii) the tube is oriented such that the central axis of the tube is parallel to the first horizontal axis, the second horizontal axis, or the vertical axis. The process further comprises heating the wrapped bundle to a temperature sufficient to shrink the tube to conform to the outermost surfaces of the collated bundle to form a shrink wrapped bundle.

[0102] In some embodiments, the first opening and the second opening are each reduced to a substantially circular opening having a maximum diameter less than the minimum dimension of a shape defined by the outer perimeter of the collated bundle projected onto a plane perpendicular to the central axis.

[0103] In some embodiments, the temperature sufficient to shrink the tube is in the range of from 120°C to 170°C, from 130°C to 165°C, from 140°C to 160°C, or from 145°C to 155°C.

[0104] In some embodiments, the wrapping of the collated bundle is performed such that the machine direction of the film is perpendicular to the central axis of the tube. Certain Embodiments

[0105] In certain embodiments, a multilayer film comprises at least a first outer layer, a second outer layer, and a core layer disposed between the first outer layer and the second outer layer. The core layer comprises a first polymer composition, wherein the first polymer composition comprises at least 50 wt% of a first metallocene linear low density polyethylene (mLLDPE), based on the weight of the first polymer composition. The multilayer film is biaxially oriented.

[0106] The first mLLDPE comprises from 80 wt% to 99 wt% ethylene derived units and 1 wt% to 20 wt% units derived from one or more C3to C20^-olefins, based on the weight of the first mLLDPE. The first mLLDPE has: i) a density in the range of from 0.900 g / cm3to 0.940 g / cm3; ii) a composition distribution breadth index (CDBI) less than or equal to 40%; iii) a melt index (I2) in the range of from 0.1 g / 10 min to 5.0 g / 10 min; and iv) a broad orthogonal comonomer distribution.

[0107] The first outer layer comprises a second polymer composition, and the second outer layer comprises a third polymer composition, wherein the second and third polymer compositions are the same or different and each independently comprises: i) a narrow-CD mLLDPE, having a CDBI greater than or equal to 50% and a melt index (I2) greater than or equal to 1.2 dg / min.; ii) a long chain branched (LCB) mLLDPE, having a CDBI greater than or equal to 60% and a melt index (I2) less than 1.2 dg / min.; iii) a high density polyethylene (HDPE); or iv) a combination thereof

[0108] In further embodiments of the multilayer film, in addition to the foregoing limitations, the multilayer film can be further characterized by one or more of the following: a) the broad orthogonal comonomer distribution comprises at least a first peak and a second peak in a comonomer distribution analysis, wherein the first peak has a maximum at a log(Mw) value of from 4.0 to 5.4 and a temperature rising elution fractionation (TREF) elution temperature of from 70.0°C to 100.0°C, and the second peak in the comonomer distribution analysis has a maximum at a log(Mw) value of 5.0 to 6.0 and a TREF elution temperature of 40.0°C to 60.0°C;b) the broad orthogonal comonomer distribution comprises a T75−T25value in the range of from 5 to 10, wherein T25 is the temperature in degrees Celsius at which 25% of the of to100, 150, 200, or 250 µm; f) the thickness of the core layer is in the range of from 25%, 35%, 45%, or 55% to 75%, 80%, 85%, or 90% of the total thickness of the multilayer film; g) the biaxial orientation comprises a machine direction (MD) orientation stretch ratio into 6.0:1, and a transverse direction (TD) orientation stretch ratio in a range of from 6.5:1 to 11.5:1, from 7.0:1 to 11.0:1, from 7.5:1 to 10.5:1, or from 8.0:1 to 10.0:1; h) the film has one or more of:vi) the first polymer composition comprises the first mLLDPE in an amount in the range of from 50 wt% to 95 wt% and a HDPE in an amount in the range of from 5 wt% to 50 wt%, based on the total weight of the first polymer composition; vii) the first outer layer and the second outer layer each independently comprise a narrow-CD mLLDPE in an amount greater than or equal to 50 wt%, based on the total weight of the first outer layer and the second outer layer, respectively; and viii) the first outer layer and / or the second outer layer each independently comprise an antiblock additive.

[0109] In certain embodiments, a process for collation shrink packaging comprises arranging two or more items adjacent to one another in one or more rows of two or more items to form a collated bundle. The collated bundle defines a cartesian coordinate system having a first horizontal axis parallel to the one or more rows, a second horizontal axis perpendicular to the one or more rows, and a vertical axis. The process further comprises wrapping the collated bundle in a multilayer film at a temperature in the range of from 10°C to 40°C to form a wrapped bundle, wherein: i) the multilayer film forms a tube encasing the collated bundle items; ii) the tube as a first opening at one end of the bundle and a second opening at the opposite end of the bundle; and iii) the tube is oriented such that the central axis of the tube is parallel to the first horizontal axis, the second horizontal axis, or the vertical axis.

[0110] The process further comprises heating the wrapped bundle to a temperature sufficient to shrink the tube to conform to the outermost surfaces of the collated bundle to form a shrink wrapped bundle.

[0111] The biaxially oriented multilayer film used in the process comprises at least a first outer layer, a second outer layer, and a core layer disposed between the first outer layer and the second outer layer, the core layer comprising a first polymer composition, the first polymer composition comprising at least 50 wt% of a first metallocene linear low density polyethylene (mLLDPE) and optionally up to 50 wt% of a second polymer composition, based on the weight of the first polymer composition, wherein: a) the first mLLDPE comprises from 80 wt% to 99 wt% ethylene derived units and 1 wt% to 20 wt% units derived from one or more C3to C20^-olefins, based on the weight of the first mLLDPE, and has:i) a density in the range of from 0.900 g / cm3to 0.940 g / cm3; a distribution breadth index less than or to to or atTest Methods / Polymer Characterization

[0115] Density (g / cm3): Density measurements were made following ASTM D-1505.

[0116] Dynamic Mechanical Analysis (DMA) rheological measurements (e.g. small-strain (10%) oscillatory shear measurements) were carried out on a dynamic Rheometrics SR5 Stress rotational rheometer with 25 mm diameter parallel plates in a frequency sweep mode under full nitrogen blanketing. The polymer samples are appropriately stabilized with the anti-oxidant additives and then inserted into the test fixture for at least one minute preheating to ensure the normal force decreasing back to zero. All DMA experiments are conducted at 10% strain, 0.05 to 100 rad / s and 190° C. Orchestrator Software is used to determine the viscoelastic parameters including the storage modulus (G^), loss modulus (G^), phase angle (^), complex modulus (G^) and complex viscosity (^*). The values of storage modulus G^ were estimated at a constant value of loss modulus G^ at 500 Pa at 190° C. (G^ at G^(500 Pa). This is to characterize and discriminate the viscoelastic properties of the comparative and inventive copolymers. This test technique provides an opportunity to study the various characteristics of a polymer melt where the elastic and viscous modulus (G^ and G^), viscosity (^*), and tan ^ as a function of dynamic oscillation (frequency) are generated to provide information on the rheological behavior in correlation with the molecular architecture.

[0117] Gel permeation chromatography (GPC) 4D Methodology: a) Unless otherwise indicated, the distribution and the moments of molecular weight (Mw, Mn, Mz, Mw / Mn, etc.), the comonomer content (C2, C3, C6, etc.), the branching index (g^), and CCDI (Mw-specific, 5-95, and Mn-Mz) are determined by using a high temperature Gel Permeation Chromatography (Polymer Char GPC-IR) equipped with a multiple-channel band- filter based Infrared detector IR5, an 18-angle light scattering detector and a viscometer. Three Agilent PLgel 10-^m Mixed-B LS columns are used to provide polymer separation. Aldrich reagent grade 1,2,4- trichlorobenzene (TCB) with 300 ppm antioxidant butylated hydroxytoluene (BHT) is used as the mobile phase. The TCB mixture is filtered through a 0.1- ^m Teflon filter and degassed with an online degasser before entering the GPC instrument. The nominal flow rate is 1.0 ml / min. and the nominal injection volume is 200 ^l. The whole system including transfer lines, columns, and detectors are contained in an oven maintained at 145°C. Given amount of polymer sample is weighed and sealed in a standard vial with 80-^l flow marker (heptane) added to it. After loading the vial in the autosampler, polymer is automatically dissolved in the instrument with 8 ml added TCB solvent. The polymer isdissolved at l60°C with continuous shaking for about 1 hour for most polyethylene samples or 2 hours for polypropylene samples. The TCB densities used in concentration calculation are 1.463 g / ml at room temperature and 1.284 g / ml at l45°C. The sample solution concentration is from 0.2 to 2.0 mg / ml, with lower concentrations being used for higher molecular weight samples. The concentration (c), at each point in the chromatogram is calculated from the baseline-subtracted IR5 broadband signal intensity (I), using the following equation: c = ^I, where ^ is the mass constant. The mass recovery is calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass which is equal to the pre-determined concentration multiplied by injection loop volume. The conventional molecular weight (IR MW) is determined by combining universal calibration relationship with the column calibration which is performed with a series of monodispersed polystyrene (PS) standards ranging from 700 to 10M g / mole. The MW at each elution volume is calculated with following equation: where the variables withwhile those without a subscript are for the test samples. In this method, ^PS = 0.67 and KPS = 0.000175, while ^ and K for other materials are as calculated and published in literature (Sun, T. et al. Macromolecules 2001, 34, 6812), except that for purposes of this invention and claims thereto, ^ = 0.695 and K = 0.000579 for linear ethylene polymers, ^ = 0.705 and K = 0.0002288 for linear propylene polymers, ^ = 0.695 and K = 0.000181 for linear butene polymers, ^ is 0.695 and K is 0.000579 x (1 - 0.0087 x w2b + 0.0000l8 x (w2b)2) for ethylene-butene copolymer where w2b is a bulk weight percent of butene comonomer, ^ is 0.695 and K is 0.000579 x (l - 0.0075 x w2b) for ethylene-hexene copolymer where w2b is a bulk weight percent of hexene comonomer, and ^ is 0.695 and K is 0.000579 x (l - 0.0077 x w2b) for ethylene-octene copolymer where w2b is a bulk weight percent of octene comonomer. Concentrations are expressed in g / cm3, molecular weight is expressed in g / mole, and intrinsic viscosity (hence K in the Mark-Houwink equation) is expressed in dl / g unless otherwise noted. b) The comonomer composition is determined by the ratio of the IR5 detector intensity corresponding to CH2 and CH3 channel calibrated with a series of PE and PP homo / copolymer standards whose nominal value are predetermined by NMR or FTIR. In particular, this provides the methyls per 1000 total carbons (CH3 / 1000TC) as a function of molecular weight.The short-chain branch (SCB) content per 1000TC (SCB / 1000TC) is then computed as a function of molecular weight by applying a chain-end correction to the CH3 / 1000TC function, assuming each chain to be linear and terminated by a methyl group at each end. The weight % comonomer is then obtained from the following expression in which f is 0.3, 0.4, 0.6, 0.8, and so on for C3, C4, C6, C8, and so on co-monomers, respectively: c) The bulk composition of the polymer from the GPC-IR and GPC-4D analyses is obtained by considering the entire signals of the CH3and CH2channels between the integration limits of the concentration chromatogram. First, the following ratio is obtained d) Then the same calibration of mentioned previously inobtaining the CH3 / 1000TC as a function of molecular weight, is applied to obtain the bulk CH3 / 1000TC. A bulk methyl chain ends per 1000TC (bulk CH3end / l000TC) is obtained by weight- averaging the chain-end correction over the molecular-weight range. Then and bulk SCB / 1000TC is converted to bulk w2 in the same manner as described above. e) The LS detector is the 18-angle Wyatt Technology High Temperature DAWN HELEOSII. The LS molecular weight (M) at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (Light Scattering from Polymer Solutions, Huglin, M. B., Ed.; Academic Press, 1972.):Here, ^R(^) is the measured excessintensity at scattering angle ^, c is the polymer concentration determined from the IR5 analysis, A2 is the second virial coefficient, P(^) is the form factor for a monodisperse random coil, and K0 is the optical constant for the system: where NA is Avogadro’s number,index increment for the system. The refractive index, n=1.500 for TCB at 145°C and ^ = 665 nm. For analyzing polyethylenehomopolymers, ethylene-hexene copolymers, and ethylene-octene copolymers, dn / dc=0.1048 ml / mg and A2 = 0.0015; for analyzing ethylene-butene copolymers, dn / dc=0.1048*(l- 0.00126*w2) ml / mg and A2= 0.0015 where w2 is weight percent butene comonomer. f) A high temperature Agilent (or Viscotek Corporation) viscometer, which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure. The specific viscosity, ^s, for the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity, ^s, at each point in the chromatogram is calculated from the equation [^]= ^s / c, where c is concentration and is determined from the IR5 broadband channel output. The viscosity MW at each point is calculated as M = KPSMaps+1 / [^], where ^ps is 0.67 and Kps is 0.000175. g) The branching index (g^vis) calculated using the output of the GPC-IR5-LS-VIS method as follows. The averageviscosity, [^]avg, of the sample is calculated by: where the summations are over theslices, i, between the integration limits. h) The branching index g^vjsis defined as g^vjs= ([^]avg) / (KMv^), where Mvis the viscosity- average molecular weight based on molecular weights determined by LS analysis and the K and a are for the reference linear polymer, which are, for purposes of this invention and claims thereto, ^ = 0.695 and K = 0.000579 for linear ethylene polymers, ^ = 0.705 and K=0.0002288 for linear propylene polymers, ^ = 0.695 and K=0.000181 for linear butene polymers, ^ = 0.695 and K is 0.000579 x ( l- 0.0087 w2b + 0.0000l8 x (w2b)2) for ethylene-butene copolymer where w2b is a bulk weight percent of butene comonomer, ^ is 0.695 and K is 0.000579*(1 - 0.0075 x w2b) for ethylene-hexene copolymer where w2b is a bulk weight percent of hexene comonomer, and ^ is 0.695 and K is 0.000579*(1 - 0.0077 x w2b) for ethylene-octene copolymer where w2b is a bulk weight percent of octene comonomer. Concentrations are expressed in g / cm3, molecular weight is expressed in g / mole, and intrinsic viscosity (hence K in the Mark- Houwink equation) is expressed in dl / g unless otherwise noted. Calculation of the w2b values is as discussed above.

[0118] High load melt index (g / 10 min. or dg / min.): HLMI, also referred to as I21or I21.6in recognition of the 21.6 kg loading used in the test, was measured according to ASTM D-1238, 190°C, 21.6 kg.

[0119] Melt index (g / 10 min. or dg / min.): MI, also referred to as I2or I2.16in recognition of the 2.16 kg loading used in the test, was measured according to ASTM D-1238, 190°C, 2.16 kg.

[0120] Small angle oscillatory shear (SAOS) frequency sweep melt rheology experiments were performed at 190°C using a 25 mm cone)(1° and plate configuration on a MCR301 controlled strain / stress rheometer (Anton Paar GmbH). Sample test disks (25 mm diameter, 1 mm thickness) were prepared via compression molding of pellets (which where necessary can be made from fiber samples) at 190°C using a Schwaben Than laboratory press (200T). Typical cycle for sample preparation is 1 minute without pressure followed by 1.5 minute under pressure (50 bars) and then cooling during 5 minutes between water cooled plates. The sample was first equilibrated at 190°C for 13 min to erase any prior thermal and crystallization history. An angular frequency sweep was next performed from 500 rad / s to 0.0232 rad / s using 6 points / decade and a strain value of 10% lying in the linear viscoelastic region determined from strain sweep experiments. All experiments were performed in a nitrogen atmosphere to minimize any degradation of the sample during rheological testing.

[0121] Haze is total haze measured according to ASTM D1003; Gloss 60° angle and Gloss 20° angle are both measured in accordance with ASTM D2457; Clarity is measured in accordance with ASTM D1746; the Elmendorf Tear values are both measured in accordance with ASTM D1922;

[0122] “Shrink Force” and “Contracting Force”, reported in Newton (N), are measured using Retramat™ equipment based on ISO 14616. The method consists in exposing 2 film samples to a given temperature, during a given time, and to cool them down at room temperature, simulating what happens inside a shrinkage installation. Retramat equipment is equipped with a heated oven. During the test, one of the samples is connected to a force transducer, while the other is connected to a displacement transducer. A thermocouple provides for following up the temperature at a few millimeters from the middle of the sample. The 3 parameters (force - displacement - temperature) are continuously displayed on the Retramat and recorded on a lab PC. Shrink force is defined as force developed by the film when it reaches the temperature corresponding to that at which the stress was induced at the time of manufacture. Contracting force is defined as force developed bythe film during its cooling process. The conditions for the test are: oven heated at 160°C, oven around the sample for 30 sec. EXAMPLES

[0123] The following examples are included to demonstrate some embodiments of the invention. It should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventor to function well in the practice of the invention, and thus can be considered to constitute preferred modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention. - Experimental materials 1-4 are shown in Table 1 below.TABLE 1 PE Grade Name Density MI Label (g / cm3) (dg / min*) Available from- Examples 1-14

[0125] In Examples 1-14, films having different layer arrangements and formulations were prepared as described in more detail below. In each example, six (6) standard 500 ml cans (66 mm diameter x 168 mm height) were shrink wrapped in a 2x3 pattern in a shrink tunnel under the specified conditions with the bull eye of the packaging on the sides of the pack having 2 cans. The machine direction (MD) of the film as applied to each 6-pack of cans is indicated as “tunnel,” wherein MD was the same as the path of travel through the shrink tunnel or “vertical,” wherein MD was perpendicular to the path of travel through the shrink tunnel. Shrink packaging performance of each example is reported in the tables below.- Examples 1-11

[0126] In comparative Examples 1-11, shrink films were prepared having a thickness of 30 µm and a layer distribution A / B / C of relative thickness 1 / 2 / 1, respectively. The A and C layers were each 50 wt% PE1 and 50 wt% PE4. The B layer was 40 wt% PE4, 45 wt% HDPE1, and 15 wt% LDPE1. Test conditions and shrink performance for Examples 1-11 are reported in Table 2 below. TABLE 2 Shrink Thick- Film Ex. ness Width Film MD Tunnel Shrink performance No direction Tem- Example 12

[0127] In comparative Example 12, a shrink film was prepared having a thickness of 50 µm and a layer distribution A / B / C of relative thickness 1 / 2 / 1, respectively. The A and C layers were each 100 wt% PE2. The B layer was 60 wt% PE2 and 40 wt% PE4. Test conditions and shrink performance for Example 12 are reported in Table 3 below. TABLE 3 Shrink E Thick- Film Fil MD T l- Example 13 and 14

[0128] In inventive 13 and 14, shrink films were prepared having a thickness of 30A / B / C / D / E of relative thickness 1 / 1 / 10 / 1 / 1, respectively, a MD stretch ratio of about 4.5:1 to 5.0:1, and a TD stretch ratio of about 8.5:1 to 9.5:1. The A and E layers were each 98 wt% PE3 and 2 wt% AB1. The B and D layers were each 100 wt% PE3. The C layer was 85 wt% PE6 and 15 wt% HDPE2. Test conditions and shrink performance for Examples 13 and 14 are reported in Table 4 below. TABLE 4 Shrink Ex. Thick- Film Film MD Tunnel ness Width1Shrink performance15-17, films having different compositions were compared for shrink performance. Inventive Example 15 was a biaxial oriented polyethylene shrink film (BOPE) as disclosed herein. Comparative Example 16 was a conventional collation shrink film (CS). Comparative Example 17 was a low density polyethylene collation shrink film (LDPE). Inventive Example 15 demonstrated a shrink force of 1,346 mN at 165°C. The shrink force of inventive Example 15 was a factor of nearly 50 times greater than the shrink force in comparative Example 16, which was achieved at temperature of 210°C, 45°C higher than the temperature for Example 15. The shrink force of inventive Example 15 was a factor of approximately 10 times greater than the shrink force in comparative Example 17, which was achieved at temperature of 195°C, 30°C higher than the temperature for Example 15. This is shown graphically in FIG. 1, showing the Retramat™ traces of shrink force versus time, wherein maximum shrink force was achieved for each type of film at temperatures as disclosed above. In FIG. 1, the four traces indicated as Ex.15 represent four experiments performed using the film of Example 15; the two traces indicated as Ex.16 were represent two experiments performed using the film of Example 16; and the single trace indicated as Ex. 17 represents a single experiment performed using the film of Example 17. Table 5 discloses the shrink temperature (already described above, but not shown in the FIG. 1 trace); as well as the quantitative load measurements apparent from the Retramat™ traces obtained in FIG. 1 (shrink force, illustrated by the initial peak in the Load value on the Retramat™ trace, in this case obtained around 20-30 sec for each film; and holding force, illustrated by the lowest load force in the stabilized region of approximately constant value load in the Retramat™ trace).

[0130] Based on this testing data, the shrink force of the biaxially oriented polyethylene films disclosed herein (Ex.15) is much higher than both conventional collation shrink film (Ex.16) and LDPE film (Ex. 17). Furthermore, shrink temperature of the biaxially oriented polyethylene films disclosed herein is much is lower than both conventional CS film and LDPE film. Holding force is not critical in these experiments as it can be controlled by adjusting by film gauge and / or film formulation, as is known to those skilled in the art. Rather, the key findings of these experiments are in the substantially greater shrink force obtained with the BOPE film (Ex. 15) and particularly in the lower shrink temperature of Ex. 15 as compared to the others. Such a film having lower shrink temperature can provide many advantages owing to reduced stickiness of the film when obtaining shrinkage for packaging (because higher temperatures, which could induce stickiness, can be avoided with such lower shrink temperature, while still obtaining the desired shrink wrap effect). TABLE 5 Retramat™ Test Conditions and Results Ex.15 Ex.16 Ex.17 Film type BOPE Conv CS LDPE

[0131] Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims. Ranges for various characteristics and attributes disclosed herein are listed as sequentially narrowing ranges. However, it should be understood that any lower endpoint of any ranges can be paired with any upper endpoint for the same characteristic or attribute, and such pairings arealso intended to be disclosed herein. All patents, test procedures, and other documents cited in this application are fully incorporated herein by reference for all jurisdictions in which such incorporation is permitted. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the processes, machines, means, methods, and / or steps described in the specification. As one of the ordinary skill in the art will readily appreciate from the disclosure of the present invention, processes, machines, means, methods, and / or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein, may be utilized according to the present invention. Accordingly, the appended claims are intended to include within their scope such processes, machines, means, methods, and / or steps.

Claims

CLAIMS What is claimed is:

1. A multilayer film comprising at least a first outer layer, a second outer layer, and a core layer disposed between the first outer layer and the second outer layer, the core layer comprising a first polymer composition, the first polymer composition comprising at least 50 wt% of a first metallocene linear low density polyethylene (mLLDPE), based on the weight of the first polymer composition, wherein: a) the first mLLDPE comprises from 80 wt% to 99 wt% ethylene derived units and 1 wt% to 20 wt% units derived from one or more C3 to C20 ^-olefins, based on the weight ofii) a composition distribution breadth index (CDBI) less than or equal to 40%; iii) a melt index (I2) in the range of from 0.1 g / 10 min to 5.0 g / 10 min; and b)outer layer comprises a third polymer composition, wherein the second and third polymer compositions are the same or different and each independently comprises: i) a narrow-CD mLLDPE, having a CDBI greater than or equal to 50% and a melt index (I2) greater than or equal to 1.2 dg / min.; ii) a long chain branched (LCB) mLLDPE, having a CDBI greater than or equal to 60% and a melt index (I2) less than 1.2 dg / min.; iii) a high density polyethylene (HDPE); or iv) a combination thereof; and c) the multilayer film is biaxially oriented.

2. The multilayer film of claim 0, wherein the broad orthogonal comonomer distribution of the first mLLDPE is illustrated by the first mLLDPE having at least a first peak and a second peak in a comonomer distribution analysis, wherein the first peak has a maximum at a log(Mw) value of from 4.0 to 5.4 and a temperature rising elution fractionation (TREF) elution temperature of from 70.0°C to 100.0°C, and the second peak in the comonomer distribution analysis has a maximum at a log(Mw) value of 5.0 to 6.0 and a TREF elution temperature of 40.0°C to 60.0°C.

3. The multilayer film of claim 0 or claim 2, wherein the broad orthogonal comonomer distribution of the first mLLDPE is illustrated by the first mLLDPE having a T75−T25 value in the range of from 5 to 10, wherein T25 is the temperature in degrees Celsius at which 25% of the first mLLDPE is eluted, and T75is the temperature in degrees Celsius at which 75% of the first mLLDPE is eluted, via temperature rising elution fractionation (TREF).

4. The multilayer film of claim 0 or any one of claims 2-3, wherein the first polymer composition further comprises: a) a narrow-CD mLLDPE, having a CDBI greater than or equal to 50% and a melt index (I2) greater than or equal to 1.2 dg / min.; b) a long chain branched (LCB) mLLDPE, having a CDBI greater than or equal to 60% and a melt index (I2) less than 1.2 dg / min.; c) a high density polyethylene (HDPE); or d) a combination thereof.

5. The multilayer film of claim 0 or any one of claims 2-4, wherein the multilayer film is free of low density polyethylene.

6. The multilayer film of claim 0 or any one of claims 2-5, wherein the multilayer film has a thickness less than or equal to 250 µm.

7. The multilayer film of claim 0 or any one of claims 2-6, wherein the thickness of the core layer is in the range of from 25% to 90% of the total thickness of the multilayer film.

8. The multilayer film of claim 0 or any one of claims 2-7, wherein the biaxial orientation comprises a machine direction (MD) orientation stretch ratio in a range of from 2.0:1 to 7.5:1 and a transverse direction (TD) orientation stretch ratio in a range of from 6.5:1 to 11.5:

1.

9. The multilayer film of claim 0 or any one of claims 2-8, wherein the film has one or more of: a) a machine direction (MD) shrinking force in a range of from 700 mN to 1,400 mN; b) a normalized machine direction (MD) shrinking force in a range of from 23.3 mN / µm to 46.7 mN / µm;c) a transverse direction (TD) shrinking force in a range of from 700 mN to 1,400 mN; and d) a normalized transverse direction (TD) shrinking force in a range of from 23.3 mN / µm to 46.7 mN / µm.

10. The multilayer film of claim 0 or any one of claims 2-9, wherein the film has a shrink temperature in the range of from 120°C to 170°C.

11. The multilayer film of claim 0 or any one of claims 2-10, wherein the first polymer composition comprises the first mLLDPE in an amount in the range of from 50 wt% to 95 wt% and a HDPE in an amount in the range of from 5 wt% to 50 wt%, based on the total weight of the first polymer composition.

12. The multilayer film of claim 0 or any one of claims 2-11, wherein the first outer layer and the second outer layer each independently comprise a narrow-CD mLLDPE in an amount greater than or equal to 50 wt%, based on the total weight of the first outer layer and the second outer layer, respectively.

13. The multilayer film of claim 0 or any one of claims 2-12, wherein the first outer layer and / or the second outer layer each independently comprise an antiblock additive.

14. A process for collation shrink packaging, the process comprising: a) arranging two or more items adjacent to one another in one or more rows of two or more items each to form a collated bundle, wherein a cartesian coordinate system is defined by a first horizontal axis parallel to the one or more rows, a second horizontal axis perpendicular to the one or more rows, and a vertical axis; b) wrapping the collated bundle in a multilayer film at a temperature in the range of from 10°C to 40°C to form a wrapped bundle, wherein: i) the multilayer film forms a tube encasing the collated bundle items; ii) the tube has a first opening at one end of the bundle and a second opening at the opposite end of the bundle; and iii) the tube is oriented such that the central axis of the tube is parallel to the first horizontal axis, the second horizontal axis, or the vertical axis;c) heating the wrapped bundle to a temperature sufficient to shrink the tube to conform to the outermost surfaces of the collated bundle to form a shrink wrapped bundle; wherein the multilayer film comprises at least a first outer layer, a second outer layer, and a core layer disposed between the first outer layer and the second outer layer, the core layer comprising a first polymer composition, the first polymer composition comprising at least 50 wt% of a first metallocene linear low density polyethylene (mLLDPE) and optionally up to 50 wt% of a second polymer composition, based on the weight of the first polymer composition, wherein: i) the first mLLDPE comprises from 80 wt% to 99 wt% ethylene derived units and 1 wt% to 20 wt% units derived from one or more C3to C20^-olefins, based on the weight of the first mLLDPE, and has: (1) a density in the range of from 0.900 g / cm3to 0.940 g / cm3; (2) a composition distribution breadth index (CDBI) less than or equal to 40%; (3) a melt index (I2) in the range of from 0.1 g / 10 min to 5.0 g / 10 min; and (4) a broad orthogonal comonomer distribution; ii) the first outer layer comprises a second polymer composition, and the second outer layer comprises a third polymer composition, wherein the second and third polymer compositions are the same or different and each independently comprises: (1) a narrow-CD mLLDPE, having a CDBI greater than or equal to 50% and a melt index (I2) greater than or equal to 1.2 dg / min.; (2) a long chain branched (LCB) mLLDPE, having a CDBI greater than or equal to 60% and a melt index (I2) less than 1.2 dg / min.; (3) a high density polyethylene (HDPE); or (4) a combination thereof; and iii) the film is biaxially oriented.

15. The process of claim 0, wherein the first polymer composition further comprises: a) a narrow-CD mLLDPE, having a CDBI greater than or equal to 50% and a melt index (I2) greater than or equal to 1.2 dg / min.; b) a long chain branched (LCB) mLLDPE, having a CDBI greater than or equal to 60% and a melt index (I2) less than 1.2 dg / min.;c) a high density polyethylene (HDPE); or d) a combination thereof.

16. The process of claim 0 or claim 15, wherein the first opening and the second opening are each reduced to a substantially circular opening having a maximum diameter less than the minimum dimension of a shape defined by the outer perimeter of the collated bundle projected onto a plane perpendicular to the central axis.

17. The process of claim 0 or any one of claims 15-16, wherein the temperature sufficient to shrink the tube is in the range of from 120°C to 170°C.

18. The process of claim 0 or any one of claims 15-17, wherein the wrapping of the collated bundle is performed such that the machine direction of the film is perpendicular to the central axis of the tube.

19. The process of claim 0 or any one of claims 15-18, wherein the first polymer composition comprises the first mLLDPE in an amount in the range of from 50 wt% to 95 wt% and a HDPE in an amount in the range of from 5 wt% to 50 wt%, based on the total weight of the first polymer composition..

20. The process of claim 0 or any one of claims 15-19, wherein the first outer layer and the second outer layer each independently comprise a narrow-CD mLLDPE in an amount greater than or equal to 50 wt%, based on the total weight of the first outer layer and the second outer layer, respectively.

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