Longitudinal oriented polyethylene films for labels and related methods

Abstract

The longitudinally oriented polyethylene film can be used as a facestock material for labels. The non-restrictive alignment film may include: a first layer comprising a long chain branched metallocene linear low density polyethylene (LCB-mLLDPE); a second layer comprising high density polyethylene; a third layer comprising from 0 wt% to about 90 wt% of a metallocene linear low density polyethylene (mLLDPE) and from about 10 wt% to 100 wt% of an ethylene-based elastomer and / or a propylene-based elastomer, wherein the third layer does not form a surface of the alignment film; wherein the alignment film has a polyethylene content of about 90 wt% or more; and wherein the alignment film has a uniaxial longitudinal orientation.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 366,349, filed on June 14, 2022, entitled “MACHINE DIRECTION ORIENTED POLYETHYLENE FILMS FOR LABELS AND RELATED METHODS,” the entire contents of which are incorporated herein by reference. Field of the Invention

[0003] The present application relates to polyethylene films suitable for use as facestock materials for labels and methods of producing the same.

[0004] background

[0005] In many label applications, it is desirable to cut the facestock of the label from a polymer material film rather than paper. Polymer films can provide properties that paper lacks, such as durability, strength, water resistance, abrasion resistance, gloss, transparency, and other properties.

[0006] The polymer film used to produce the label facestock should have enough "give" or flexibility to conform well to the substrate or container on which the label is applied (a particularly demanding requirement when the label is applied to flexible substrates such as compressible plastic containers, such as shampoo bottles and condiment containers, and for rigid substrates such as glass bottles that may have irregular shapes on their surfaces). On the other hand, the labels cut from the film should be dimensionally stable enough to maintain print registration, and have sufficient stiffness to allow them to be properly dispensed as in-mold labels, or over a peel plate or peel trailing edge, on which the liner or carrier is peeled off at a speed high enough to be commercially viable.

[0007] Polyethylene is a commonly used polymer in facestock materials for labels, especially in household personal care and chemical bottles, due to its consistency and environmental resistance. Currently, the market is turning to seek thinner label solutions, which is partly driven by sustainability. The commonly commercially available thickness of polyethylene films used as facestock for labels is about 80 μm to about 85 μm. Attempts to reduce film thickness have further shown to reduce the stiffness properties of the facestock, which may result in poor cutting ability or dimensional stability during subsequent conversion processes. SUMMARY OF THE INVENTION

[0009] The present application relates to polyethylene films suitable for use as facestock materials for labels and methods of producing the same.

[0010] A non-limiting example method of the present disclosure includes: blowing a film comprising a first layer, a second layer, and a third layer, wherein the first layer comprises a long-chain branched metallocene linear low density polyethylene (LCB-mLLDPE), wherein the second layer comprises a high density polyethylene, and wherein the third layer comprises 0 wt % to about 90 wt % of a metallocene linear low density polyethylene (mLLDPE) and about 10 wt % to 100 wt % of an ethylene-based elastomer and / or a propylene-based elastomer; blocking the film using the third layer as a blocking layer to produce a blocking film; and orienting the blocking film in a machine direction to produce an oriented film, wherein the oriented film has a polyethylene content of about 90 wt % or greater.

[0011] A non-limiting example oriented film of the present disclosure comprises: a first layer comprising long chain branched metallocene linear low density polyethylene (LCB-mLLDPE); a second layer comprising high density polyethylene; a third layer comprising 0 wt % to about 90 wt % of a metallocene linear low density polyethylene (mLLDPE) and about 10 wt % to 100 wt % of an ethylene-based elastomer and / or a propylene-based elastomer, wherein the third layer does not form a surface of the oriented film; wherein the oriented film has a polyethylene content of about 90 wt % or greater; and wherein the oriented film has a uniaxial longitudinal orientation.

[0012] A non-limiting example method of the present disclosure includes: blowing a film comprising a first layer and a second layer, wherein the first layer comprises a long-chain branched metallocene linear low-density polyethylene (LCB-mLLDPE) and / or a high-density polyethylene, and wherein the second layer comprises 0 wt % to about 90 wt % of a metallocene linear low-density polyethylene (mLLDPE) and about 10 wt % to 100 wt % of an ethylene-based elastomer and / or a propylene-based elastomer; bonding the film using the second layer as a bonding layer to produce a bonding film; and orienting the bonding film in a machine direction to produce an oriented film, wherein the oriented film has a polyethylene content of about 90 wt % or greater.

[0013] A non-limiting example oriented film of the present disclosure comprises: a first layer comprising long chain branched metallocene linear low density polyethylene (LCB-mLLDPE) and / or high density polyethylene; a second layer comprising 0 wt % to about 90 wt % of a metallocene linear low density polyethylene (mLLDPE) and about 10 wt % to 100 wt % of an ethylene-based elastomer and / or a propylene-based elastomer, wherein the second layer does not form a surface of the oriented film; wherein the oriented film has a polyethylene content of about 90 wt % or greater; and wherein the oriented film has a uniaxial longitudinal orientation.

[0014] These and other features and properties of the disclosed compositions and methods of the present disclosure and their advantageous applications and / or uses will be apparent from the following detailed description.

[0015] BRIEF DESCRIPTION OF THE DRAWINGS

[0016] To aid those of ordinary skill in the relevant art in making and using the subject matter herein, reference is made to the accompanying drawings. The following drawings are included to illustrate certain aspects of the present disclosure and should not be construed as an exclusive configuration. The disclosed subject matter is capable of significant modifications, alterations, combinations, and equivalences in form and function as will occur to those of ordinary skill in the art having the benefit of the present disclosure.

[0017] Figure 1A Non-limiting examples illustrating the methods of the present disclosure.

[0018] Figure 1B-1D Description and Figure 1A Non-limiting example film compositions corresponding to the methods.

[0019] 2 is a graph illustrating VGP (Van Gurp Palmen) curves for certain commercial examples of suitable metallocene-catalyzed LLDPEs having some long chain branching as described herein.

[0020] Details

[0021] The present application relates to polyethylene films suitable for use as facestock materials for labels and methods for producing the same. More specifically, the methods of the present disclosure include blowing and bonding methods to produce thicker multilayer films, which can then be uniaxially oriented in the machine direction (e.g., by stretching). The resulting oriented film (which can be 70 μm thick or less) can be used to produce labels.

[0022] By using layers, each layer can improve the desired properties of the final label product. In addition, uniaxial orientation can enhance at least some mechanical properties, which can allow the production of low film thickness labels with improved properties.

[0023] Furthermore, the compositions and methods of the present disclosure produce oriented films with improved optical properties, such as higher clarity and lower haze.

[0024] Definition and test methods

[0025] Unless otherwise indicated, room temperature is 25°C.

[0026] "Olfin" or "alkene" is a linear, branched or cyclic carbon and hydrogen compound having at least one double bond.

[0027] "Polymer" has two or more identical or different monomer (mer) units. "Homopolymer" is a polymer having identical monomer units. The term "polymer" as used herein includes, but is not limited to, homopolymers, copolymers, terpolymers, etc. The term "polymer" as used herein also includes impact, block, graft, random and alternating copolymers. Unless otherwise specifically stated, the term "polymer" shall also include all possible geometric configurations. Such configurations may include isotactic, syndiotactic and random symmetries.

[0028] As used herein, unless otherwise specified, the term "copolymer(s)" refers to a polymer formed by the polymerization of at least two different monomers (i.e., monomer units). For example, the term "copolymer" includes copolymerization products of propylene and α-olefins such as ethylene, 1-hexene. A "terpolymer" is a polymer having three monomer units that are different from each other. Thus, the term "copolymer" also includes terpolymers and tetrapolymers such as copolymer products of a mixture of ethylene, propylene, 1-hexene, and 1-octene.

[0029] "Different" as used to refer to monomeric monomeric units means that the monomeric units differ from each other by at least one atom or are isomerically different. An "ethylene polymer" or "ethylene copolymer" is a polymer or copolymer comprising at least 50 mole % ethylene derived units, a "propylene polymer" or "propylene copolymer" is a polymer or copolymer comprising at least 50 mole % propylene derived units, and so forth. For purposes of the present disclosure, polyethylene and ethylene polymers are referred to herein as "polyethylene" and "ethylene copolymers".

[0030] As used herein, when a polymer is referred to as "comprising, consisting of, or consisting essentially of a monomer," the monomer is present in the polymer in the polymerized / derivative form of the monomer. For example, when a copolymer is said to have an "ethylene" content of 35 wt% to 55 wt%, it is understood that the monomer units in the copolymer are derived from ethylene in the polymerization reaction, and the derived units are present at 35 wt% to 55 wt% based on the weight of the copolymer.

[0031] In g / cm 3 The density reported is determined according to ASTM D792-20 (plasters are molded according to ASTM D4703-10a, Procedure C, Plaque Preparation, including conditioning the plaques at 23°C for at least 40 hours to approach equilibrium crystallinity). Briefly, the mass of a sample of solid plastic is measured in air. The sample is then immersed in a liquid, in which the apparent mass of the sample while immersed is determined and the specific gravity (relative density) is calculated.

[0032] As used herein, Mn is the number average molecular weight, Mw is the weight average molecular weight, and Mz is the z-average molecular weight. Molecular weight distribution (MWD) is defined as Mw divided by Mn. Unless otherwise indicated, all molecular weights (e.g., Mw, Mn, Mz) are reported in g / mol.

[0033] For polyethylene compositions, molecular weight values ​​were determined by using high temperature gel permeation chromatography (Polymer Char GPC-IR) equipped with an infrared detector IR5, an 18-angle light scattering detector and a viscometer based on a multi-channel bandpass filter. Three Agilent PLgel 10 μm mixed-B LS columns were used to provide polymer separation. The detailed analysis principle and molecular weight determination method and g'(vis) are described in paragraphs

[0044] -

[0051] of PCT Publication WO2019 / 246069A1, which is incorporated herein by reference (note that the equation c= / / / mentioned in paragraph

[0044] about the concentration (c) at each point in the chromatogram is c=βI, where β is a mass constant and I is the IR5 broadband signal intensity (I) minus the baseline). Unless specifically mentioned, all molecular weight moments used or referred to in this disclosure are determined according to conventional molecular weight (IR molecular weight) determination methods (such as those mentioned in paragraphs

[0044] -

[0045] of the just-mentioned publication), noting that for the equation in such paragraph

[0044] , a=0.695 and K=0.000579 (1-0.75Wt) are used, where Wt is the weight fraction of the comonomer, and further noting that the comonomer composition is determined by the ratio of the IR5 detector intensities corresponding to the CH2 and CH3 channels calibrated with a series of PE and PP homo / copolymer standards, the nominal values ​​of which are predetermined by NMR or FTIR as indicated in paragraph

[0045] of the just-mentioned PCT publication (providing methyls / 1000 total carbons (CH3 / 1000TC)). Other parameters required can be found in the paragraphs mentioned in the WO2019 / 246069A1 disclosure, but for convenience some are included here: 1,2,4 trichlorobenzene (TCB) at 145°C n = 1.500; I = 665nm; dn / dc = 0.1048ml / mg.

[0034] For the polypropylene elastomer composition, the molecular weight values ​​were determined using a high temperature size exclusion chromatograph (SEC) (either from Waters Corporation or from Polymer Laboratories) equipped with a differential refractive index detector (DRI), an online light scattering (LS) detector and a viscometer. Three Polymer Laboratories PLgel 10 mm mixed-B columns were used. The nominal flow rate was 0.5 cm 3 / min, and the nominal injection volume is 300 μL. Various transfer lines, columns and differential refractometers (DRI detectors) are accommodated in an oven maintained at 145°C. Polystyrene is used to calibrate the instrument. The solvent for SEC experiments is prepared by dissolving 6 g of butylated hydroxytoluene as an antioxidant in 4 L of Aldrich reagent grade TCB. The TCB mixture is then filtered through a 0.7 μm glass prefilter and subsequently through a 0.1 μm Teflon filter. The TCB is then degassed with an online degasser before entering SEC. By placing the dry polymer in a glass container, adding the required amount of TCB, then heating the mixture at 160°C and continuously stirring for several hours to prepare the polymer solution. All amounts are measured by gravimetric analysis. The TCB density used to represent the polymer concentration in mass / volume units is 1.463 g / mL at room temperature and 1.324 g / mL at 135°C. The injection concentration range is 1.0 mg / mL-2.0 mg / mL, with lower concentrations used for higher molecular weight samples. Before running each sample, the DRI detector and injector were purged. The flow rate in the instrument was then increased to 0.5 mL / min, and the DRI was allowed to stabilize for 8-9 hours before injecting the first sample. The LS laser was turned on 1 hour to 1.5 hours before running the sample. The concentration c at each point in the chromatogram was calculated from the baseline-subtracted DRI signal IDRI using the following equation:

[0035] c=K DRI I DRI / (dn / dc)

[0036] Where K DRI is the constant determined by calibration of the DRI, and dn / dc is the same as described below for LS analysis. Throughout this description of the SEC method the units of parameters are as follows: concentration is in g / cm 3 The molecular weight is expressed in kg / mol and the intrinsic viscosity is expressed in dL / g.

[0037] The light scattering detector used was a Wyatt Technology High Temperature mini-DAWN. The molecular weight (M) at each point in the chromatogram was determined by analyzing the LS output using the Zimm model for static light scattering (MB Huglin, Light Scattering from Polymer Solutions, Academic Press, 1971):

[0038]

[0039] where ΔR(θ) is the excess Rayleigh scattering intensity measured at the scattering angle θ, c is the polymer concentration determined from the DRI analysis, A2 is the second virial coefficient, P(θ) is the shape factor of the monodisperse random coil (described in the reference above), and K o is the optical constant of the system:

[0040]

[0041] Where N A is Avogadro's constant, and dn / dc is the refractive index increment of the system. The refractive index of TCB at 135°C and λ=690nm is n=1.500. In addition, for ethylene polymers A2=0.0015 and dn / dc=0.104, while for propylene polymers A2=0.0006 and dn / dc=0.104. n / d c =0.104.

[0042] Molecular weight averages are usually defined by taking into account the discontinuous nature of the distribution, where the macromolecules are represented by the number of molecules containing N i Molecular weight M i The weight average molecular weight M W Defined as the molecular weight of each part M i Multiply by its weight fraction w i : The sum of the products of:

[0043]

[0044] Because the weight fraction w i : defined as having a molecular weight M i The weight of the molecule divided by the total weight of all molecules present:

[0045]

[0046] Number average molecular weight M n Defined as the molecular weight of each part M i Multiply by its mole fraction x i The sum of the products of :

[0047]

[0048] Since the mole fraction x i Defined as N i Divide by the total number of molecules:

[0049]

[0050] In SEC, a high temperature Viscotek Corporation viscometer is used, which has four capillaries arranged in a Wheatstone bridge configuration and two pressure sensors. One sensor measures the total pressure drop across the detector, and the other sensor placed between the two sides of the bridge measures the pressure difference. The specific viscosity ηs of the solution flowing through the viscometer is calculated from their output. The intrinsic viscosity [η] at each point in the chromatogram is calculated by the following equation:

[0051] η s =c[η]+0.3(c[η]) 2

[0052] where c is determined by the DRI output.

[0053] The output of the SEC-DRI-LS-VIS method was used to calculate the branching index (g' also referred to as g'(vis)) as follows: Average intrinsic viscosity [η] of the sample avg By the following calculation:

[0054]

[0055] where the sum is taken over all chromatographic slices i between the integration limits.

[0056] The DSC run was set up using a PerkinElmer DSC 8000. The peak melting point or melting temperature (T) was determined using the following DSC program: m ), peak crystallization temperature or crystallization temperature (T c ) and heat of fusion or heat flow (ΔH f or H f ). A sample weighing about 5 mg was carefully sealed in an aluminum airtight pan. The heat flow was normalized by the sample mass. The material was kept at -20°C for 5 min and then the material was heated from -20°C to 200°C at 10°C / min. After equilibrium (3 min at 200°C), the sample was cooled to -20°C at 10°C / min and equilibrated for 5 min. After measuring T c After a cooling process, a second melting process is performed to determine Tm. The material is once again heated from -20°C to 200°C at 10°C / min. The melting (Tm) is calculated by integrating the peak position over the temperature range that completely includes the peak (baseline). m ) and crystallization (T c )Peak temperature.

[0057] Melt flow index (MFI) was measured on a Goetfert MI-4 melt indexer according to ASTM 1238-13. Test conditions were set at 190°C and 2.16 kg load for polyethylene and at 230°C and 2.16 kg load for polypropylene (unless otherwise specified). A sample of 5 to 6 g was loaded into the instrument barrel at 190°C and compressed manually. Thereafter, the material was automatically compacted in the barrel by lowering all available weight onto the piston to remove all air bubbles. Data acquisition was started after a 6 min pre-melt time. In addition, the sample was pressed through a die of 8 mm length and 2.095 mm diameter.

[0058] The Vicat softening temperature can be measured according to ASTM D152517-e1.

[0059] As used herein, the terms "machine direction" and "MD" refer to the direction of orientation (or stretching) in the plane of the film.

[0060] As used herein, the terms "transverse direction" and "TD" refer to the perpendicular direction in the plane of the film relative to the MD.

[0061] The film thickness (or thickness) of the film shall be determined by ASTM D6988-13 and expressed in μm unless otherwise specified.

[0062] Transparency can be measured by ASTM D1476-09.

[0063] Haze can be measured by ASTM D1003-13.

[0064] Gloss can be measured by ASTM D2457-13.

[0065] The bending stiffness coefficient can be determined by DIN 53121:2014-08.

[0066] The longitudinal force at 1% strain, longitudinal force at break, and longitudinal elongation can be determined by ASTM D882-18.

[0067] Membranes and related methods

[0068] The films of the present disclosure can be prepared by blowing multilayer films, blocking multilayer films, and orienting multilayer films in the machine direction.

[0069] Figure 1A A non-limiting example of a method 100 of the present disclosure is illustrated, and Figure 1B-1DA non-limiting example film composition corresponding to method 100 is described. Method 100 includes blowing 102 a film 104 including a first layer 120, a second layer 122, and a third layer 124, wherein the first, second, and third layers 120, 122, and 124 have different compositions. The film 104 is then blocked 106 such that the third layer 124 adheres to itself to produce a blocked film 108 having a structure in the following order: first layer 120, second layer 122, third layer 124' (i.e., a third layer 124 blocked to another third layer 124), second layer 122, and first layer 120. The blocked film 108 is then uniaxially oriented 110 in the machine direction (MD) to produce a machine direction oriented (MDO) film 112, wherein each layer 120, 122, and 124' of the blocked film 108 is thinner than its thinner layers 120", 122", and 124", such as in Figure 1C As described in .

[0070] Figures 1A-1D The method 100 and structures 104, 108 and 112 can be adapted for films having other numbers of layers, including films having 2 to 10 layers (or 2 to 5 layers, or 4 to 10 layers) after the blowing process, which produce films having 3 to 19 layers (or 3 to 9 layers, or 7 to 19 layers) after the blocking and orientation process.

[0071] The layer of the blown film that is stuck together (also referred to herein as "blocking layer") can comprise 0 wt % to about 90 wt % of metallocene linear low density polyethylene (mLLDPE) and about 10 wt % to 100 wt % of an elastomer based on ethylene and / or an elastomer based on propylene. Advantageously, low-density elastomers can provide adhesion in the blocking process. Preferably, the blocking layer is substantially free of components other than mLLDPE and / or an elastomer based on propylene, and especially polymer components--that is, the blocking layer can be composed of mLLDPE and / or an elastomer based on propylene or is substantially composed of mLLDPE and / or an elastomer based on propylene (wherein "substantially composed of..." allows additives or impurities, including polymer additives, as long as they are used in a small amount (e.g., 5 wt % or less, preferably 1 wt % or less, more preferably 0.5 wt % or less, based on the quality of the layer) common to additives). In certain embodiments, the blocking layer is completely devoid of polymer components other than mLLDPE and / or propylene-based elastomers; and optionally, the blocking layer may be composed of mLLDPE and / or propylene-based elastomers, such that such layer is devoid of other polymer components and additives.

[0072] Those layers that are not layers that experience blocking (also referred to herein as "non-blocking layers") may comprise long-chain branched metallocene linear low-density polyethylene (LCB-mLLDPE) and / or high-density polyethylene. Preferably, one or more of the layers that are not layers that experience blocking comprise, consist of or consist essentially of LCB-mLLDPE and / or high-density polyethylene (again, where "consisting essentially of" allows for impurities in the order of 1,000 ppm or less, preferably 100 ppm or less, for example 10 ppm or less; and optional additives in the order of 5 wt% or less, preferably 1 wt% or less, preferably 0.5 wt% or less; the ppm and wt% are based on the mass of the layer in question). By way of non-limiting example, Figure 1D The following may be included: a first layer 120" comprising (or consisting of or consisting essentially of) LCB-mLLDPE, a second layer 122" comprising (or consisting of or consisting essentially of) high-density polyethylene, and a third layer 124" comprising (or consisting of or consisting essentially of) 0 wt% to about 90 wt% of a metallocene linear low-density polyethylene (mLLDPE) and (or consisting of or consisting essentially of) about 10 wt% to 100 wt% of an ethylene-based elastomer and / or a propylene-based elastomer. In another non-limiting example, Figure 1D The following may be included: a first layer 120" comprising (or consisting of or consisting essentially of) high-density polyethylene, a second layer 122" comprising (or consisting of or consisting essentially of) LCB-mLLDPE, and a third layer 124" comprising (or consisting of or consisting essentially of) 0 wt% to about 90 wt% mLLDPE and about 10 wt% to 100 wt% propylene-based elastomer. In yet another non-limiting example, Figure 1D The following may be included: a first layer 120" comprising (or consisting of or consisting essentially of) a blend of LCB-mLLDPE and high-density polyethylene, a second layer 122" comprising (or consisting of or consisting essentially of LCB-mLLDPE) LCB-mLLDPE, and a third layer 124" comprising (or consisting of or consisting essentially of) 0 wt% to about 90 wt% of a metallocene linear low-density polyethylene (mLLDPE) and about 10 wt% to 100 wt% of an ethylene-based elastomer and / or a propylene-based elastomer. In another non-limiting example, Figure 1DIt may include a first layer 120" comprising (or consisting of or consisting essentially of) LCB-mLLDPE, a second layer 122" comprising (or consisting of or consisting essentially of) a blend of LCB-mLLDPE and high-density polyethylene, and a third layer 124" comprising (or consisting of or consisting essentially of) 0 wt% to about 90 wt% of a metallocene linear low-density polyethylene (mLLDPE) and about 10 wt% to 100 wt% of an ethylene-based elastomer and / or a propylene-based elastomer. The composition of the surface non-blocking layer (e.g., the first layer 120 of FIG. 1 ) after the film is blown may be selected to allow effective printing thereon after the orientation process.

[0073] Without being bound by theory, it is believed that including a layer comprising (or consisting of, or consisting essentially of) LCB-mLLDPE and / or high density polyethylene imparts strength and stiffness to the blocking film. MD orientation of the blocking film then reduces the film thickness to a desired thickness and can further improve the mechanical properties of the film while maintaining the desired optical properties of the film.

[0074] It is pointed out above that the blocking film can contain 0 to 90 weight % mLLDPE and 10 to 100 weight % ethylene-based elastomer and / or propylene-based elastomer; however, in various embodiments herein, different endpoints of each of these ranges of each component are contemplated (i.e., different relative blending amounts). For example, the blocking layer can contain (or consist of, or consist essentially of):

[0075] mLLDPE ranges from a low of any of 0, 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, or 80 wt % to a high of any of 10, 20, 25, 30, 40, 50, 60, 70, 75, 80, 85, or 90 wt %, wherein ranges from any of the aforementioned lower ends to any of the aforementioned upper ends are contemplated herein with the proviso that the upper end is greater than the lower end (e.g., 0 to 90 such as 0 to 50 wt %, or 25 to 75 wt %, or 50 to 80 wt %, or 70 to 90 wt %, etc.); and

[0076] · Ethylene-based and / or propylene-based elastomers in a range from a low of any of about 10, 15, 20, 25, 30, 40, 50, 60, 70, 75, 80, or 90 weight percent to a high of any of about 20, 30, 40, 50, 60, 70, 75, 80, 85, 90, 95, 96, 97, 98, 99, or 100 weight percent, again wherein ranges from any of the foregoing low points to any of the foregoing high points are encompassed (provided that the upper end is greater than the lower end), e.g., 10 to 100 weight percent, or 50 to 100 weight percent, or 25 to 75 weight percent, 20 to 50 weight percent, or 10 to 30 weight percent, etc. Preferably, when a propylene-based elastomer is used, the propylene-based elastomer is present in no greater than about 50 wt % (or about 5 wt % to about 50 wt %, or about 5 wt % to about 30 wt %, or about 20 wt % to about 50 wt %) of the blocking layer (or any other range among those disclosed above, up to 50 wt %). mLLDPE and elastomeric compositions are further discussed herein. The wt % discussed is based on the blocking layer.

[0077] Non-adhesive layer can comprise the blend (or consisting of or consisting essentially of) of LCB-mLLDPE, high density polyethylene (HDPE) or LCB-mLLDPE and HDPE.Non-adhesive layer can comprise about 90 % by weight or larger (about 90 % by weight to 100 % by weight or about 90 % by weight to about 99 % by weight or about 90 % by weight to about 95 % by weight) LCB-mLLDPE, HDPE or their blend.When using in blend, the weight ratio of LCB-mLLDPE and HDPE can be about 99:1 to about 1:99 (or about 99:1 to about 50:50 or about 75:25 to about 25:75 or about 50:50 to about 1:99).This paper further discusses LCB-mLLDPE and HDPE compositions.The % by weight discussed and ratio are based on each non-adhesive layer discussed.

[0078] The oriented films of the present disclosure can have a polyethylene content of about 90 wt % or greater (or about 90 wt % to 100 wt %, or about 90 wt % to about 99 wt %, or about 95 wt % to 100 wt %, or about 95 wt % to about 99 wt %, or about 97 wt % to 100 wt %, or about 97 wt % to about 99 wt %), based on the total weight of the oriented film.

[0079] The oriented films of the present disclosure may have a cumulative amount of LCB-mLLDPE and high density polyethylene of about 70 wt % or greater (or about 70 wt % to 95 wt %, or about 70 wt % to about 80 wt %, or about 75 wt % to 85 wt %, or about 80 wt % to about 90 wt %, or about 85 wt % to 95 wt %), based on the total weight of the oriented film.

[0080] The adhesive film of the present disclosure may have a thickness of about 200 μm to about 450 μm (or about 200 μm to about 275 μm, or about 250 μm to about 325 μm, or about 275 μm to about 350 μm, or about 300 μm to about 450 μm).

[0081] Orientation The blocking film of the present disclosure may include: stretching the film at a temperature lower than the melting temperature of any polymer in the blocking film. The film can be stretched by passing it through a series of rollers, wherein the temperature and speed of a single roller are controlled to achieve the desired film thickness and stretch ratio. Typically, this series of rollers. The example of the roller that can be used during orientation may include, but is not limited to, preheating rollers, various stretching stages with or without annealing rollers between stages, one or more conditioning and annealing rollers, and one or more cooling rollers. Orienting the film can be accomplished by inducing a speed difference between two or more adjacent rollers.

[0082] The degree of orientation of a film can be described using a stretch ratio. The stretch ratio is the speed of the fast roller divided by the speed of the slow roller. For example, orienting a film using an apparatus with a slow roller speed of 1 m / min and a fast roller speed of 7 m / min means a stretch ratio of 7 (also referred to herein as 7 times or 7x). The amount of physical stretching of a film is close to, but not exactly, the stretch ratio, because relaxation of the film can occur after orientation, although usually only to a negligible degree.

[0083] Larger stretch ratios result in thinner films with larger orientations in MD. When the blocking films described herein are oriented, the stretch ratio can be 4x to 7x (or 4x to 6x, or 5x to 6.5x, or 6x to 6x). Those skilled in the art can determine the appropriate temperature and roller speed of each roller in a given MDO stage of film production without too much experimentation to produce the desired stretch ratio.

[0084] The oriented film of the present disclosure may have a thickness of about 45 μm to about 75 μm (or about 45 μm to about 60 μm, or about 50 μm to about 65 μm, or about 55 μm to about 75 μm).

[0085] In the oriented film of the present disclosure, a thickness ratio between the cumulative thickness of the blocking layer and the non-blocking layer may be about 1:50 to about 1:2 (or 1:50 to about 1:25, or about 1:30 to about 1:15, or about 1:20 to about 1:2).

[0086] In the oriented film of the present disclosure, when two or more different non-adhesive layers are used (e.g. Figure 1C The first layer 120 and the second layer 122 of the non-adhesive layer may have a thickness ratio of about 1:10 to about 10:1 (or about 1:7 to about 7:1, or about 1:5 to about 5:1).

[0087] The oriented film of the present disclosure may have a bending stiffness of about 2 mN*mm to about 4 mN*mm (or about 2 mN*mm to about 3.5 mN*mm, or about 2.5 mN*mm to about 4 mN*mm).

[0088] The oriented film of the present disclosure may have a longitudinal force at 1% strain of about 10 N to about 20 N (or about 10 N to about 15 N, or about 13 N to about 17 N, or about 15 N to about 20 N).

[0089] The oriented film of the present disclosure may have a longitudinal force at break of about 75 N to about 200 N (or about 75 N to about 150 N, or about 100 N to about 175 N, or about 150 N to about 200 N).

[0090] The oriented film of the present disclosure may have a machine direction elongation of about 150% or less (or about 15% to about 150%, or about 15% to about 50%, or about 30% to about 100%, or about 75% to about 150%).

[0091] The oriented films of the present disclosure may have a total haze of less than about 20% (or about 1% to about 20%, or about 1% to about 10%, or about 5% to about 15%).

[0092] The oriented film of the present disclosure may have a gloss of about 50 gloss units or greater (or about 50 gloss units to about 90 gloss units, or about 55 gloss units to about 85 gloss units, or about 70 gloss units to about 90 gloss units).

[0093] The oriented film of the present disclosure may have a transparency of about 50% or more (or about 50% to about 90%, or about 60% to about 80%, or about 70% to about 90%).

[0094] The oriented film of the present disclosure can be used as a surface material. The oriented film can be printed before being applied as a label. An adhesive can be applied to at least a portion of the surface of the oriented film before being applied as a label.

[0095] mLLDPE

[0096] Metallocene-catalyzed linear low density polyethylene (mLLDPE) can be used in the tie layer of the various films described herein.

[0097] The mLLDPE may be 80 wt% to 99.9 wt% ethylene derived units with the remainder being derived from one or more C3-C 12A copolymer of units of an alpha-olefin comonomer (and in particular one or more of butene, hexene, octene, preferably one of those, and more preferably hexene). The weight percent is based on the total mass of the ethylene-derived units plus the comonomer-derived units in the polyethylene. Such polyethylene is referred to as a "flat composition distribution", recognizing that the comonomer is introduced into the shorter and longer molecular chains within the polymer in relatively equal amounts (in weight percent). These may also be referred to as "narrow-CD" or "narrow composition distribution" polyethylene; or equivalently high-CDBI mLLDPE. Composition distribution refers to the distribution of comonomers in polymer chains of different lengths (different molecular weights), and CDBI refers to the composition distribution breadth index, which is defined as the weight percentage of copolymer molecules (chains) having a comonomer content within 50% of the median total molar comonomer content, and it is described in U.S. Pat. No. 5,382,630, which is incorporated herein by reference. The CDBI of a copolymer is readily determined using known techniques for separating individual fractions of a copolymer sample. One such technique is temperature rising elution fractionation (TREF) described in Wild et al. J. Poly. Sci., Poly. Phys. Ed., Vol. 20, p. 441 (1982) and U.S. Pat. No. 5,008,204, which are incorporated herein by reference. Thus, a higher CDBI value indicates a narrow composition distribution (meaning that the comonomer is relatively evenly distributed across polymer chains of different molecular weights).

[0098] The narrow-CD polyethylene may have a CDBI of at least 50%, more preferably at least 60%, for example in the range of 50-90% or 60-80%.

[0099] mLLDPE (narrow-CD or other) may more particularly have an ethylene derived content ranging from a low of any of 80, 85, 86, 87, 87.5, 88, 90, 91, 92, 93, 94, or 95 weight percent to a high of any of 88, 90, 93, 94, 95, 96, 97, 98, 99, or 99.9 weight percent; wherein ranges from any of the foregoing lows to any of the foregoing highs are contemplated, provided that the upper end is greater than the lower end (e.g., 85 to 95 weight percent, e.g., 86 to 92 weight percent ethylene derived units, or 94 to 99 weight percent ethylene derived units). The balance is comprised of C3-C 12 α-olefin comonomer derived units (such as hexene).

[0100] mLLDPE (narrow-CD or other) can provide a reduced softening point relative to the molding process, and in addition provide excellent sealing, optical and mechanical properties to the film made therefrom. mLLDPE preferably also has one or more, preferably all, of the following additional properties:

[0101] The peak melting temperature is in the range of 105-120°C, preferably 110°C or 111°C to 115°C or 116°C. The peak melting temperature (also referred to herein as "melting point") is determined by using a differential scanning calorimeter (DSC). DSC measurements can be performed using a TA DSC8000 instrument at a heating / cooling rate of 10K / min under a N2 atmosphere. The sample is 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.

[0102] The Vicat softening temperature is within the softening point range, within the range of 70°C to 130°C, preferably within the range of 90°C to 110°C, for example, 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 (wherein ranges from any of the foregoing low points to any of the foregoing high points are encompassed, provided that the high points are greater than the low points, for example, 90°C to 110°C or 97°C to 103°C).

[0103] Melt index (190°C, 2.16 kg load) in the range of 0.1-5.0 g / 10 min, for example, 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; wherein ranges from any of the above lower ends to any of the above upper ends are also encompassed.

[0104] The long chain branching index (LCB index, also referred to herein as g'(vis) or g' index) is greater than 0.95, preferably greater than or equal to 0.96 or 0.97.

[0105] mLLDPE may also have one or more of the following, preferably all:

[0106] The weight average molecular weight (Mw) is in the range of 45,000-120,000 g / mol, for example, 50,000-115,000 g / mol or 60,000 to 110,000 g / mol (wherein the range from any of the above lower ends to any of the above upper ends, for example, 45,000 to 110,000 g / mol is also encompassed);

[0107] The number average molecular weight (Mn) is in the range of 20,000-55,000 g / mol, for example, in the range of from 25,000, 30,000, 35,000 or 40,000 to a high point of 30,000, 35,000, 40,000, 45,000, 50,000 or 55,000 g / mol, wherein the range from any of the above lower ends to any of the above upper ends (provided that the upper end is greater than the lower end), for example, 35,000-55,000 g / mol;

[0108] Molecular weight distribution (Mw / Mn) ranging from 1.5 or 2.0 to 3.5 or 4; and

[0109] Density 0.905-0.940g / cm 3 In the range of, for example, from 0.905, 0.910, 0.911, 0.912 or 0.915 g / cm 3 The lower 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 / cm 3 The range of any of the above lower ends to any of the above upper ends is included (provided that the upper end is greater than the lower end), for example, 0.910-0.915 g / cm 3 .

[0110] Examples of suitable polyethylenes for mLLDPE (eg, narrow-CD mLLDPE) include EXCEED PE available from ExxonMobil Chemical Company. TM High performance polyethylene and other commercially available mLLDPE.

[0111] For the polyethylene described above, as well as any other polyethylene described herein, the molecular weight moments and distributions (Mw, Mn, Mz, Mw / Mn, Mz / Mn, etc.) and monomer / comonomer content (C2, C4, C6 and / or C8 and / or other, etc.) and (g') were determined by using a high temperature gel permeation chromatography (Polymer Char GPC-IR) equipped with an infrared detector IR5 based on a multi-channel bandpass filter, an 18-angle light scattering detector and a viscometer. vis). Three Agilent PLgel 10 μm mixed-B LS columns were used to provide polymer separation. The detailed analysis principle and molecular weight determination method and g'(vis) are described in PCT Publication WO2019 / 246069A1, paragraphs

[0044] -

[0051] , which is incorporated herein by reference (note that the equation c= / / / mentioned in paragraph

[0044] regarding the concentration (c) at each point in the chromatogram is c=βI, where β is the mass constant and I is the IR5 broadband signal intensity (I) minus the baseline). Unless specifically mentioned, all molecular weight moments used or referred to in this disclosure are determined according to conventional molecular weight (IR molecular weight) determination methods (such as those mentioned in paragraphs

[0044] -

[0045] of the just-mentioned publication), noting that for the equation in such paragraph

[0044] , a=0.695 and K=0.000579 (1-0.75Wt) are used, where Wt is the weight fraction of the comonomer, and further noting that the comonomer composition is determined by the ratio of the IR5 detector intensities corresponding to the CH2 and CH3 channels calibrated with a series of PE and PP homo / copolymer standards, the nominal values ​​of which are predetermined by NMR or FTIR as indicated in paragraph

[0045] of the just-mentioned PCT publication (providing methyls / 1000 total carbons (CH3 / 1000TC)). Other parameters required can be found in the paragraphs mentioned in the WO2019 / 246069A1 disclosure text, but for convenience, some are included here: TCB at 145°C n = 1.500; I = 665nm; dn / dc = 0.1048ml / mg.

[0112] It is believed that when used in films, mLLDPE according to the above description provide excellent sealing, toughness and puncture properties. In addition, they provide benefits for orientation processes such as double bubble formation processes because they impart relatively low melting and softening points to the composition, aiding bubble formation and stability (especially in conjunction with one or more other polyethylenes, as discussed below).

[0113] In certain embodiments, mLLDPE may be used in the skin layers (or corresponding skin layer formulations), where the properties just mentioned may be particularly suitable. However, mLLDPE may also be arranged in the core layer in various embodiments, and in some cases, it may be present in at least one core layer and at least one skin layer of the film according to various embodiments herein.

[0114] Long chain branched mLLDPE

[0115] Long chain branched (LCB) mLLDPE can be used in the non-blocking layer of the various films described herein.

[0116] Advantageously, LCB-mLLDPE can impart high bubble stability (e.g., in blown film processes, including double bubble blown processes), preferably while still imparting suitable film performance properties. Note that these mLLDPEs are considered to be long chain branched compared to other linear low density polyethylenes, and in particular compared to other metallocene LLDPEs; while their total long chain branching will still be less than that of LDPEs with very high degrees of long chain branching. This small amount of LCB can be demonstrated, for example, by a high melt index ratio (MIR) and / or specific rheological properties (e.g., η 20 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.01 / η 100 Another useful parameter indicating the presence of LCBs is illustrated in Figure 2: Van Gurp Palmen (VGP) plot. In particular, polyethylene copolymers (even LLDPE) with some LCBs will exhibit an inflection point in their VGP curves, whereas LLDPE without any LCBs will show no such inflection point. See, for example, Enable in Figure 2. TM Brand LLDPE (an example of LCB-mLLDPE) (compared to XP8318 LLDPE without LCB also shown in Figure 2).

[0117] Yet another useful parameter to illustrate the presence of some LCB can be found in the melt index ratio. The melt index ratio (MIR) is the ratio of the high load melt index (HLMI, ASTM D1238 at 190°C, 21.6 kg) to the melt index (MI2, ASTM D1238 at 190°C, 2.16 kg).

[0118] Thus, LCB-mLLDPE useful in the present composition may have one or more of the following properties (which may be useful markers for a medium LCB):

[0119] The MIR ranges from a low of any of 20, 25, 26, 27, 28, 29, 30 or 31 to a high of any of 40, 35, 34, 33, 32, 31 or 30, wherein ranges from any of the aforementioned lows to any of the aforementioned highs (e.g., 27 to 33, e.g., 28 to 32 or 29 to 31) are contemplated herein.

[0120] The complex shear viscosity (η*) at 0.01 rad / sec and 190°C is 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 lower end to any upper end (e.g., 6,000 to 8,000 Pa·s).

[0121] The complex shear viscosity (η*) at 100 rad / sec and 190°C is in the range of 900-2000 Pa·s; for example, from the lower end of any one of 900, 1,000, 1,100 or 1,200 Pa·s to the upper end of any one of 1,200, 1,300, 1,400, 1,500 or 2,000 Pa·s, wherein the range from any of the above low points to any of the above high points (e.g., 1,100 to 1,300 Pa·s) is also encompassed.

[0122] The shear thinning ratio (η* at 0.01 / 100) is less than 15, or in the range of 3 to 15, or 4 to 12, or 5 to 10, or 5.5 to 8.

[0123] The inflection point in the Van Gurp Palmen plot of phase angle versus complex modulus (Pa) for LCB-mLLDPE.

[0124] Finally, yet another indicator of LCB can be found in the LCB index (g' or alternatively g'vis), which for LCB-mLLDPE can be less than 1, e.g. in the range from 0.9 to 0.99 or 0.94 to 0.98, although still substantially higher than the g' of polyethylene with large amounts of LCB, such as LDPE made using free radical polymerization.

[0125] LCB mLLDPE, such as the mLLDPE described above, preferably has 80 to 99.9 wt% ethylene derived units, with the remainder derived from one or more C3-C 12 Copolymers of alpha-olefins (and in particular one or more of butene, hexene, octene, preferably one of those, and more preferably hexene). The weight % is based on the total mass of ethylene derived units plus comonomer derived units in the polyethylene.

[0126] The LCB mLLDPE preferably has a CDBI greater than or equal to 50%, preferably greater than or equal to 70%, such as in the range of from a low of any of 50, 60 or 70% to a high of any of 80, 85, 90, 95 or 99%, with ranges from any of the above lower ends to any of the above upper ends being encompassed. The LCB mLLDPE may also have a MWD (Mw / Mn) in the range of 2.5-5.5, such as in the range of from 3 or 3.5 to 4.5 or 5.

[0127] In addition, the LCB mLLDPE can have a melt flow index (190°C, 2.16 kg load) in the range of 0.1-0.7 g / 10 min, for example, in the range from a low of any one of 0.1, 0.15, 0.2 or 0.22 to a high of any one of 0.22, 0.25, 0.26, 0.27, 0.30, 0.40, 0.45, 0.50, 0.60 or 0.70 g / 10 min, wherein the range from any of the above lower ends to any of the above upper ends (provided that the upper end is greater than the lower end) is also encompassed, for example, 0.15-0.30 g / 10 min, or 0.15 to 0.27 g / 10 min.

[0128] LCB-mLLDPE can exhibit high stiffness and excellent processability. In addition to the properties noted above, LCB-mLLDPE can have one or more, preferably all, of the following properties:

[0129] a peak melting temperature (determined by DSC as described above) in the range of 115°C to 135°C, preferably 120°C, 121°C, 123°C or 125°C to 130°C or 133°C;

[0130] a Vicat softening temperature in the range of 110-130°C, for example 115°C to 125°C, or from a low of any one of 110, 115, 118, 119 or 120°C to a high of any one of 123, 124, 125, 127, 130 or 135°C, with ranges from any of the foregoing lows to any of the foregoing highs (e.g. 115°C to 125°C) encompassed; and

[0131] Density 0.930-0.950g / cm 3 range, for example, from 0.935, 0.936, 0.937 or 0.938 g / cm 3 Any low point to 0.942, 0.943, 0.944, 0.945 or 0.950 g / cm 3 any of the above low points, wherein the present invention contemplates a range from any of the above low points to any of the above high points (e.g., 0.935 to 0.945 g / cm 3 ).

[0132] Examples of commercially available LCB-mLLDPE include, but are not limited to, ENABLE TM Brand polyethylene, such as ENABLE TM 4002 high performance polyethylene.

[0133] High-density polyethylene

[0134] High density polyethylene (HDPE) may be used in the non-blocking layer of the various films described herein.

[0135] HDPE may have a g / cm2 or greater. 3 (or 0.940g / cm 3 Up to 0.970g / cm 3 , or 0.945g / cm 3 Up to 0.965g / cm 3 、0.950g / cm 3 Up to 0.970g / cm 3 ) density.

[0136] The HDPE can have a melt index (190° C., 2.16 kg load) of about 0.1 g / 10 min to about 1.5 g / 10 min (or 0.5 g / 10 min to 1.0 g / 10 min).

[0137] The HDPE may have a melt index (ratio of the melt index measured at 190°C, 21.6 kg load to the melt index measured at 190°C, 2.16 kg load) of about 35 to about 60 (or about 35 to about 50, or about 45 to about 60).

[0138] The HDPE may have a Vicat softening temperature of about 120°C to about 150°C (or about 125°C to about 135°C, or about 130°C to about 140°C).

[0139] Suitable HDPE may be a polyethylene homopolymer or an ethylene-α-olefin copolymer (wherein the α-olefin may be any of those discussed above in conjunction with LDPE).

[0140] Suitable HDPE may be produced by any suitable process known to those skilled in the art such as gas phase fluidized bed polymerisation or slurry polymerisation, or a combination thereof (eg in the case of a reactor or other bimodal HDPE composition, which may be produced in two or more reactors in series).

[0141] Non-limiting examples of commercially available HDPE may include, but are not limited to, HTA 108 (HDPE, available from ExxonMobil), HTA 001HD5 (HDPE, available from ExxonMobil), HTA 001HP5 (HDPE, available from ExxonMobil), HTA 002HD5 (HDPE, available from ExxonMobil), the like, and any combination thereof.

[0142] Ethylene-based elastomers

[0143] Ethylene-based elastomers may be ethylene-derived units and derived from C3-C 10 The ethylene-based elastomer may contain at least 85 weight percent ethylene-derived units, based on the weight of the ethylene-based elastomer.

[0144] Ethylene-based elastomers may have a density of 0.855 g / cm 3 -0.920g / cm 3 (or 0.860g / cm 3 -0.905g / cm 3 , or 0.865g / cm 3 -0.890g / cm 3 ) range.

[0145] The ethylene-based elastomer may have a CDBI greater than 60 (or greater than 80, or greater than 90), wherein the fraction with a Mw less than 15,000 g / mol is disregarded when determining the CDBI as described in WO 93 / 03093 (columns 7 and 8) and Wild et al., 20 J. POLY. SCI., POLY. PHYS. ED., 441 (1982) and U.S. Pat. No. 5,008,204.

[0146] The ethylene-based elastomer may have a single melting peak appearing in the region of 50°C to 110°C.

[0147] The ethylene-based elastomer may have a Mw of greater than 70,000 g / mol to less than 130,000 g / mol.

[0148] The ethylene-based elastomer may have a H greater than 75 J / g (or from 75 J / g to 130 J / g). f .

[0149] The ethylene-based elastomer may have a molecular weight distribution (Mw / Mn) of less than 4.0 (or 1.1 to 3.5).

[0150] Examples include those sold under the trade name EXACT TMPlastomer (ExxonMobil Chemical Company) or AFFINITY TM Polyolefin plastomers (Dow Chemical Company) are ethylene-based elastomers sold by Dow Chemical.

[0151] Propylene-based elastomers

[0152] Propylene-based elastomers may be propylene-derived units and units derived from ethylene or C4-C 10 The propylene-based elastomer may contain at least 60 wt. % propylene-derived units, based on the weight of the propylene-based elastomer. The propylene-based elastomer may have limited crystallinity due to adjacent isotactic propylene units and a melting point as described herein. The crystallinity and melting point of the propylene-based elastomer may be reduced compared to highly isotactic polypropylene by introducing errors in propylene insertion. The propylene-based elastomer generally does not have any substantial intermolecular heterogeneity in stereoregularity and comonomer composition, and generally does not have any substantial heterogeneity in intramolecular composition distribution.

[0153] The amount of propylene derived units present in the propylene-based elastomer can be present in an amount from at least 60 wt%, at least 65 wt%, at least 70 wt%, at least 75 wt%, at least 80 wt%, at least 84 wt%, at least 85 wt%, at least 88 wt%, at least 90 wt%, at least 92 wt%, at least 94 wt%, at least 96 wt%, or at least 98 wt% of the propylene-based elastomer. Additionally or alternatively, the amount of propylene derived units present in the propylene-based elastomer can be present in an amount of up to 98 wt%, up to 96 wt%, up to 94 wt%, up to 92 wt%, up to 90 wt%, up to 88 wt%, up to about 85 wt%, up to 84 wt%, or up to 80 wt% of the propylene-based elastomer. Explicitly disclosed ranges include any combination of the above recited values ​​such as 60 wt % to 98 wt %, 70 wt % to 98 wt %, 80 wt % to 98 wt %, 85 wt % to 98 wt %, 90 wt % to 98 wt %, 70 wt % to 96 wt %, 75 wt % to 96 wt %, 80 wt % to 96 wt %, 85 wt % to 96 wt %, 90 wt % to 96 wt %.

[0154] Derived from ethylene or C4-C 10Units or comonomers of at least one of the alpha-olefins may be present in an amount from 1 wt% to 35 wt%, or from 2 wt% to 35 wt%, or from 5 wt% to 35 wt%, or from 7 wt% to 32 wt%, or from 8 wt% to 25 wt%, or from 10 wt% to 25 wt%, or from 12 wt% to 20 wt%, or from 8 wt% to 20 wt%, or from 8 wt% to 18 wt%, or from 5 wt% to 20 wt%, or from 5 wt% to 15 wt%, or from 2 wt% to 10 wt%, or from 2 wt% to 6.0 wt%, based on the weight of the elastomer of propylene.

[0155] In preferred embodiments, the comonomer is ethylene, 1-hexene or 1-octene. In some embodiments, the propylene-based elastomer comprises ethylene-derived units or consists essentially of units derived from propylene and ethylene, i.e., the propylene-based elastomer does not contain any other comonomer except in amounts that are typically present as impurities in ethylene and / or propylene feed streams used in polymerization processes, or in amounts that would materially affect the 1% secant flexural modulus and / or melt mass flow rate of the propylene-based elastomer, or in amounts where any other comonomer is intentionally added to the polymerization process. In such an embodiment, the propylene-based elastomer can comprise from 2 wt% to 25 wt%, or from 5 wt% to 25 wt%, or from 10 wt% to 25 wt%, or from 6 wt% to 22 wt%, or from 12 wt% to 20 wt%, or from 7 wt% to 20 wt%, or from 5 wt% to 20 wt%, or from 5 wt% to 15 wt%, or from 8 wt% to 17 wt%, or from 9 wt% to 16 wt%, or from 2 wt% to 10 wt%, or from 2 wt% to 6.0 wt% ethylene-derived units, based on the weight of the propylene-based elastomer.

[0156] The propylene-based elastomer may contain more than one comonomer. Preferred embodiments of propylene-based elastomers having more than one comonomer include propylene-ethylene-octene, propylene-ethylene-hexene, and propylene-ethylene-butene polymers. 10 In embodiments where at least one comonomer is an α-olefin, the amount of one comonomer may be less than 5 wt % of the propylene-based elastomer, but the total amount of comonomers of the propylene-based elastomer is 5 wt % or greater of the total propylene-based elastomer.

[0157] In some embodiments, the propylene-based elastomer may further comprise a diene. The optional diene may be any hydrocarbon structure having at least two unsaturated bonds, wherein at least one of the unsaturated bonds is readily incorporated into the polymer. For example, the optional diene can be selected from linear acyclic olefins such as 1,4-hexadiene and 1,6-octadiene; branched acyclic olefins such as 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene and 3,7-dimethyl-1,7-octadiene; monocyclic alicyclic olefins such as 1,4-cyclohexadiene, 1,5-cyclooctadiene and 1,7-cyclododecadiene; polycyclic alicyclic fused and bridged cyclic olefins such as tetrahydroindene, norbornadiene, methyl-tetrahydroindene, dicyclopentadiene, bicyclo-(2.2.1)-hept-2,5-diene, norbornadiene, alkenyl norbornenes, alkylidene norbornenes such as ethylidene norbornene ("ENB"), cycloalkenyl norbornenes and cycloalkylidene ("cycloalkylene") olefins. iene) norbornene (e.g., 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene); and cycloalkenyl substituted olefins, such as vinylcyclohexene, allylcyclohexene, vinylcyclooctene, 4-vinylcyclohexene, allylcyclodecene, vinylcyclododecene, and tetracyclo-(A-11,12)-5,8-dodecene. The amount of diene-derived units present in the propylene-based elastomer can range from an upper limit of 15 wt%, 10 wt%, 7 wt%, 5 wt%, 4.5 wt%, 3 wt%, 2.5 wt%, or 1.5 wt% to a lower limit of 0%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.5 wt%, or 1 wt%, based on the total weight of the propylene-based elastomer. In some embodiments, the propylene-based elastomer does not contain any diene-derived units.

[0158] The propylene-based elastomer may have a triad tacticity of at least 75%, at least 80%, at least 82%, at least 85%, or at least 90% of the three propylene units, as described by 13 CNMR measurement. Preferably, the propylene-based elastomer has a triad tacticity of 50% to 99%, 60% to 99%, 75% to 99%, or 80% to 99%. In some embodiments, the propylene-based elastomer may have a triad tacticity of 60% to 97%.

[0159] Propylene-based elastomers may have a heat of fusion (“ΔH f”) is 75 J / g or less, 70 J / g or less, 50 J / g or less, or 45 J / g or less, or 35 J / g or less. The propylene-based elastomer may have a ΔH of 0.5 J / g, 1 J / g, or 5 J / g. f For example, ΔH f The value may be anywhere from 1.0 J / g, 1.5 J / g, 3.0 J / g, 4.0 J / g, 6.0 J / g, or 7.0 J / g to 30 J / g, 35 J / g, 40 J / g, 50 J / g, 60 J / g, 70 J / g, or 75 J / g.

[0160] The propylene-based elastomer may have a percent crystallinity of 2% to 65%, 0.5% to 40%, 1% to 30%, or 5% to 35% of the crystallinity of isotactic polypropylene, as determined according to the DSC procedure described herein. The thermal energy of the highest order propylene (i.e., 100% crystallinity) is determined to be 189 J / g. In some embodiments, the copolymer has a crystallinity of less than 40% of the crystallinity of isotactic polypropylene, or in the range of 0.25%-25%, or in the range of 0.5%-22%. Embodiments of propylene-based elastomers may have a stereoregularity index m / r from a lower limit of 4 or 6 to an upper limit of 8 or 10 or 12. In some embodiments, the propylene-based elastomer has an isotacticity index greater than 0%, or in a range having an upper limit of 50% or 25% and a lower limit of 3% or 10%.

[0161] The propylene-based elastomer can have a 1% secant flexural modulus (as measured according to ASTM D790-17) of at least 5.0 MPa, at least 10 MPa, at least 20 MPa, at least 30 MPa, at least 40 MPa, at least 50 MPa, at least 60 MPa, at least 70 MPa, at least 80 MPa, at least 90 MPa, at least 100 MPa, at least 125 MPa, at least 150 MPa, at least 175 MPa, at least 200 MPa, at least 225 MPa, at least 250 MPa, at least 275 MPa, at least 300 MPa, at least 325 MPa, at least 350 MPa, at least 375 MPa, at least 400 MPa, at least 425 MPa, at least 450 MPa, at least 475 MPa, or 500 MPa. Additionally or alternatively, the propylene-based elastomer can have a 1% secant flexural modulus (as measured according to ASTM D790-17) of at most 500 MPa, at most 475 MPa, at most 450 MPa, at most 425 MPa, at most 400 MPa, at most 375 MPa, at most 350 MPa, at most 325 MPa, at most 300 MPa, at most 275 MPa, at most 250 MPa, at most 225 MPa, at most 200 MPa, at most 175 MPa, at most 150 MPa, at most 125 MPa, at most 100 MPa, at most 90 MPa, at most 80 MPa, at most 70 MPa, at most 60 MPa, at most 50 MPa, at most 40 MPa, at most 30 MPa, at most 20 MPa, at most 10 MPa, or 5.0 MPa. The ranges expressly disclosed include any combination of the above listed values ​​such as 5.0 MPa to 500 MPa, 5.0 to 250 MPa, 5.0 MPa to 100 MPa, 5.0 MPa to 50 MPa, 5 MPa to 20 MPa, 20 MPa to 500 MPa, 20 MPa to 250 MPa, 20 MPa to 100 MPa, 20 MPa to 50 MPa, 40 MPa to 500 MPa, 40 MPa to 250 MPa, 40 to 100 MPa, 40 MPa to 70 MPa, 40 MPa to 60 MPa, 50 MPa to 500 MPa, 50 MPa to 2 MPa, 50 MPa to 100 MPa, 100 MPa to 500 MPa, 100 MPa to 250 MPa, 200 MPa to 500 MPa, 200 MPa to 450 MPa, 200 MPa to 400 MPa, 200 MPa to 350 MPa, 200 MPa to 300 MPa, 300 MPa to 500 MPa, 300 MPa to 450 MPa, 300 MPa to 400 MPa, 300 MPa to 350 MPa, 350 MPa to 500 MPa, 350 MPa to 450 MPa, 350 MPa to 400 MPa.

[0162] The propylene-based elastomer can have a melt flow index (2.16 kg load at 230° C.) of at least 1 g / 10 min, at least 15 g / 10 min, at least 50 g / 10 min, at least 100 g / 10 min, at least 1,000 g / 10 min, at least 2,500 g / 10 min, at least 5,000 g / 10 min, at least 7,500 g / 10 min, at least 10,000 g / 10 min, at least 12,500 g / 10 min, at least 15,000 g / 10 min, at least 17,500 g / 10 min, at least 20,000 g / 10 min, at least 22,500 g / 10 min, at least 25,000 g / 10 min, at least 27,500 g / 10 min, or 30,000 g / 10 min. Additionally or alternatively, the propylene-based elastomer may have a melt flow index (2.16 kg load at 230° C.) of at most 30,000 g / 10 min, at most 27,500 g / 10 min, at most 25,000 g / 10 min, at most 22,500 g / 10 min, at most 20,000 g / 10 min, at most 17,500 g / 10 min, at most 15,000 g / 10 min, at most g / 10min, up to 12,500 g / 10min, up to 10,000 g / 10min, up to 7,500 g / 10min, up to 5,000 g / 10min, up to 2,500 g / 10min, up to 1,000 g / 10min, up to 100 g / 10min, up to 50 g / 10min, up to 15 g / 10min or 5 g / 10min.The expressly disclosed ranges include any combination of the above-recited values ​​such as 1 g / 10min to 5 g / 10min, 1 g / 10min to 15 g / 10min, 5 g / 10min to 30,000 g / 10min, 5 g / 10min to 20,000 g / 10min, 5 g / 10min to 10,000 g / 10min, 5 g / 10min to 1,000 g / 10min, 5 g / 10min to 100 g / 10min, 5 g / 10min to 50 g / 10min, 5 g / 10min to 15 g / 10min, 1,000 g / 10min to 30,000 g / 10min, 1,000 g / 10min to 20,000 g / 10min, 1,000 g / 10min to g / 10min to 30,000 g / 10min, 10,000 g / 10min to 20,000 g / 10min, 10,000 g / 10min to 15,000 g / 10min, 20,000 g / 10min to 30,000 g / 10min, 20,000 g / 10min to 27,500 g / 10min, 22,500 g / 10min to 30,000 g / 10min, 22,500 g / 10min to 27,500,000 g / 10min, and 22,500 g / 10min to 25,000 g / 10min.

[0163] The propylene-based elastomer may have a melting point temperature (T m ) is 105°C or less, 100°C or less, 90°C or less, 80°C or less, or 70°C or less. In some embodiments, the propylene-based elastomer has a T m 25°C to 105°C, 60°C to 105°C, 70°C to 105°C, or 90°C to 105°C.

[0164] The propylene-based elastomer may have a density of 0.850 g / cm 3 Up to 0.920g / cm 3 , or 0.860g / cm 3 Up to 0.890g / cm 3 .

[0165] The propylene-based elastomer may have an elongation at break (as measured according to ASTM D638-14) of at least 200%, at least 500%, at least 1000%, at least 1500%, at least 2000%, or at least 3000%.

[0166] The propylene-based elastomer may have a weight average molecular weight (Mw) of 5,000 to 5,000,000 g / mole, or 10,000 to 1,000,000 g / mole, 20,000 to 750,000 g / mole, or 30,000 to 400,000 g / mole.

[0167] The propylene-based elastomer may have a number average molecular weight (Mn) of 2,500 to 250,000 g / mole, 10,000 to 250,000 g / mole, or 25,000 to 200,000 g / mole.

[0168] The propylene-based elastomer may have a z-average molecular weight (Mz) of 10,000 to 7,000,000 g / mole, 80,000 to 700,000 g / mole, or 100,000 to 500,000 g / mole.

[0169] The propylene-based elastomer may have a molecular weight distribution (Mw / Mn) of 1.5 to 20, or 1.5 to 15, preferably 1.5 to 5, and more preferably 1.8 to 3, and most preferably 1.8 to 2.5.

[0170] Various propylene-based elastomers having any combination of the above-described properties are contemplated herein.

[0171] The propylene-based elastomer may comprise a copolymer prepared according to the procedures described in WO 02 / 36651, U.S. Pat. No. 6,992,158 and / or WO 00 / 01745, the contents of which are incorporated herein by reference. Preferred methods for producing propylene-based elastomers may be found in U.S. Pat. Nos. 7,232,871 and 6,881,800, the contents of which are incorporated herein by reference. The propylene-based elastomers described herein are not limited to any particular polymerization process for preparing the propylene-based elastomer, and the polymerization process is not limited to any particular type of reaction vessel.

[0172] Suitable propylene-based elastomers are available under the trade name VISTAMAXX TM (available from ExxonMobil Chemical Company) (e.g. VISTAMAXX TM 3000, VISTAMAXX TM 3588FL、VISTAMAXX TM 6102、VISTAMAXX TM 8880),VERSIFY TM(available from The Dow Chemical Company), certain grades of TAFMER TM XM or NOTIO TM (available from Mitsui Company), and certain grades of SOFTEL TM (available from Basell Polyolefins) are commercially available. The specific grade(s) of commercially available propylene-based elastomer suitable for use in the present invention can be readily determined using methods well known in the art.

[0173] Unless otherwise indicated, all numerical values ​​used in this specification and the related claims expressing the amount of ingredients, properties such as molecular weight, reaction conditions, etc. should be understood as being modified in all cases by the term "about". Therefore, unless indicated to the contrary, the numerical parameters listed in the following specification and the appended claims are approximate values, which may vary depending on the desired properties sought to be obtained by the embodiment of the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be interpreted in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0174] One or more illustrative embodiments including one or more inventive elements are proposed herein. For the sake of clarity, all features of physical implementation are not described or shown in this application. It should be understood that in the development of physical embodiments including one or more elements of the present invention, in order to achieve the developer's goal, many specific decisions must be made to achieve, for example, system-related, business-related, government-related and other constraints are observed, which change from time to time with the implementation. Although the developer's efforts may be time-consuming, such efforts are routine tasks for those of ordinary skill in the art who benefit from the present disclosure.

[0175] Although compositions and methods are described herein in terms of "comprising" various components or steps, the compositions and methods may also "consist essentially of" or "consist of" the various components and steps.

[0176] Additional embodiments

[0177] Embodiment 1. A method comprising: blowing a film comprising a first layer, a second layer and a third layer, wherein the first layer comprises a long-chain branched metallocene linear low-density polyethylene (LCB-mLLDPE), wherein the second layer comprises a high-density polyethylene, and wherein the third layer comprises 0 wt % to about 90 wt % of a metallocene linear low-density polyethylene (mLLDPE) and about 10 wt % to 100 wt % of an ethylene-based elastomer and / or a propylene-based elastomer; bonding the film using the third layer as a bonding layer to produce a bonding film; and orienting the bonding film in a machine direction to produce an oriented film, wherein the oriented film has a polyethylene content of about 90 wt % or greater.

[0178] Embodiment 2. The method of Embodiment 1, wherein the second layer is between the first layer and the third layer and is adjacent to each of the first layer and the third layer.

[0179] Embodiment 3. The method of Embodiment 1, wherein the first layer is between the second layer and the third layer and is adjacent to each of the second layer and the third layer.

[0180] Embodiment 4. The method of any of Embodiments 1-3, wherein the first layer consists essentially of (or alternatively consists of) LCB-mLLDPE.

[0181] Embodiment 5. The method of any of Embodiments 1-4, wherein the second layer consists essentially of (or alternatively consists of) high-density polyethylene.

[0182] Embodiment 6. The method of any one of embodiments 1-5, wherein the oriented film has a cumulative amount of LCB-mLLDPE and high density polyethylene of about 70 wt% or greater.

[0183] Embodiment 7. The method according to any of Embodiments 1-6, wherein the propylene-based elastomer is present and has a density of about 0.850 g / cm 3 To about 0.920g / cm 3 .

[0184] Embodiment 8. The method according to any one of embodiments 1-7, wherein the propylene-based elastomer is present and has a melt flow index of about 1 g / cm2 measured at 230°C and 2.16 kg load. 3 About 10g / cm 3 .

[0185] Embodiment 9. The method of any of Embodiments 1-8, wherein the propylene-based elastomer is present and has an ethylene content of about 1 wt% to about 35 wt%.

[0186] Embodiment 10. The method according to any of embodiments 1-9, wherein the mLLDPE is a copolymer of ethylene and 1-hexene.

[0187] Embodiment 11. The method according to any of embodiments 1-10, wherein the LCB-mLLDPE is a copolymer of ethylene and 1-hexene.

[0188] Embodiment 12. The method of any of Embodiments 1-11, wherein the high density polyethylene is a homopolymer.

[0189] Embodiment 13. The method according to any one of embodiments 1-12, wherein the adhesive film has a thickness of about 200 μm to about 450 μm.

[0190] Embodiment 14. The method according to any one of embodiments 1-13, wherein the oriented film has a thickness of about 45 μm to about 75 μm.

[0191] Embodiment 15. The method according to any of embodiments 1-14, wherein the orientation of the film is performed at a stretch ratio of about 4 to about 7.

[0192] Embodiment 16. An oriented film, comprising: a first layer comprising long-chain branched metallocene linear low-density polyethylene (LCB-mLLDPE); a second layer comprising high-density polyethylene; a third layer comprising 0 wt % to about 90 wt % of a metallocene linear low-density polyethylene (mLLDPE) and about 10 wt % to 100 wt % of an ethylene-based elastomer and / or a propylene-based elastomer, wherein the third layer does not form a surface of the oriented film; wherein the oriented film has a polyethylene content of about 90 wt % or greater; and wherein the oriented film has a uniaxial longitudinal orientation.

[0193] Embodiment 17. The film of claim 16, wherein the first layer consists essentially of (or alternatively consists of) LCB-mLLDPE.

[0194] Embodiment 18. The method of any of Embodiments 16-17, wherein the second layer consists essentially of (or alternatively consists of) high-density polyethylene.

[0195] Embodiment 19. The method of any of Embodiments 16-18, wherein the oriented film has a cumulative amount of LCB-mLLDPE and high density polyethylene of about 70 wt% or greater.

[0196] Embodiment 20. A method comprising: blowing a film comprising a first layer and a second layer, wherein the first layer comprises a long-chain branched metallocene linear low-density polyethylene (LCB-mLLDPE) and / or a high-density polyethylene, and wherein the second layer comprises 0 wt % to about 90 wt % of a metallocene linear low-density polyethylene (mLLDPE) and about 10 wt % to 100 wt % of an ethylene-based elastomer and / or a propylene-based elastomer; bonding the film using the second layer as a bonding layer to produce a bonding film; and orienting the bonding film in a machine direction to produce an oriented film, wherein the oriented film has a polyethylene content of about 90 wt % or greater.

[0197] Embodiment 21. An oriented film, comprising: a first layer comprising long-chain branched metallocene linear low-density polyethylene (LCB-mLLDPE) and / or high-density polyethylene; a second layer comprising 0 wt % to about 90 wt % of a metallocene linear low-density polyethylene (mLLDPE) and about 10 wt % to 100 wt % of an ethylene-based elastomer and / or a propylene-based elastomer, wherein the second layer does not form a surface of the oriented film; wherein the oriented film has a polyethylene content of about 90 wt % or greater; and wherein the oriented film has a uniaxial longitudinal orientation.

[0198] In order to facilitate a better understanding of the embodiments of the present invention, the following examples of preferred or representative embodiments are given. The following examples should in no way be construed as limiting or defining the scope of the present invention. Example

[0199] Four membranes were prepared according to the following procedure.

[0200] Film 1 (comparative) - A 5 layer film was coextruded using a commercially available blown film machine, 900 mm wide, using a die diameter of 250 mm and an output of 200 kg / h. The layers were, in order: (1) 70 wt% LD 100BW (low density polyethylene, available from ExxonMobil) blended with 30 wt% HTA 108 (high density polyethylene, available from Exxon Mobil), (2) 70 wt% LD 100BW blended with 30 wt% HTA 108, (3) 55 wt% LD 100BW blended with 45 wt% DOWLEX 5538 (medium density polyethylene, available from Dow), (4) 70 wt% LD 100BW blended with 30 wt% HTA 108, and (5) 70 wt% LD 100BW blended with 30 wt% HTA 108. The relative layer thicknesses are 1:1:4:1:1.

[0201] Film 2 (Comparative) - Commercially available 80 μm clear polyethylene facestock suitable for use in labels.

[0202] Film 3 (Invention) - A 5 layer film was coextruded using a commercially available blown film machine using a die diameter of 250 mm at an output of 200 kg / h. The layers in order were (1) 100 wt% ENABLE TM 4002MC (LCB-mLLDPE, available from ExxonMobil), (2) 100 wt% HTA 108, (3) 100 wt% ENABLE TM 4002MC, (4) 100 wt% HTA 108 and (5) 80 wt% EXCEED TM 1012MA with 20 wt% VISTAMAXX TM 6102FL (propylene-based elastomer, available from ExxonMobil). The relative layer thicknesses were 1.5:2.5:5.5:2.5:1. The total thickness was about 150 μm. The block blown film was bonded to produce a 300 μm thick film having layers (1), (2), (3), (4), (5 bilayer), (4), (3), (2), (1). The block film was then uniaxially oriented in the machine direction using a commercially available MDO apparatus including preheating, drawing, annealing and cooling sections. For the orientation process, preheating was performed at about 114°C, stretching was performed at about 122°C, and annealing and cooling were performed at about 114°C reduced to about 30°C. The stretch ratio was about 5.4.

[0203] Film 4 (Invention) - The same procedure as Film 3 was used but with a stretch ratio of about 5.0.

[0204] The properties of four films are provided in Table 1. In Table 1, transparency is reported as the measurement result of regular transmitted light deflected less than 0.1 degrees from the axis of the incident light. The film is placed in a film sample holder and gently held against the left wall of the measurement chamber. Visually confirm that the sample has no obvious defects that can affect the results, no wrinkles and stretching. Haze is defined as the percentage of transmitted light passing through the film with a deflection greater than 2.5°. Using a pair of scissors, the test sample is cut from the web of each test material / structure into samples large enough to cover a microscope slide. Gloss is defined as the light reflection property of a plastic film or sheet under a 45° angle incident beam. When measuring the gloss of a blown film or sheet, the sample is cut in a manner that represents the entire enclosed area of ​​the film bubble or sheet. The bending stiffness coefficient is determined by the measurement results associated with the cantilever beam method, which measures the force required to bend the band to a certain angle. In this test, the sample is clamped vertically at one end, and a force is applied to the free end of the sample perpendicular to its plane (two-point bending). The sample width is 38mm. The test speed was 30° / min (18.33 mm / min) when the preload was reached and 30° / min (18.33 mm / min) during the actual test. Finally, the longitudinal force at 1% strain, the longitudinal force at break and the longitudinal elongation were determined using similar test film specimens and a similar test progression to obtain the relevant respective measurement results. The specimens for this test were rectangular in shape, 15 mm in width and with an initial distance of 50 mm between the grips. This test method uses a constant rate of separation of the grips clamping the ends of the test specimen. The load is measured by means of a load cell and the deformation is measured by means of the crosshead position. No additional extensometer was used in this test. The test speed was 5 mm / min when the preload was reached, 5 mm / min to measure the 1% secant modulus (force at 1% strain) and 500 mm / min to measure the breaking point (breaking force).

[0205] Table 1

[0206]

[0207] Films 3 and 4 have superior optical properties, including significant improvements in haze, gloss, and clarity, compared to reference sample films 1 and 2. These improved optical properties translate into labels with superior appearance.

[0208] In addition, films 3 and 4 show comparable bending stiffness to reference sample films 1 and 2, even though the film thickness is reduced by 25-30% in the thickness of films 3 and 4. Maintaining bending stiffness can allow for good label printing and high-speed labeling. Advantageously, because films 3 and 4 are thinner, the labels will use less polymer for the application.

[0209] Therefore, the present invention is well suited to obtain the results and advantages mentioned and inherent therein. The specific embodiments and configurations disclosed above are illustrative only, as it is obvious that different but equivalent means can be adopted to modify and implement the present invention for those skilled in the art who benefit from the teachings herein. In addition, except as described in the following claims, it is not intended to limit the details of the construction or design shown herein. It is therefore obvious that the specific illustrative embodiments disclosed above can be changed, combined or modified, and all such changes are considered to be within the scope and spirit of the present invention. In the absence of any element not specifically disclosed herein and / or any optional element disclosed herein, the invention disclosed illustratively herein can be appropriately implemented. Although compositions and methods are described in terms of "comprising", "containing" or "including" various components or steps, the compositions and methods can also be "essentially composed of various components and steps" or "composed of various components and steps". All numerical values ​​and ranges disclosed above can be changed to a certain extent. Whenever a numerical range with a lower limit and an upper limit is disclosed, any numerical value and any included range falling within the range are specifically disclosed. In particular, each range of values ​​disclosed herein (having the following format "from about a to about b", or equivalently "from about a to b", or equivalently "from about ab") should be understood to recite each value and range contained within the broader range of values. In addition, the terms in the claims have their ordinary, general meaning unless otherwise explicitly and clearly defined by the patentee. In addition, the indefinite articles "a" or "an" as used in the claims are defined herein to mean one or more than one of the elements it introduces.

Claims

1. Methods, including: Blowing a film comprising a first layer, a second layer and a third layer, The first layer comprises long-chain branched metallocene linear low-density polyethylene (LCB-mLLDPE), wherein the second layer comprises high density polyethylene, and wherein the third layer comprises 0 wt % to 90 wt % of a metallocene linear low density polyethylene (mLLDPE) and 10 wt % to 100 wt % of an ethylene-based elastomer and / or a propylene-based elastomer; bonding the films using the third layer as an adhesive layer to produce an adhesive film; and The blocking film is oriented in a machine direction to produce an oriented film, wherein the oriented film has a polyethylene content of 90 wt % or more.

2. The method of claim 1, wherein the second layer is between the first layer and the third layer and is adjacent to each of the first layer and the third layer.

3. The method of claim 1, wherein the first layer is between and adjacent to each of the second and third layers.

4. The method of claim 1 or any one of claims 2-3, wherein the first layer consists essentially of LCB-mLLDPE.

5. The method of claim 1 or any one of claims 2-4, wherein the second layer consists essentially of high density polyethylene.

6. The method of claim 1 or any one of claims 2-5, wherein the oriented film has a cumulative amount of LCB-mLLDPE and high density polyethylene of 70 wt% or more.

7. The method of claim 1 or any one of claims 2-6, wherein the propylene-based elastomer is present and has an ethylene-derived content of 1 wt% to 35 wt%, based on the mass of the propylene-based elastomer, and further has one or both of the following: 0.850 g / cm 3 Up to 0.920g / cm 3 The density and 1g / cm 3 Up to 10g / cm 3 The melt flow index is measured at 230°C and 2.16 kg load.

8. The method of claim 1 or any one of claims 2-7, wherein the mLLDPE is a copolymer of ethylene and 1-hexene.

9. The method of claim 1 or any one of claims 2-8, wherein the LCB-mLLDPE is a copolymer of ethylene and 1-hexene.

10. The method according to claim 1 or any one of claims 2-9, wherein the adhesive film has a thickness of 200 μm to 450 μm. The method according to claim 10 , wherein the alignment film has a thickness of 45 μm to 75 μm.

12. The method of claim 1 or any one of claims 2-11, wherein the orientation of the film is carried out at a draw ratio of 4 to 7.

13. Oriented film, comprising: a first layer comprising long-chain branched metallocene linear low-density polyethylene (LCB-mLLDPE); a second layer comprising high density polyethylene; a third layer comprising 0 to 90 wt % of a metallocene linear low density polyethylene (mLLDPE) and 10 to 100 wt % of an ethylene-based elastomer and / or a propylene-based elastomer, wherein the third layer does not form a surface of the oriented film; wherein the oriented film has a polyethylene content of 90 wt % or greater; and The oriented film has a uniaxial longitudinal orientation.

14. The oriented film according to claim 13, wherein the first layer consists of LCB-mLLDPE.

15. An oriented film according to claim 13 or claim 14, wherein the second layer consists of high density polyethylene.

16. The oriented film according to any one of claims 13 to 15, wherein the oriented film has a cumulative amount of LCB-mLLDPE and high density polyethylene of 70 wt% or more.

17. A method comprising: Blowing a film comprising a first layer and a second layer, wherein the first layer comprises long chain branched metallocene linear low density polyethylene (LCB-mLLDPE) and / or high density polyethylene, and wherein the second layer comprises 0 wt % to 90 wt % of a metallocene linear low density polyethylene (mLLDPE) and 10 wt % to 100 wt % of an ethylene-based elastomer and / or a propylene-based elastomer; bonding the film using the second layer as an adhesive layer to produce an adhesive film; and The blocking film is oriented in a machine direction to produce an oriented film, wherein the oriented film has a polyethylene content of 90 wt % or more.

18. Oriented film, comprising: a first layer comprising long chain branched metallocene linear low density polyethylene (LCB-mLLDPE) and / or high density polyethylene; a second layer comprising 0 to 90 wt % of a metallocene linear low density polyethylene (mLLDPE) and 10 to 100 wt % of an ethylene-based elastomer and / or a propylene-based elastomer, wherein the second layer does not form a surface of the oriented film; wherein the oriented film has a polyethylene content of 90 wt % or greater; and The oriented film has a uniaxial longitudinal orientation.

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