FILM STRUCTURE COMPRISING MULTILAYERS OF POLYETHYLENE

Abstract

MULTILAYER FILM STRUCTURE. This is a multilayer film structure made entirely of polyethylene having alternating layers of (A) a linear low-density polyethylene and (B) a high-density polyethylene that exhibits improved performance properties compared to a film structure where layers (A) and (B) are arranged in a block or random manner.

Description

1 / 76 “FILM STRUCTURE COMPRISING MULTILAYERS OF POLYETHYLENE” FIELD OF TECHNIQUE

[001] Film structures are provided all of polyethylene having alternating and adjacent layers of (A) a linear low-density polyethylene and (B) a high-density polyethylene. The film structures have relatively good robustness, optical properties and wave properties at a given stiffness. FUNDAMENTALS OF THE TECHNIQUE

[002] In multilayer film structures, each film layer can contribute its own characteristic property or properties to end-use performance, such as gas or water vapor barrier properties, sealability, robustness, stiffness, and mechanical strength. However, in addition to the properties attributed to the presence of an individual layer, the final performance properties of a multilayer film structure can be a function of the interfacial compatibility and interface adhesion between adjacent film layers. SUMMARY OF THE INVENTION

[003] Without wishing to adhere to any theory, in a multilayer film structure comprising layers of semicrystalline polymeric materials, interlayer adhesion can be improved by promoting co-crystallization across the interfaces between the layers, thus forming a homogeneous lattice of interfacial crystals.

[004] Currently, it is reported that the performance properties of an all-polyethylene multilayer film structure are improved with the appropriate arrangement and type of polyethylene materials in the film structure.

[005] A multilayer film structure made entirely of polyethylene is provided, wherein the film structure comprises at least five alternating layers and Petition 870240100454, dated 11 / 26 / 2024, page 10 / 169 2 / 76 adjacent to: (A) a linear low-density polyethylene having a density of 0.910 g / cm3 to 0.940 g / cm3 and a melt index, I2, of 0.1 to 10 g / 10 min; and (B) a high-density polyethylene having a density of at least 0.945 g / cm3, a melt index, I2, of 0.1 to 10 g / 10 min and comprising 0 to 1 percent, by weight, of a nucleating agent or a mixture of nucleating agents.

[006] In one embodiment, the difference in density between linear low-density polyethylene (A) and high-density polyethylene (B) is at least 0.015 g / cm3.

[007] In one embodiment, the difference in density between linear low-density polyethylene (A) and high-density polyethylene (B) is at least 0.030 g / cm3.

[008] In one embodiment, high-density polyethylene is a polyethylene homopolymer composition, wherein the polyethylene homopolymer composition comprises: (i) 95 to 30 percent by weight of a first ethylene homopolymer having a density of 0.950 to 0.975 g / cm3; and (ii) 5 to 70 percent by weight of a second ethylene homopolymer having a density of 0.950 to 0.975 g / cm3, wherein the ratio of the melt index, I2, of the second ethylene homopolymer to the melt index, I2, of the first ethylene homopolymer is at least 10.

[009] In one embodiment, the high-density polyethylene comprises 100 to 10,000 ppm of a nucleating agent or a mixture of nucleating agents.

[010] In one embodiment, the nucleating agent or mixture of nucleating agents comprises a salt of a dicarboxylic acid compound.

[011] In one embodiment, the film structure has five alternating and adjacent layers in the following pattern: A / B / A / B / A. Petition 870240100454, dated 11 / 26 / 2024, p. 11 / 169 3 / 76

[012] In one embodiment, the film structure has five alternating and adjacent layers in the following pattern: B / A / B / A / B.

[013] In one embodiment, the film structure has seven alternating and adjacent layers in the following pattern: A / B / A / B / A / B / A.

[014] In one embodiment, the film structure has seven alternating and adjacent layers in the following pattern: B / A / B / A / B / A / B.

[015] In one embodiment, the film structure has nine alternating and adjacent layers in the following pattern: A / B / A / B / A / B / A / B / A.

[016] In one embodiment, the film structure has nine alternating and adjacent layers in the following pattern: B / A / B / A / B / A / B / A / B.

[017] In one embodiment, the film structure has eleven alternating and adjacent layers in the following pattern: A / B / A / B / A / B / A / B / A / B / A.

[018] In one embodiment, the film structure has eleven alternating and adjacent layers in the following pattern: B / A / B / A / B / A / B / A / B / A / B.

[019] In one embodiment of the development, a film structure has at least one shell layer comprising (A) a linear low-density polyethylene having a density of 0.910 g / cm3a 0.940 g / cm3e and a melt index, b of 0.1 a 10 g / 10 min. BRIEF DESCRIPTION OF THE DRAWINGS

[020] Figure 1 shows the modulated differential scanning calorimetry (MDSC) analysis, specifically the second total heating heat flux, for a film structure consisting of a development modality as well as for a comparative film structure.

[021] Figure 2 shows the CTREF profiles for a linear low-density polyethylene (LLDPE) and a high-density polyethylene (HDPE). DESCRIPTION OF MODALITIES

[022] It should be understood that any numerical range mentioned herein Petition 870240100454, dated 11 / 26 / 2024, page 12 / 169 4 / 76 document is intended to include all subranges integrated therein. For example, a range of “1 to 10” is intended to include all subranges between and including the quoted minimum value of 1 and the quoted maximum value of 10; that is, having a minimum value equal to or greater than 1 and a maximum value equal to or less than 10. Because the disclosed numerical ranges are continuous, they include every value between the minimum and maximum values. Except where otherwise indicated, the various numerical ranges specified in this application are approximations.

[023] Depending on the usage in question, the term “monomer” refers to a small molecule that can react chemically and become chemically bonded to itself or to other monomers to form a polymer.

[024] Depending on the usage in question, the term “α-olefin” is used to describe a monomer having a linear hydrocarbon chain containing from 3 to 20 carbon atoms having a double bond at one end of the chain; an equivalent term is “linear α-olefin”.

[025] By the terms “ethylene homopolymer” or “polyethylene homopolymer” which are used interchangeably, it is understood that the polymer being referred to is the product of a polymerization process, in which only ethylene has been deliberately added or is present as a polymerizable monomer.

[026] By the terms “ethylene copolymer” or “polyethylene copolymer” which are used interchangeably, it is understood that the polymer being referred to is the product of a polymerization process, in which ethylene and one or more olefins have been deliberately added or were deliberately present as a polymerizable monomer.

[027] In one embodiment of the present disclosure, a film structure comprises alternating and adjacent layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene. Correspondingly, in one embodiment, the film structure of Petition 870240100454, dated 11 / 26 / 2024, page 13 / 169 5 / 76 present revelation will be an all-polyethylene film structure and will be a multi-layered film structure. Linear low-density polyethylene

[028] In one embodiment of the present disclosure, a “linear low-density polyethylene” is a copolymer of ethylene and one or more olefins.

[029] In the embodiments of the disclosure, a linear low-density polyethylene is a copolymer of ethylene and one or more C3-C20 alpha-olefins and / or C4-C18 diolefins.

[030] In the embodiments of the disclosure, a linear low-density polyethylene is a copolymer of ethylene and one or more of propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene.

[031] In one embodiment of the revelation, a linear low-density polyethylene is a copolymer of ethylene and 1-octene.

[032] In the embodiments of the disclosure, a linear low-density polyethylene is a copolymer of ethylene and one or more C3-C20 alpha-olefins and comprises at least 70 percent by weight of ethylene, or at least 80 percent by weight of ethylene, or at least 90 percent by weight of ethylene.

[033] In the embodiments of the disclosure, a linear low-density polyethylene is a copolymer of ethylene and 1-octene and comprises at least 70 percent by weight of ethylene, or at least 80 percent by weight of ethylene, or at least 90 percent by weight of ethylene.

[034] In the embodiments of the disclosure, a linear low-density polyethylene has a density of 0.910 to 0.940 g / cm3, or 0.910 to 0.939 g / cm3, or 0.910 to 0.936 g / cm3, or 0.910 to 0.936 g / cm3. g / cm3, or from 0.912 to 0.940 g / cm3, or from 0.912 to 0.939 g / cm3, or from 0.912 to 0.936 g / cm3, or from 0.912 to 0.932 g / cm3, or from 0.914 to 0.930 g / cm3, or from 0.914 to 0.930 g / cm3, or from 0.914 to 0.939 g / cm3, or from 0.914 to 0.936 g / cm3, or from 0.914 to Petition 870240100454, of 26 / 11 / 2024, p. 14 / 169 6 / 76 0.932 g / cm3, or 0.916 to 0.940 g / cm3, or 0.916 to 0.939 g / cm3, or 0.916 a 0.936 g / cm3, or 0.916 to 0.932 g / cm3, or 0.910 to 0.930 g / cm3, or 0.910 a 0.928 g / cm3, or 0.910 to 0.926 g / cm3, or 0.910 to 0.924 g / cm3, or 0.912 a 0.930 g / cm3, or 0.912 to 0.928 g / cm3, or 0.912 to 0.926 g / cm3, or 0.912 a 0.924 g / cm3, or 0.914 to 0.930 g / cm3, or 0.914 to 0.928 g / cm3, or 0.914 a 0.926 g / cm3, or from 0.914 to 0.924 g / cm3.

[035] In the development embodiments, a linear low-density polyethylene has a melting index, bde of 0.01 to 100 g / 10 min, or of 0.1 to 50 g / 10 min, or of 0.1 to 10 g / 10 min, or of 0.1 to 5 g / 10 min, or of 0.5 to 5 g / 10 min, or of 0.1 to 3 g / 10 min, or of 0.5 to 3 g / 10 min.

[036] In embodiments, the linear low-density polyethylene of the present disclosure may be a homogeneous ethylene copolymer or a heterogeneous ethylene copolymer.

[037] The term “homogeneous ethylene copolymer” refers to a subset of ethylene copolymers that are produced using a homogeneous catalyst formulation. Homogeneous catalysts are single-site catalysts; non-limiting examples thereof include metallocene catalysts, restricted geometry catalysts, and phosphinimine catalysts, all of which are well known to those skilled in the art.

[038] The term “heterogeneous ethylene copolymer” refers to a subset of ethylene copolymers that are produced using a heterogeneous catalyst formulation. Heterogeneous catalysts are multi-site catalysts; non-limiting examples thereof include Ziegler-Natta catalysts or chromium catalysts, both of which are well known to those skilled in the art.

[039] Typically, ethylene copolymers have a narrow molecular weight distribution, such as, for example, a permeation chromatography value Petition 870240100454, dated 11 / 26 / 2024, page 15 / 169 7 / 76 in gel (GPC) Mw / Mn less than about 2.8, where Mw and Mn refer to the weight-average and number-average molecular weights, respectively. In contrast, Mw / Mn of heterogeneous ethylene copolymers are typically higher than Mw / Mn of homogeneous ethylene copolymers. In general, homogeneous ethylene copolymers also have a narrow comonomer distribution, that is, each macromolecule within the molecular weight distribution has a similar comonomer content. Frequently, the composition distribution amplitude index “CDBI” is used to quantify how the comonomer is distributed within an ethylene copolymer, as well as to differentiate ethylene copolymers produced with different catalysts or processes. “CDBI50” is defined as the percentage of ethylene copolymer whose composition is within 50% of the median comonomeric composition, and this definition is consistent with what was described in US Patent No. 5,206,075 assigned to Exxon Chemical Patents Inc.The CDBIso of an ethylene copolymer can be calculated from TREF (Temperature Elevation Fractionation) curves; the TREF method is described in Wild, et al., J. Polym. Sci., Part B, Polym. Phys., Vol. 20 (3), pages 441-455. Typically, the CDBIso of homogeneous ethylene copolymers is greater than about 70%. In contrast, the CDBIso of heterogeneous ethylene copolymers is generally less than the CDBI50 of homogeneous ethylene copolymers.

[040] It is well known to those skilled in the art that homogeneous ethylene copolymers are often further subdivided into “linear homogeneous ethylene copolymers” and “substantially linear homogeneous ethylene copolymers.” These two subgroups differ in the proportion of long-chain branching present. More specifically, linear homogeneous ethylene copolymers have less than about 0.01 long-chain branches per 1000 carbon atoms, while substantially linear ethylene copolymers have more than about 0.01 to about 3.0 long-chain branches per 1000 carbon atoms. Petition 870240100454, dated 11 / 26 / 2024, page 16 / 169 8 / 76 long chain per 1000 carbon atoms. A long-chain branch is macromolecular in nature (that is, it can be similar in length to the macromolecule to which the long-chain branch is attached). In this disclosure, the term “homogeneous ethylene copolymer” refers to linear homogeneous ethylene copolymers and substantially linear homogeneous ethylene copolymers.

[041] In the development modalities, linear low-density polyethylene can be unimodal or multimodal.

[042] As used herein, the term “unimodal” refers to molecular weight distribution (MWD) in a gel permeation chromatography (GPC) curve that does not exhibit substantially multiple component polymers (i.e., there are no bumps, ridges or tails or they are not substantially discernible in the GPC curve). As used herein, “multimodal” refers to MWD in a GPC curve that exhibits two or more component polymers, wherein one component polymer may be present as a bump, ridge or tail relative to the MWD of the other component polymer.

[043] In the development modalities, linear low-density polyethylene has a molecular weight distribution, Mw / Mn less than 10.0, or less than 9.0, or less than 7.0, or less than 6.0, or less than 5.5, or less than 5.0, or less than 4.5, or less than 4.0, or less than 3.8. In some development methods, linear low-density polyethylene has an Mw / Mn ratio of 2.0 to 10.0, or 2.0 to 8.0, or 2.0 to 6.0, or 2.0 to 5.5, or 2.0 to 5.0, or 2.0 to 4.5, or 2.0 to 4.0, or 2.2 to 6.0, or 2.2 to 5.5, or 2.2 to 5.0, or 2.2 to 4.5, or 2.2 to 4.0, or 2.5 to 6.0, or 2.5 to 5.5, or 2.5 to 5.0, or 2.5 to 4.5, or 2.5 to 4.0. In still other forms of development, linear low-density polyethylene has an Mw / Mn ratio of 3.0 to 5.5, or 3.0 to 4.5, or 3.0 to 4.0, or 3.2 to 5.5, or 3.2 to 5.0, or 3.2 to 4.5. Petition 870240100454, dated 11 / 26 / 2024, p. 17 / 169 9 / 76

[044] In the development embodiments, linear low-density polyethylene has an average molecular weight distribution Z, Mz / Mw of 1.5 to 6.0. In additional development embodiments, linear low-density polyethylene has an Mz / Mn of 1.5 to 5.5, or 1.5 to 5.0, or 1.5 to 4.0, or 1.5 to 3.5, or 1.5 to 3.0, or 1.5 to 2.5.

[045] In the development embodiments, linear low-density polyethylene can be made using gas-phase, solution-phase or flow-paste polymerization processes, or any combination thereof, using any type of reactor or reactor configuration known in the art, for example, fluidized bed gas-phase reactors, loop reactors, stirred tank reactors, parallel batch reactors, series reactors, and / or any combination thereof.

[046] In one embodiment of the development, linear low-density polyethylene is made in a solution-phase polymerization process.

[047] In one embodiment of the disclosure, linear low-density polyethylene is a heterogeneous ethylene copolymer.

[048] In one embodiment of the development, linear low-density polyethylene is made with a heterogeneous catalyst formulation.

[049] In one embodiment of the development, linear low-density polyethylene is made with a Ziegler-Natta catalyst formulation.

[050] In one embodiment of the development, linear low-density polyethylene is made with a heterogeneous catalyst formulation in a solution-phase polymerization process.

[051] In one embodiment of the development, linear low-density polyethylene is made with a Ziegler-Natta catalyst formulation in a solution-phase polymerization process.

[052] A number of heterogeneous catalyst formulations are well known in the art, including, as non-limiting examples, formulations of Petition 870240100454, dated 11 / 26 / 2024, page 18 / 169 10 / 76 Ziegler-Natta catalyst and chrome.

[053] In one embodiment of the revelation, a heterogeneous catalyst formulation is a Ziegler-Natta catalyst.

[054] Ziegler-Natta catalysts include in-line or batch Ziegler-Natta catalyst formulations. The term “in-line Ziegler-Natta catalyst formulation” refers to the continuous synthesis of a small amount of an active Ziegler-Natta catalyst and immediately injecting that catalyst into at least one continuously operating reactor, where the catalyst polymerizes ethylene and one or more optional α-olefins to form an ethylene interpolymer. The terms “batch Ziegler-Natta catalyst formulation” or “batch Ziegler-Natta procatalyst” refer to the synthesis of a much larger amount of catalyst or procatalyst in one or more mixing vessels that are external to, or isolated from, the continuously operating solution polymerization process. Once prepared, the batch Ziegler-Natta catalyst formulation, or batch Ziegler-Natta procatalyst, is transferred to a catalyst storage tank.The term “pro-catalyst” refers to an inactive catalyst formulation (inactive with respect to ethylene polymerization); the pro-catalyst is converted into an active catalyst by adding an aluminum alkyl co-catalyst. As needed, the pro-catalyst is pumped from the storage tank to at least one continuously operating reactor, where an active catalyst is formed and polymerizes ethylene and one or more optional α-olefins to form an ethylene interpolyethylene. The pro-catalyst may be converted into an active catalyst in the reactor or external to the reactor.

[055] A wide variety of chemical compounds can be used to synthesize an active Ziegler-Natta catalyst formulation. Several chemical compounds that can be combined to produce an active Ziegler-Natta catalyst formulation are described below. Those skilled in the art will understand that the embodiments of this disclosure are not limited to Petition 870240100454, dated 11 / 26 / 2024, page 19 / 169 11 / 76 specific chemical compounds revealed.

[056] An active Ziegler-Natta catalyst formulation may be formed from: a magnesium compound, a chloride compound, a metal compound, an aluminum alkyl co-catalyst and an aluminum alkyl. As will be assessed by those skilled in the art, Ziegler-Natta catalyst formulations may contain additional components; a non-limiting example of an additional component is an electron donor, for example, amines or ethers.

[057] A non-limiting example of an active in-line ZieglerNatta catalyst formulation can be prepared as follows. In the first step, a solution of a magnesium compound (component (v)) is reacted with a solution of the chloride compound (component (vi)) to form a magnesium chloride support suspended in solution. Non-limiting examples of magnesium compounds include Mg(R1)2; wherein the R1 groups may be identical or different linear, branched, or cyclic hydrocarbyl radicals containing 1 to 10 carbon atoms. Non-limiting examples of chloride compounds include R2Cl; wherein R2 represents a hydrogen atom, or a linear, branched, or cyclic hydrocarbyl radical containing 1 to 10 carbon atoms. In the first step, the magnesium compound solution may also contain an aluminum alkyl group (component (ix)).Non-limiting examples of alkyl aluminum include Al(R3)s, wherein the R3 groups may be identical or different linear, branched, or cyclic hydrocarbyl radicals containing from 1 to 10 carbon atoms. In the second step, a solution of the metal compound (component (vii)) is added to the magnesium chloride solution and the metal compound is supported on the magnesium chloride. Non-limiting examples of suitable metal compounds include M(X)n or MO(X)n; where M represents a metal selected from Group 4 to Group 8 of the Periodic Table, or mixtures of metals selected from Group 4 to Group 8; O represents oxygen, and; X represents chloride or bromide; n is an integer from 3 to 6 that satisfies the oxidation state. Petition 870240100454, dated 11 / 26 / 2024, page 20 / 169 12 / 76 of the metal. Additional non-limiting examples of suitable metal compounds include Group 4 to Group 8 metal alkyls, metal alkoxides (which can be prepared by reacting a metal alkyl with an alcohol), and mixed-ligand metal compounds containing a mixture of halide, alkyl, and alkoxide ligands. In the third step, a solution of an aluminum alkyl co-catalyst (component (viii)) is added to the metal compound supported on magnesium chloride. A wide variety of aluminum alkyl co-catalysts are suitable, as expressed by formula (VI): AI(R4)P(OR5)q(X)r (VI) wherein the R4 groups may be identical or different hydrocarbyl groups having from 1 to 10 carbon atoms; the OR5 groups may be identical or different alkoxy or aryloxy groups wherein R5 is a hydrocarbyl group having from 1 to 10 carbon atoms bonded to oxygen; X is chloride or bromide, and (p+q+r) = 3, provided that p is greater than 0. Non-limiting examples of commonly used alkyl aluminum co-catalysts include trimethyl aluminum, triethyl aluminum, tributyl aluminum, dimethyl aluminum methoxide, diethyl aluminum ethoxide, dibutyl aluminum butoxide, dimethyl aluminum chloride or bromide, diethyl aluminum chloride or bromide, dibutyl aluminum chloride or bromide, and ethyl aluminum dichloride or dibromide.

[058] The process described in the previous paragraph, for synthesizing an active in-line Ziegler-Natta catalyst formulation, can be carried out in a variety of solvents; non-limiting examples of solvents include linear or branched Cs to C12 alkanes or mixtures thereof.

[059] To produce an active in-line Ziegler-Natta catalyst formulation in one embodiment of the discovery, the amount and molar ratios of the five components, (v) to (ix) are optimized as described in US Patent No. 9,512,282.

[060] Additional forms of heterogeneous catalyst formulations Petition 870240100454, dated 11 / 26 / 2024, page 21 / 169 13 / 76 include formulations where the “metallic compound” is a chromium compound; non-limiting examples include silyl chromate, chromium oxide, and chromocene. In some embodiments, the chromium compound is supported on a metal oxide such as silica or alumina. Heterogeneous catalyst formulations containing chromium may also include co-catalysts; non-limiting examples of co-catalysts include trialkylaluminum compounds, alkylaluminoxane, and dialkoxyalkylaluminum compounds and the like.

[061] In the disclosure embodiments, linear low-density polyethylene may contain conventional type additives, including (1) primary antioxidants (such as, for example, cross-linked phenols, including vitamin E); (2) secondary antioxidants (such as, for example, phosphites and phosphonites); and (3) processing aids (such as, for example, fluoroelastomer and / or processing aid linked to polyethylene glycol).

[062] Still other additives that can be added to linear low-density polyethylene in the development modalities include nitrones, antacids, UV absorbers, metal deactivators, pigments, dyes, fillers and reinforcing agents, nanoscale organic or inorganic materials, antistatic agents, lubricating agents such as calcium stearates, and slip additives such as erucimide and behenamide. High-density polyethylene

[063] In the development modalities, a high-density polyethylene can be an ethylene homopolymer or an ethylene copolymer.

[064] In the embodiments of the disclosure, a high-density polyethylene is a copolymer of ethylene and one or more of C3-C20 alpha-olefins and / or C4-C18 diolefins.

[065] In the disclosure embodiments, α-olefins suitable for polymerization with ethylene to produce a high-density polyethylene include α-olefins such as, without limitation, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene.

[066] In the development methods, a high-density polyethylene is a Petition 870240100454, dated 11 / 26 / 2024, page 22 / 169 14 / 76 ethylene copolymer of ethylene and one or more of propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene.

[067] In one embodiment of the revelation, a high-density polyethylene is a copolymer of ethylene and 1-octene.

[068] In the development modalities, a high-density polyethylene is a homopolymer of ethylene.

[069] In the embodiments of the disclosure, a high-density polyethylene has a density greater than 0.940 g / cm3, or at least 0.941 g / cm3, or at least 0.945 g / cm3, or at least 0.949 g / cm3, or at least 0.950 g / cm3, or at least 0.955 g / cm3, or at least 0.960 g / cm3, or at least less than 0.965 g / cm3.

[070] In the development embodiments, a high-density polyethylene has a density of 0.945 to 0.975 g / cm3, or 0.945 to 0.970 g / cm3, or 0.945 to 0.967 g / cm3, or 0.949 to 0.975 g / cm3, or 0.949 to 0.970 g / cm3, or 0.949 to 0.967 g / cm3, or from 0.950 to 0.975 g / cm3, or from 0.950 to 0.970 g / cm3, or from 0.950 to 0.967 g / cm3, or from 0.955 to 0.975 g / cm3, or from 0.955 to 0.970 g / cm3, or from 0.955 to 0.967 g / cm3, or from 0.960 to 0.975 g / cm3, or from 0.960 to 0.970 g / cm3, or from 0.960 to 0.967 g / cm3.

[071] In the development embodiments, a high-density polyethylene has a melting index, bde of 0.01 to 100 g / 10 min, or of 0.1 to 50 g / 10 min, or of 0.1 to 10 g / 10 min, or of 0.1 to 8 g / 10 min, or of 0.5 to 10 g / 10 min, or of 0.8 to 8 g / 10 min, or of 0.5 to 8 g / 10 min, or of 0.1 to 5 g / 10 min, or of 0.5 to 5 g / 10 min.

[072] In the development methods, high-density polyethylene can be unimodal or multimodal.

[073] In one embodiment of the revelation, a high-density polyethylene has a molecular weight distribution, Mw / Mn, of about 3.0 to about 20.0.

[074] In the development modalities, a high-density polyethylene can be made using any of the well-known catalysts capable of generating Petition 870240100454, dated 11 / 26 / 2024, p. 23 / 169 15 / 76 high-density polyethylenes, such as chromium catalysts, ZieglerNatta catalysts and self-styled “single-site catalysts” such as, without limitation, metallocene catalysts, restricted geometry catalysts and phosphinimine catalysts.

[075] In the development embodiments, linear high-density polyethylene can be made using gas-phase, solution-phase or fluid paste polymerization processes, or any combination thereof, using any type of reactor or reactor configuration known in the art, for example, fluidized bed gas-phase reactors, loop reactors, stirred tank reactors, parallel batch reactors, series reactors, and / or any combination thereof.

[076] In one embodiment of the development, high-density polyethylene is made in a solution-phase polymerization process.

[077] In one embodiment of the development, high-density polyethylene is made with a single-site catalyst formulation.

[078] In one embodiment of the development, high-density polyethylene is made with a single-site catalyst formulation in a solution-phase polymerization process.

[079] In one embodiment of the disclosure, a high-density polyethylene comprises from 0 to 1 percent, by weight, of a nucleating agent or a mixture of nucleating agents.

[080] In one embodiment of the development, a high-density polyethylene comprises from 100 to 3000 ppm (parts per million) of a nucleating agent or a mixture of nucleating agents.

[081] In one embodiment of the revelation, a high-density polyethylene is a polyethylene homopolymer.

[082] In one embodiment of the disclosure, a polyethylene homopolymer is a polyethylene homopolymer composition comprising a plurality Petition 870240100454, dated 11 / 26 / 2024, page 24 / 169 16 / 76 of polyethylene homopolymer components.

[083] In one embodiment of the disclosure, a high-density polyethylene is a polyethylene homopolymer composition comprising at least one first ethylene homopolymer and at least one second ethylene homopolymer that is different from the first ethylene homopolymer.

[084] In one embodiment of the revelation, the first ethylene homopolymer has a melting index, b, which is lower than the melting index, I2, of the second ethylene homopolymer.

[085] In one embodiment of the disclosure, the first ethylene homopolymer has a melting index, I2, that is at least 50 percent lower than the melting index, I2, of the second ethylene homopolymer.

[086] In one embodiment of the disclosure, the first ethylene homopolymer has a melting index, I2, that is at least 10 times smaller than the melting index, I2, of the second ethylene homopolymer.

[087] In one embodiment of the disclosure, the first ethylene homopolymer has a weight-average molecular weight, Mw, that is greater than the weight-average molecular weight, Mw, of the second ethylene homopolymer.

[088] As will be recognized by those skilled in the art, the melting index, I2, is generally inversely proportional to the molecular weight. Therefore, in one embodiment of the disclosure, the first ethylene homopolymer has a comparatively low melting index, I2 (or, alternatively stated, a comparatively high molecular weight) compared to the second ethylene homopolymer.

[089] In one embodiment of the development, the first ethylene homopolymer has a density of 0.950 to 0.975 g / cm3. In another embodiment of the development, the first ethylene homopolymer has a density of 0.955 to 0.970 g / cm3. In yet another embodiment of the development, the first ethylene homopolymer has a Petition 870240100454, dated 11 / 26 / 2024, p. 25 / 169 17 / 76 density of 0.955 to 0.965 g / cm3.

[090] In one embodiment of the revelation, the first ethylene homopolymer has a melting index, b less than about 1.0 gram / 10 minutes (g / 10 min).

[091] In one embodiment of the revelation, the first ethylene homopolymer has a melting index, I2 of about 0.01 to about 1.0 gram / 10 minutes (g / 10 min).

[092] In one embodiment of the revelation, the first ethylene homopolymer has a melting index, I2 of about 0.1 to about 2.0 grams / 10 minutes (g / 10 min).

[093] In one embodiment of the revelation, the first ethylene homopolymer has a melting index, I2 of about 0.8 to about 2.0 grams / 10 minutes (g / 10 min).

[094] In one embodiment of the disclosure, the molecular weight distribution (Mw / Mn) of the first ethylene homopolymer is from about 1.7 to about 20.0. In further embodiments of the disclosure, the molecular weight distribution (Mw / Mn) of the first ethylene homopolymer is from about 2.0 to about 20.0, or from about 1.7 to about 4.0, or from about 2.0 to about 4.0.

[095] In one embodiment of the disclosure, the first ethylene homopolymer may comprise one or more high-density ethylene homopolymer subcomponents.

[096] In one embodiment of the disclosure, the first ethylene homopolymer comprises from 95 to 5 percent, by weight, (%, by weight) of the total weight of the first and second ethylene homopolymers. In one embodiment of the disclosure, the first ethylene homopolymer comprises from 95 to 20 percent, by weight, (%, by weight) of the total weight of the first and second ethylene homopolymers. In one embodiment of the disclosure, the first ethylene homopolymer comprises from 95 to 30 percent, by weight, (%, by weight) of the total weight of the first and second ethylene homopolymers. Petition 870240100454, dated 11 / 26 / 2024, page 26 / 169 18 / 76 In one embodiment of the disclosure, the first ethylene homopolymer comprises 95 to 40 percent by weight (%, by weight) of the total weight of the first and second ethylene homopolymers. In one embodiment of the disclosure, the first ethylene homopolymer comprises 90 to 30 percent by weight (%, by weight) of the total weight of the first and second ethylene homopolymers. In one embodiment of the disclosure, the first ethylene homopolymer comprises 85 to 30 percent by weight (%, by weight) of the total weight of the first and second ethylene homopolymers. In one embodiment of the disclosure, the first ethylene homopolymer comprises 80 to 30 percent by weight (%, by weight) of the total weight of the first and second ethylene homopolymers. In one embodiment of the disclosure, the first ethylene homopolymer comprises 75 to 30 percent by weight (%, by weight) of the total weight of the first and second ethylene homopolymers.In one embodiment of the disclosure, the first ethylene homopolymer comprises 70 to 30 percent, by weight, (%, by weight) of the total weight of the first and second ethylene homopolymers. In one embodiment of the disclosure, the first ethylene homopolymer comprises 65 to 35 percent, by weight, (%, by weight) of the total weight of the first and second ethylene homopolymers. In one embodiment of the disclosure, the first ethylene homopolymer comprises 60 to 40 percent, by weight, (%, by weight) of the total weight of the first and second ethylene homopolymers.

[097] In one embodiment of the revelation, the second ethylene homopolymer has a melting index, I2, that is greater than the melting index, I2, of the first ethylene homopolymer.

[098] In one embodiment of the disclosure, the second ethylene homopolymer has a melting index, I2, that is at least 50 percent greater than the melting index, I2, of the first ethylene homopolymer.

[099] In one embodiment of the disclosure, the second ethylene homopolymer has a melting index, I2, that is at least 10 times greater than the melting index, I2 Petition 870240100454, dated 11 / 26 / 2024, page 27 / 169 19 / 76 of the first ethylene homopolymer.

[0100] In one embodiment of the disclosure, the second ethylene homopolymer has a melting index, l2, that is at least 50 times greater than the melting index, I2, of the first ethylene homopolymer.

[0101] In one embodiment of the disclosure, the second ethylene homopolymer has a weight-average molecular weight, Mw, that is less than the weight-average molecular weight, Mw, of the first ethylene homopolymer.

[0102] As will be recognized by those skilled in the art, the melting index, I2, is generally inversely proportional to the molecular weight. Therefore, in one embodiment of the disclosure, the second ethylene homopolymer has a comparatively high melting index, I2 (or, alternatively stated, a comparatively low molecular weight) compared to the first ethylene homopolymer.

[0103] In one embodiment of the development, the second ethylene homopolymer has a density of 0.950 to 0.975 g / cm3. In another embodiment of the development, the second ethylene homopolymer has a density of 0.955 to 0.970 g / cm3. In yet another embodiment of the development, the second ethylene homopolymer has a density of 0.955 to 0.965 g / cm3.

[0104] In one embodiment of the disclosure, the second ethylene homopolymer has a melting index, I2 greater than about 5.0 g / 10 min. In further embodiments, the second ethylene homopolymer may have a melting index greater than about 5.0 at about 50 g / 10 min, or greater than 5.0 at about 40.0 g / 10 min, or greater than 5.0 at about 30 g / 10 min, or greater than 5.0 at about 20.0 g / 10 min.

[0105] In one embodiment of the revelation, the second ethylene homopolymer has a melting index, I2, of 15.0 to 30.0 g / 10 min.

[0106] In one embodiment of the revelation, the second ethylene homopolymer has a melting index, I2 greater than about 100 g / 10 min, or greater than 500 g / 10 Petition 870240100454, dated 11 / 26 / 2024, p. 28 / 169 20 / 76 min, or greater than approximately 1000 g / 10 min, or greater than approximately 5000 g / 10 min.

[0107] In one embodiment of the disclosure, the molecular weight (Mw / Mn) distribution of the second ethylene homopolymer is from about 1.7 to about 20.0. In further embodiments of the disclosure, the molecular weight (Mw / Mn) distribution of the second ethylene homopolymer is from about 2.0 to about 20.0, or from about 1.7 to about 4.0, or from about 2.0 to about 4.0.

[0108] In one embodiment of the disclosure, the second ethylene homopolymer may comprise one or more high-density ethylene homopolymer subcomponents.

[0109] In one embodiment of the disclosure, the second ethylene homopolymer comprises from 5 to 95 percent, by weight, (%, by weight) of the total weight of the first and second ethylene homopolymers. In one embodiment of the disclosure, the second ethylene homopolymer comprises from 5 to 80 percent, by weight, (%, by weight) of the total weight of the first and second ethylene homopolymers. In one embodiment of the disclosure, the second ethylene homopolymer comprises from 5 to 70 percent, by weight, (%, by weight) of the total weight of the first and second ethylene homopolymers. In one embodiment of the disclosure, the second ethylene homopolymer comprises from 5 to 60 percent, by weight, (%, by weight) of the total weight of the first and second ethylene homopolymers. In one embodiment of the disclosure, the second ethylene homopolymer comprises from 10 to 70 percent, by weight, (%, by weight) of the total weight of the first and second ethylene homopolymers.In one embodiment of the disclosure, the second ethylene homopolymer comprises 15 to 70 percent by weight (%, by weight) of the total weight of the first and second ethylene homopolymers. In one embodiment of the disclosure, the second ethylene homopolymer comprises 20 to 70 percent by weight (%, by weight) of the total weight of the first and second ethylene homopolymers. In one embodiment of the disclosure, the second ethylene homopolymer comprises 25 to 70 percent by weight (%, by weight). Petition 870240100454, dated 11 / 26 / 2024, page 29 / 169 21 / 76 of the total weight of the first and second ethylene homopolymers. In one embodiment of the disclosure, the first ethylene homopolymer comprises 30 to 70 percent by weight (%, by weight) of the total weight of the first and second ethylene homopolymers. In one embodiment of the disclosure, the second ethylene homopolymer comprises 35 to 65 percent by weight (%, by weight) of the total weight of the first and second ethylene homopolymers. In one embodiment of the disclosure, the second ethylene homopolymer comprises 40 to 60 percent by weight (%, by weight) of the total weight of the first and second ethylene homopolymers.

[0110] In one embodiment of the disclosure, the ratio between the melting index, I2 of the second ethylene homopolymer and the melting index, I2 of the first ethylene homopolymer, (that is, ο I2 of the second ethylene homopolymer divided by I2 of the first ethylene homopolymer) is at least 10 (that is, the ratio is at least 10 / 1).

[0111] In one embodiment of the disclosure, the ratio between the melting index, I2 of the second ethylene homopolymer and the melting index, I2 of the first ethylene homopolymer, (that is, ο I2 of the second ethylene homopolymer divided by I2 of the first ethylene homopolymer) is at least 50 (that is, the ratio is at least 50 / 1).

[0112] In one embodiment of the revelation, the polyethylene homopolymer composition has a bimodal profile in a gel permeation chromatography.

[0113] In one embodiment of the revelation, the polyethylene homopolymer composition has a multimodal profile in a gel permeation chromatography.

[0114] In one embodiment of the disclosure, the polyethylene homopolymer composition comprises one or more nucleating agents.

[0115] In one embodiment of the disclosure, the polyethylene homopolymer composition comprises from 100 to 3000 ppm (parts per million) of a nucleating agent or a mixture of nucleating agents.

[0116] In one embodiment of the disclosure, the polyethylene homopolymer composition has a density of at least 0.950 grams per cubic centimeter, Petition 870240100454, dated 11 / 26 / 2024, p. 30 / 169 22 / 76 g / cm3. In another embodiment of the disclosure, the polyethylene homopolymer composition has a density of at least 0.955 grams per cubic centimeter, g / cm3.

[0117] In the development embodiments, the polyethylene homopolymer composition has a density of 0.950 to 0.975 g / cm3, or 0.952 to 0.973 g / cm3, or 0.955 to 0.970 g / cm3, or 0.955 to 0.967 g / cm3, or 0.960 to 0.975 g / cm3, or 0.960 to 0.970 g / cm3, or 0.962 to 0.970 g / cm3, or 0.965 to 0.970 g / cm3.

[0118] In one embodiment of the development, the polyethylene homopolymer composition has a melting index, b, of 0.5 to 10 g / 10 min. In another embodiment of the development, the polyethylene homopolymer composition has a melting index, I2, of 0.8 to 8 g / 10 min. In another embodiment of the development, the polyethylene homopolymer composition has a melting index, I2, of 0.8 to 5 g / 10 min. In another embodiment of the development, the polyethylene homopolymer composition has a melting index, I2, of 0.8 to 3 g / 10 min.

[0119] In one embodiment of the disclosure, the polyethylene homopolymer composition has a molecular weight distribution (Mw / Mn) of about 3.0 to about 20.0.

[0120] In the embodiments of the present disclosure, the polyethylene homopolymer composition can be made through any blending process, examples of which are not limited to: physical blending of particulate resins; co-feeding of different resins to a common extruder; melt blending (in any conventional polymer blending apparatus); solution blending; and reactor blending where a polymerization process employs two or more reactors configured in series or in parallel, or a combination thereof.

[0121] In one embodiment of the disclosure, the polyethylene homopolymer composition is prepared by a solution polymerization process using two Petition 870240100454, dated 11 / 26 / 2024, page 31 / 169 23 / 76 reactors that operate under different polymerization conditions. This provides a uniform in-situ mixing of the first and second components of ethylene homopolymer. An example of this process is described in Patent Application Publication No. US 2006 / 0047078.

[0122] In one embodiment of the disclosure, the polyethylene homopolymer composition is prepared by melt blending a first and second ethylene homopolymers in an extruder.

[0123] In one embodiment of the disclosure, the polyethylene homopolymer composition is prepared by a solution polymerization process using two reactors operating under different polymerization conditions. This provides a uniform in-situ blend of the first and second ethylene homopolymer components. This blend can, for example, be made in accordance with the Patent Application Publications published in the U.S. US2013 / 0225743, US2015 / 0203671, US2017 / 0002186, US20170130040 or US2008 / 0118749.

[0124] In one embodiment of the development, high-density polyethylene is prepared with a single-site catalyst formulation.

[0125] In one embodiment of the disclosure, the catalyst components constituting the single-site catalyst formulation are not particularly limited, i.e., a wide variety of catalyst components may be used. A non-limiting embodiment of a single-site catalyst formulation comprises the following three or four components: (i) a bulky ligand-metal complex; (ii) an alumoxane cocatalyst; (iii) an ionic activator; and optionally (iv) a crosslinked phenol.

[0126] Non-limiting examples of component (i) are represented by formula (I): (LA)aM(PI)b(Q)n (I) where (LA) represents a bulky ligand; M represents an atom of Petition 870240100454, dated 11 / 26 / 2024, p. 32 / 169 24 / 76 metal; PI represents a phosphinimine ligand; Q represents a leaving group; a is 0 or 1; b is 1 or 2; (a+b) = 2; n is 1 or 2; and the sum of (a+b+n) equals the valence of the metal M.

[0127] In one embodiment of the disclosure, LA is selected from the group consisting of unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl and substituted fluorenyl.

[0128] In one embodiment of the revelation, M is a metal selected from the group consisting of titanium, hafnium, and zirconium.

[0129] In additional non-limiting embodiments of the disclosure, the bulky linker LA in formula (I) includes unsubstituted or substituted cyclopentadienyl linkers or cyclopentadienyl type linkers, substituted heteroatom and / or heteroatom containing cyclopentadienyl type linkers. In additional non-limiting embodiments, the bulky linker LA in formula (I) includes cyclopentaphenanthreneyl linkers, unsubstituted or substituted indenyl linkers, benzindenyl linkers, unsubstituted or substituted fluorenyl linkers, octahydrofluorenyl linkers, cyclooctatetraendyl linkers, cyclopentacyclododecene linkers, azenyl linkers, azulene linkers, pentalene linkers, phosphoyl linkers, phosphinimine linkers, pyrrolyl linkers, pyrozolyl linkers, carbazolyl linkers, borabenzene linkers and the like, including hydrogenated versions thereof, for example, tetrahydroindenyl linkers.In other embodiments, LA may be any other ligand structure capable of η-linking to metal M; such embodiments include η3-linking and θ5-linking to metal M. In other embodiments, LA may comprise one or more heteroatoms, for example, nitrogen, silicon, boron, germanium, sulfur, and phosphorus, in combination with carbon atoms to form an open, acyl ring or a fused ring, or ring system, for example, a heterocyclopentadienyl auxiliary ligand. Other non-limiting embodiments for LA include amides, phosphides, alkoxides, aryloxides, imides, carbolides, borollides, porphyrins, phthalocyanines, etc. Petition 870240100454, dated 11 / 26 / 2024, p. 33 / 169 25 / 76 corrins and other bulky polyazomacrocycles.

[0130] Non-limiting examples of metal M in formula (I) include Group 4 metals, titanium, zirconium and hafnium.

[0131] In one embodiment of the revelation, the metal M is titanium, Ti.

[0132] The phosphinimine ligand, PI, is defined by formula (II): (Rp)3P = N- (II) wherein the Rp groups are independently selected from: a hydrogen atom; a halogen atom; C1-20 hydrocarbyl radicals that are unsubstituted or substituted by one or more halogen atoms; a C1e alkoxy radical; a Ce-io aryl radical; a Ce-io aryloxy radical; an amido radical; a silyl radical of formula -Si(Rs)3, wherein the Rs groups are independently selected from, a hydrogen atom, an alkyl or C1-8 alkoxy radical, a Ce-io aryl radical, a Ce-io aryloxy radical, or a germanyl radical of formula -Ge(RG)3, wherein the RG groups are defined as Rs defined in this paragraph.

[0133] The initial group Q is any ligand that can be removed from formula (I) that forms a kind of polymerization catalyst of one or more olefin(s). An equivalent term for Q is an “activatable ligand”, that is, equivalent to the term “initial group”. In some embodiments, Q is a labile monoanionic ligand having a sigma bond to M. Depending on the oxidation state of the metal, the value for n is 1 or 2 so that formula (I) represents a neutral bulky ligand-metal complex. Non-limiting examples of Q ligands include a hydrogen atom, halogens, C1-20 hydrocarbyl radicals, C1-20 alkoxy radicals, C5-10 aryl oxide radicals; these radicals may be linear, branched or cyclic or substituted by halogen atoms, C1-10 alkyl radicals, C110 alkoxy radicals, aryl or C5-10 aryloxy radicals.Additional non-limiting examples of Q ligands include weak bases such as amines, phosphines, ethers, carboxylates, dienes, and hydrocarbyl radicals having from 1 to 20 carbon atoms. Two Q ligands are also possible. Petition 870240100454, dated 11 / 26 / 2024, p. 34 / 169 26 / 76 joined together and form, for example, a substituted or unsubstituted diene ligand (e.g., 1,3-butadiene); or a group containing a delocalized heteroatom such as an acetate or acetamidinate group.

[0134] In one embodiment of the disclosure, Q is independently selected from the group consisting of a hydrogen atom, a halogen atom, a C1-10 hydrocarbyl radical, a C1-10 alkoxy radical and a C5-10 aryl oxide radical; wherein each of said hydrocarbyl, alkoxy and aryl oxide radicals may be unsubstituted or additionally substituted by a halogen atom, a C1-18 alkyl radical, a C1-8 alkoxy radical, a C1-10 aryl or aryloxy radical, an amide radical that is unsubstituted or substituted by up to two C1-8 alkyl radicals or a phosphide radical that is unsubstituted or substituted by up to two C18 alkyl radicals

[0135] In one embodiment of the disclosure, each Q is independently selected from the group consisting of a halide atom, a C1-4 alkyl radical and a benzyl radical. In another embodiment of the disclosure, activatable ligands Q are monoanionic such as a halide (e.g., chloride) or a hydrocarbyl (e.g., methyl, benzyl).

[0136] The second single-site catalyst component, component (ii), is an alumoxane co-catalyst that activates component (i) to a cationic complex. An equivalent term for “alumoxane” is “aluminoxane”; although the exact structure of this co-catalyst is uncertain, experts in the field generally agree that it is an oligomeric species containing repeating units of the general formula (III): (R)2AlO-(Al(R)-O)n-Al(R)2 (III) where the R groups can be identical or different linear, branched, or cyclic hydrocarbyl radicals containing from 1 to 20 carbon atoms and is from 0 to about 50. A non-limiting example of an alumoxane is methyl aluminoxane (or MAO). Petition 870240100454, dated 11 / 26 / 2024, page 35 / 169 27 / 76 where each R group in formula (III) is a methyl radical.

[0137] The third catalyst component (iii) of the single-site catalyst formulation is an ionic activator. In general, ionic activators are composed of a bulky cation and anion; wherein the latter is substantially uncoordinated. Non-limiting examples of ionic activators are boron ionic activators which are four-coordinate with four ligands bonded to the boron atom. Non-limiting examples of boron ionic activators include formulas (IV) and (V) shown below: [R5]+[B(R7)4]- (IV) where B represents a boron atom, R5 is an aromatic hydrocarbyl (e.g., triphenyl methyl cation) and each R7 is independently selected from phenyl radicals that are unsubstituted or substituted by 3 to 5 substituents selected from fluorine atoms, alkyl radicals or Cu alkoxy radicals that are unsubstituted or substituted by fluorine atoms; and a silyl radical of formula Si(R9)3, where each R9 is independently selected from hydrogen atoms and Cm alkyl radicals, and; compounds of formula (V); [(R8)tZH]+[B(R7)4]' (V) where B is a boron atom, H is a hydrogen atom, Z is a nitrogen or phosphorus atom, t is 2 or 3 and R8 is selected from C1-e alkyl radicals, phenyl radicals that are unsubstituted or substituted by up to three C14 alkyl radicals, or an R8 taken together with the nitrogen atom can form an aniline radical and R7 is as defined above in formula (IV).

[0138] In both formulas (IV) and (V), a non-limiting example of R7 is a pentafluorophenyl radical. In general, boron ionic activators can be described as tetra(perfluorophenyl)boron salts; non-limiting examples include aniline, carbonium, oxonium, phosphonium, and sulfonic salts of tetra(perfluorophenyl)boron with aniline and trityl (or triphenylmethyl). Additional non-limiting examples of ionic activators Petition 870240100454, dated 11 / 26 / 2024, page 36 / 169 28 / 76 incluem: triethylammoniotetra(phenyl)boron, tripropylammoniotetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tributylammonium tetra(pentafluorophenyl)boron, 28 / 76; tripropylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(m,m-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron, N,Ndimethylanilinium tetra(phenyl)boron, N, N-diethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)n-butylboron, N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron, di(isopropyl)ammonium tetra(pentafluorophenyl)boron, dicyclooxylammonium tetra(phenyl)boron, triphenylphosphonium tetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron, tri(dimethylphenyl)phosphonium tetra(phenyl)boron, tropyl tetracispentafluorophenyl borate, triphenylmethyllinium tetracispentafluorophenyl borate, benzene(diazonium)tetracispentafluorophenyl borate, tropyl tetracis(2,3,56-tetrafluorophenyl)borate, triphenylmethylinium tetracis(2,3,5,6-tetrafluorophenyl)borate, benzene(diazonium) tetracis(3,4,5-trifluorophenyl)borate, tropylium tetracis(3,4,5-trifluorophenyl)borate, benzene(diazonium) tetracis(3,4,5-trifluorophenyl)borate, tropylium tetracis(1,2,2-trifluoroethenyl)borate, triphenylmethylinium tetracis(1,2,2-trifluoroethenyl)borate, benzene(diazonium) tetracis(1,2,2-trifluoroethenyl)borate, tropylium tetracis(2,3,4,5-tetrafluorophenyl)borate, triphenylmethylinium tetracis(2,3,4,5-tetrafluorophenyl)borate, and benzene(diazonium) tetracis(2,3,4,5 (tetrafluorophenyl)borate. Readily available commercial ionic activators include N,N-dimethylaniline tetracispentafluorophenyl borate and triphenylmethylinium tetracispentafluorophenyl borate.

[0139] The optional fourth catalyst component of the single-site catalyst formulation is a crosslinked phenol, component (iv). Non-limiting examples of crosslinked phenols include butylated phenolic antioxidants, butylated hydroxytoluene, 2,4-di-tert-butyl-6-ethyl phenol, 4,4'-methylenebis(2,6-di-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene and octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate. Petition 870240100454, dated 11 / 26 / 2024, p. 37 / 169 29 / 76

[0140] To produce a single-site active catalyst formulation in a development embodiment, the amount and molar ratios of the three or four components, (i) to (iv) are optimized as described in U.S. Patent No. 9,512,282.

[0141] In one embodiment of the disclosure, the high-density polyethylene comprises a nucleating agent or a mixture of nucleating agents.

[0142] The term “nucleating agent”, as used here, means to convey its conventional meaning to individuals skilled in the art of preparing nucleated polyolefin compositions, that is, an additive that changes the crystallization behavior of a polymer as the polymer melt is cooled.

[0143] An analysis of the nucleating agents is provided in U.S. Patents Nos. 5,981,636, 6,465,551 and 6,599,971.

[0144] Commercially available nucleating agents that can be added to high-density polyethylene are dibenzylidene sorbitol esters (such as the products marketed under the brand name MILLAD® 3988 by Milliken Chemical and IRGACLEAR® by Ciba Specialty Chemicals). Additional examples of nucleating agents that can be added to high-density polyethylene include the cyclic organic structures disclosed in U.S. Patent No. 5,981,636 (and salts thereof, such as disodium bicyclo[2.2.1]heptene dicarboxylate); the saturated versions of the structures disclosed in U.S. Patent No. 5,981,636 (as disclosed in U.S. Patent No. 6,465,551; Zhao et al., by Milliken); the salts of certain cyclic dicarboxylic acids having a hexahydrophthalic acid structure (or “HHPA” structure) as disclosed in U.S. Patent No. 6,599,971 (Dotson et al., per Milliken); and phosphate esters, such as those disclosed in U.S. Patent No. 5,342.868 and those marketed under the trademarks NA11 and NA-21 together with Asahi Denka Kogyo, cyclic dicarboxylates and their salts. Petition 870240100454, dated 11 / 26 / 2024, p. 38 / 169 30 / 76 such as divalent metal or metalloid salts (particularly calcium salts) of the HHPA structures disclosed in U.S. Patent No. 6,599,971. For clarity, the HHPA structure generally comprises a ring structure with six carbon atoms in the ring and two carboxylic acid groups that are substituents on adjacent atoms of the ring structure. The other four carbon atoms in the ring may be substituted as disclosed in U.S. Patent No. 6,599,971. An example is 1,2-cyclohexane dicarboxylic acid, calcium salt (CAS Registry Number 491589-221). Still other examples of nucleating agents that may be added to high-density polyethylene include those disclosed in WO2015042561, WO2015042563, WO2015042562, and WO2011050042.

[0145] In one embodiment of the disclosure, high-density polyethylene comprises a nucleating agent or a mixture of nucleating agents comprising a salt of a dicarboxylic acid compound.

[0146] Many of the nucleating agents described above can be difficult to mix with high-density polyethylene being nucleated and it is known to use dispersing aids, such as zinc stearate, to mitigate this problem.

[0147] In one embodiment of the revelation, the nucleating agents are well dispersed in high-density polyethylene.

[0148] In the development embodiments, the proportion of nucleating agent used may be from 100 to 10,000 parts per million by weight (based on the weight of high-density polyethylene), or from 100 to 5,000 ppm, or from 100 to 3,000 ppm.

[0149] Individuals skilled in the art will appreciate that some care must be taken to ensure that the nucleating agent is well dispersed. In one embodiment of the development, the nucleating agent is added in a finely divided form (less than 50 microns, especially less than 10 microns) to high-density polyethylene to facilitate mixing. This type of “physical blending” (this Petition 870240100454, dated 11 / 26 / 2024, page 39 / 169 31 / 76 is a mixture of the nucleating agent and the resin in solid form) is generally preferred to the use of a nucleator “masterbatch” (where the term “masterbatch” refers to the practice of first melt mixing the additive – nucleator, in this case with a small amount of high-density polyethylene – then melt mixing the “masterbatch” with the remaining volume of high-density polyethylene).

[0150] In one embodiment of the disclosure, an additive such as a nucleating agent may be added to high-density polyethylene by means of a “masterbatch”, wherein the term “masterbatch” refers to the practice of first melt mixing the additive (e.g., a nucleator) with a small amount of high-density polyethylene, followed by melt mixing the “masterbatch” with the remaining volume of high-density polyethylene.

[0151] In the disclosure embodiments, high-density polyethylene may also contain other conventional additives, examples of which are not limiting: (1) primary antioxidants (such as, for example, cross-linked phenols, including vitamin E); (2) secondary antioxidants (such as, for example, phosphites and phosphonites); and (3) processing aids (such as, for example, fluoroelastomer-linked processing aid and / or polyethylene glycol).

[0152] Other non-limiting examples of additives that can be added to high-density polyethylene in the development modalities include nitrones, antacids, UV absorbers, metal deactivators, pigments, dyes, fillers and reinforcing agents, nanoscale organic or inorganic materials, antistatic agents, lubricating agents such as calcium stearate, and slip additives such as erucimide and behenamide. Film structure

[0153] In one embodiment of the present disclosure, a film structure comprises alternating and adjacent layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene. Petition 870240100454, dated 11 / 26 / 2024, page 40 / 169 32 / 76 density. Correspondingly, in one embodiment, the film structure of the present disclosure will be an all-polyethylene film structure and will be a multilayer film structure.

[0154] In one embodiment, the difference in density between linear low-density polyethylene (A) and high-density polyethylene (B) is at least 0.015 g / cm3.

[0155] In one embodiment, the difference in density between linear low-density polyethylene (A) and high-density polyethylene (B) is at least 0.030 g / cm3.

[0156] In one embodiment of the development, an all-polyethylene multilayer film structure has at least one shell layer comprising (A) a linear low-density polyethylene.

[0157] In one embodiment of the development, an all-polyethylene multilayer film structure has at least three alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene.

[0158] In one embodiment of the development, an all-polyethylene multilayer film structure has at least five alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene.

[0159] In one embodiment of the development, an all-polyethylene multilayer film structure has at least seven alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene.

[0160] In one embodiment of the development, an all-polyethylene multilayer film structure has at least nine alternating and adjacent film layers of two different polyethylene polymers: (A) a low-density polyethylene Petition 870240100454, dated 11 / 26 / 2024, page 41 / 169 33 / 76 linear density and (B) a high-density polyethylene.

[0161] In one embodiment of the development, an all-polyethylene multilayer film structure has three alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene.

[0162] In one embodiment of the development, an all-polyethylene multilayer film structure has five alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene.

[0163] In one embodiment of the development, an all-polyethylene multilayer film structure has seven alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene.

[0164] In one embodiment of the development, an all-polyethylene multilayer film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene.

[0165] In one embodiment of the development, an all-polyethylene multilayer film structure has eleven alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene.

[0166] In one embodiment of the development, an all-polyethylene multilayer film structure has three alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, provided that the film layers are arranged in the following structure: A / B / A.

[0167] In a mode of revelation, a film structure Petition 870240100454, dated 11 / 26 / 2024, page 42 / 169 34 / 76 multilayer all-polyethylene has three alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, provided that the film layers are arranged in the following structure: B / A / B.

[0168] In one embodiment of the development, an all-polyethylene multilayer film structure has five alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, provided that the film layers are arranged in the following structure: A / B / A / B / A.

[0169] In one embodiment of the development, an all-polyethylene multilayer film structure has five alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, provided that the film layers are arranged in the following structure: B / A / B / A / B.

[0170] In one embodiment of the development, an all-polyethylene multilayer film structure has seven alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, provided that the film layers are arranged in the following structure: A / B / A / B / A / B / A.

[0171] In one embodiment of the development, an all-polyethylene multilayer film structure has seven alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, provided that the film layers are arranged in the following structure: B / A / B / A / B / A / B.

[0172] In one embodiment of the development, an all-polyethylene multilayer film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a low-density polyethylene Petition 870240100454, dated 11 / 26 / 2024, page 43 / 169 35 / 76 linear and (B) a high-density polyethylene, provided that the film layers are arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0173] In one embodiment of the development, an all-polyethylene multilayer film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, provided that the film layers are arranged in the following structure: B / A / B / A / B / A / B / A / B.

[0174] In one embodiment of the development, a multilayer film structure made entirely of polyethylene has eleven alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, provided that the film layers are arranged in the following structure: A / B / A / B / A / B / A / B / A / B / A.

[0175] In one embodiment of the development, an all-polyethylene multilayer film structure has eleven alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, provided that the film layers are arranged in the following structure: B / A / B / A / B / A / B / A / B / A / B.

[0176] Non-limiting examples of processes for preparing these film structures include blown film and cast film processes.

[0177] In the blown film extrusion process, an extruder heats, melts, mixes, and conveys a thermoplastic, or a blend of thermoplastics. Once melted, the thermoplastic is forced through an annular die to produce a thermoplastic tube. In the case of co-extrusion, multiple extruders are employed to produce a multilayer thermoplastic tube. The temperature of the extrusion process is primarily determined by the thermoplastic or blend of thermoplastics being processed, for example, the melting temperature or glass transition temperature of the thermoplastic and the desired viscosity of the melt. In the case of polyolefins, Petition 870240100454, dated 11 / 26 / 2024, page 44 / 169 Typical extrusion temperatures range from 330°F to 550°F (166°C to 288°C). Upon exiting the annular die, the thermoplastic tube is inflated with air, cooled, solidified, and pulled through a pair of pressure rollers. Due to air inflation, the tube increases in diameter, forming a bubble of the desired size. Due to the pulling action of the pressure rollers, the bubble is stretched in the machine direction. Thus, the bubble is stretched in two directions: the transverse direction (TD) where the inflation air increases the bubble diameter; and the machine direction (MD) where the pressure rollers stretch the bubble. As a result, the physical properties of blown films are typically anisotropic, that is, the physical properties differ in the MD and TD directions; for example, film tear resistance and tensile properties typically differ in MD and TD.In some prior art documents, the terms “transverse direction” or “CD” are used; these terms are equivalent to the terms “transverse direction” or “TD” used in this disclosure. In the blown film process, air is also blown into the outer bubble circumference to cool the thermoplastic as it exits the annular die. The final film width is determined by controlling the inflation air or the inner bubble pressure; in other words, increasing or decreasing the bubble diameter. Film thickness is primarily controlled by increasing or decreasing the speed of the pressure rollers to control the draw rate. After exiting the pressure rollers, the bubble or tube is collapsed and can be split in the machine direction, thus creating lamination. Each sheet can be wound onto a roll of film. Each roll can be further split to create a film of desired width.Each roll is further processed into a variety of consumer products as described below.

[0178] The cast film process is similar to that in which a single extruder or multiple extruders may be used; however, the various thermoplastic materials are metered onto a flat die and extruded into a single-layer or multi-layer sheet instead of a tube. In the cast film process, the Petition 870240100454, dated 11 / 26 / 2024, page 45 / 169 37 / 76 extruded blade is solidified on a cooling roll.

[0179] In the cast film process, films are extruded from a flat die or onto a cooled roll or a pressed roll, optionally with a vacuum box and / or an air knife. Cast films can be single-layer films or co-extruded multi-layer films obtained by multiple extrusions through a single die or multiple dies. The resulting films can be used as is or can be laminated to other films or substrates, for example, by thermal extrusion, adhesive lamination or direct extrusion onto a substrate. The resulting films and laminates can be subjected to other forming operations such as embossing, stretching, thermoforming. Surface treatments such as corona can be applied and the films can be printed.

[0180] In the fused film extrusion process, a thin film is extruded through a slit onto a highly polished, cooled rotating roll, where it is cooled from one side. The roll speed controls the extraction ratio and the final thickness of the film. The film is then sent to a second roll for cooling on the other side. Finally, it passes through a system of rolls and is wound onto a reel.

[0181] Depending on the end-use application, the film structure can span a wide range of thicknesses. Non-limiting examples include films for food packaging where thicknesses can range from about 0.5 mil (13 pm) to about 4 mil (102 pm), and films for heavy-duty bags can range from about 2 mil (51 pm) to about 10 mil (254 pm).

[0182] In embodiments of the development, the thickness of a specific layer in a multilayer film structure may be about 1% (i.e., the lower limit), or about 3%, or about 5%, or about 10%, or about 15%, or about 20%, or about 25%, or about 30% of the total multilayer film thickness. In other embodiments, the thickness of a Petition 870240100454, dated 11 / 26 / 2024, p. 46 / 169 38 / 76 specific layer in a multilayer film can be up to about 95% (that is, the upper limit), in other cases about 80%, and in still other cases about 65% of the total multilayer film thickness.

[0183] Film structure can be used in a wide range of manufactured articles. Non-limiting examples of such manufactured articles include: films for food packaging (fresh and frozen foods, liquids and granular foods), backing bags, retortable packaging and bag-in-box packaging; barrier films (oxygen, moisture, aroma, oil, etc.) and modified atmosphere packaging, bundling shrink films, pallet shrink films, shrink bags, shrink packages and shrink wraps; light and heavy stretch films, hand stretch film, machine stretch wrap and stretch cover films; high clarity films; heavy bags; household wraps, packaging films and sandwich bags;Industrial and institutional films, garbage bags, can liners, magazine packaging, newspaper bags, mailbags, bags and envelopes, bubble wrap, carpet films, furniture bags, garment bags, coin purses, automotive dashboard films; medical applications such as aprons, drapes and surgical gowns; construction films and sheets, asphalt films, insulation bags, mask films, landscaping films and bags; geomembrane liners for municipal waste disposal and mining applications; lot inclusion bags; agricultural films, plant cover films and greenhouse films; retail packaging, self-service bags, boutique bags, supermarket bags, shipping bags and T-shirt bags;Oriented films, machine-oriented and biaxially oriented films, and functional film layers in oriented polypropylene (OPP) films, for example, sealant and / or toughness layers. Additional manufactured articles include multilayer laminates and / or films; laminations with paper; aluminum foil laminates or laminates containing; Petition 870240100454, dated 11 / 26 / 2024, page 47 / 169 39 / 76 vacuum-deposited aluminum; polyamide laminates; polyester laminates; extrusion-coated laminates; and hot-melt adhesive formulations.

[0184] The cast film structures of the present disclosure can be used in a variety of end uses, such as, for example, food packaging (dry foods, fresh foods, frozen foods, liquid processed foods, powders, granules), for packaging detergents, toothpastes, towels, for labels and self-adhesives. Cast film structures can also be used in unitization and industrial packaging, notably in stretch films. Cast film structures may also be suitable in hygiene and medical applications, for example, in breathable and non-breathable films used in diapers, adult incontinence products, feminine hygiene products, ostomy bags.

[0185] The desired physical properties of film structure typically depend on the application of interest. Non-limiting examples of desirable film structure properties include: optical properties (brightness and opacity), dart impact, Elmendorf tear, modulus (1% and 2% secant modulus), puncture propagation tear resistance, tensile properties (yield strength, tensile strength, elongation at break, robustness, etc.) and ripple properties.

[0186] In development methods, a multilayer film can consist of a structure of 3, 5, 7, 9 or 11 layers made in a co-extrusion process.

[0187] In one embodiment of the development, each layer of film structure can be chosen to provide a specific functionality or property. Without wishing to dwell on theory, a multilayer polyethylene film structure can be designed to achieve desired performance requirements for many end-use applications in a cost-effective, value-added, and recyclable manner. Some possible desirable properties of a structure of Petition 870240100454, dated 11 / 26 / 2024, page 48 / 169 40 / 76 film can include barrier, mechanical, sealing, and optical properties, each of which can be considerably influenced by the nature of the polymer layers in the film structure. The versatility of a multilayer film structure makes it a uniquely adaptable polymeric material for food packaging, lamination, thermoforming, capping films, shrink films, oriented films, agricultural films, medical and healthcare films, or industrial lining applications.

[0188] The films used in the film structure may optionally include, depending on their intended use, additives and adjuvants. Non-limiting examples of additives and adjuvants include antiblocking agents, antioxidants, thermal stabilizers, slip agents, processing aids, antistatic additives, colorants, dyes, fillers, light stabilizers, light absorbers, lubricants, pigments, plasticizers, nucleating agents and combinations thereof.

[0189] In one embodiment, a film structure is prepared on a multilayer blown film line.

[0190] In one embodiment, a film structure is prepared on a multilayer cast film line.

[0191] One type of development consists of a multilayer film structure having a thickness of 0.5 to 10 mils.

[0192] In the development modalities, a 1.5 mil multilayer blown film structure will have a dart impact resistance of > 85 g / mil, or > 90 g / mil, or > 95 g / mil, or > 100 g / mil.

[0193] In the development embodiments, a 1.5 mil multilayer blown film structure will have a dart impact resistance of > 85 g / mil, or > 90 g / mil, or > 95 g / mil, or > 100 g / mil, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: Petition 870240100454, dated 11 / 26 / 2024, p. 49 / 169 41 / 76 (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0194] In another embodiment of the development, a 1.5 mil multilayer blown film structure will have a dart impact resistance of 85 to 120 g / mil. In a further embodiment of the development, a 1.5 mil multilayer blown film structure will have a dart impact resistance of 90 g / mil to 110 g / mil.

[0195] In the development embodiments, a 1.5 mil multilayer blown film structure will have a dart impact resistance of 85 to 120 g / mil, or 90 to 110 g / mil, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0196] In the development modalities, a 2 mil multilayer blown film structure will have a dart impact resistance of > 85 g / mil, or > 90 g / mil, or > 95 g / mil, or > 100 g / mil.

[0197] In the development embodiments, a 2 mil multilayer blown film structure will have a dart impact resistance of > 85 g / mil, or > 90 g / mil, or > 95 g / mil, or > 100 g / mil, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0198] In another embodiment of the development, a 2 mil multilayer blown film structure will have a dart impact resistance of 85 to 120 g / mil. In a further embodiment of the development, a 2 mil multilayer blown film structure will have a dart impact resistance of 90 g / mil to 110 g / mil. Petition 870240100454, dated 11 / 26 / 2024, p. 50 / 169 42 / 76

[0199] In the development embodiments, a 2 mil multilayer blown film structure will have a dart impact resistance of 85 to 120 g / mil, or 90 g / mil to 110 g / mil, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0200] In one embodiment of the development, the dart impact resistance of an all-polyethylene multilayer film structure is increased by arranging adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene in strictly alternating layers (i.e., film structures of the type: A / B / A..., such as A / B / A, A / B / A / B / A, A / B / A / B / A / B / A, A / B / A / B / A / B / A / B / A, etc.; or film structures of the type B / A / B..., such as B / A / B, B / A / B / A / B, B / A / B / A / B / A / B, B / A / B / A / B / A / B / A / B, etc.).

[0201] In the development modalities, a 1.5 mil multilayer blown film structure will have an opacity value of £25%, or £20%, or <18%, or <15%. In the development modalities, a 1.5 mil multilayer blown film structure will have an opacity value of 8 to 25%, or 8 to 20%, or 10 to 20%, or 8 to 18%, or 10 to 18%, or 8 to 15%, or 10 to 15%.

[0202] In the development modalities, a 1.5 mil multilayer blown film structure will have an opacity value of < 25%, or < 20%, or < 18%, or < 15%, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0203] In the development modalities, a 1.5 mil multilayer blown film structure will have an opacity value of 8 to 25%, or 8 to 20%, or 10 to 20%, or 8 to 18%, or 10 to 18%, or 8 to 15%, or 10 to 15%, provided Petition 870240100454, dated 11 / 26 / 2024, p. 51 / 169 43 / 76 that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0204] In the development modalities, a 2 mil multilayer blown film structure will have an opacity value of < 25%, or < 20%, or < 18%, or < 15%. In the development modalities, a 2 mil multilayer blown film structure will have an opacity value of 8 to 25%, or 8 to 20%, or 10 to 20%, or 8 to 18%, or 10 to 18%.

[0205] In the development modalities, a 2 mil multilayer blown film structure will have an opacity value of < 25%, or < 20%, or < 18%, or < 15%, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0206] In the development modalities, a 1.5 mil multilayer blown film structure will have an opacity value of 8 to 25%, or 8 to 20%, or 10 to 20%, or 8 to 18%, or 10 to 18%, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0207] In one embodiment of the development, the opacity value of an all-polyethylene multilayer film structure is reduced by arranging adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene in strictly alternating layers (i.e., film structures of the type: A / B / A..., such as A / B / A, A / B / A / B / A, A / B / A / B / A / B / A, A / B / A / B / A / B / A / B / A, etc.; or film structures of the type B / A / B..., such as B / A / B, B / A / B / A / B, B / A / B / A / B / A / B, B / A / B / A / B / A / B / A / B, etc.). Petition 870240100454, dated 11 / 26 / 2024, p. 52 / 169 44 / 76

[0208] In the development modalities, a 1.5 mil multilayer blown film structure will have a brightness (at 45 degrees) of at least 45, or at least 50, or at least 55.

[0209] In the development embodiments, a 1.5 mil multilayer blown film structure will have a brightness (at 45 degrees) of at least 45, or at least 50, or at least 55, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0210] In the development modalities, a 2 mil multilayer blown film structure will have a brightness (at 45 degrees) of at least 45, or at least 50, or at least 55.

[0211] In the development embodiments, a 2 mil multilayer blown film structure will have a brightness (at 45 degrees) of at least 45, or at least 50, or at least 55, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0212] In one embodiment of the development, the brightness (at 45 degrees) of an all-polyethylene multilayer film structure is increased by arranging adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene in strictly alternating layers (i.e., film structures of the type: A / B / A..., such as A / B / A, A / B / A / B / A, A / B / A / B / A / B / A, A / B / A / B / A / B / A / B / A, etc.; or film structures of the type B / A / B..., such as B / A / B, B / A / B / A / B, B / A / B / A / B / A / B, B / A / B / A / B / A / B / A / B, etc.).

[0213] In development modes, a 1.5 mil multilayer blown film structure will have a puncture energy of > 50 J / mm, or > 55 J / mm, Petition 870240100454, dated 11 / 26 / 2024, p. 53 / 169 45 / 76 or > 60 J / mm.

[0214] In the development embodiments, a 1.5 mil multilayer blown film structure will have a piercing energy of > 50 J / mm, or > 55 J / mm, or > 60 J / mm, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0215] In development modes, a 1.5 mil multilayer blown film structure will have a piercing energy of 50 to 90 J / mm, or 50 to 80 J / mm, or 50 to 75 J / mm, or 55 to 75 J / mm.

[0216] In the development embodiments, a 1.5 mil multilayer blown film structure will have a piercing energy of 50 to 90 J / mm, or 50 to 80 J / mm, or 50 to 75 J / mm, or 55 to 75 J / mm, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0217] In development modes, a 2 mil multilayer blown film structure will have a puncture energy of > 50 J / mm, or > 55 J / mm, or > 60 J / mm, or > 65 J / mm, or > 70 J / mm.

[0218] In the development embodiments, a 2 mil multilayer blown film structure will have a piercing energy of > 50 J / mm, or > 55 J / mm, or > 60 J / mm, or > 65 J / mm, or > 70 J / mm, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0219] In development modes, a 2 mil multilayer blown film structure will have a perforation energy of 50 to 90 J / mm, or 60 to Petition 870240100454, dated 11 / 26 / 2024, p. 54 / 169 46 / 76 J / mm, or from 60 to 85 J / mm.

[0220] In the development embodiments, a 2 mil multilayer blown film structure will have a piercing energy of 50 to 90 J / mm, or 60 to 90 J / mm, or 60 to 85 J / mm, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0221] In one embodiment of the development, the piercing energy of an all-polyethylene multilayer film structure is increased by arranging adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene in strictly alternating layers (i.e., film structures of the type: A / B / A..., such as A / B / A, A / B / A / B / A, A / B / A / B / A / B / A, A / B / A / B / A / B / A / B / A, etc.; or film structures of the type B / A / B..., such as B / A / B, B / A / B / A / B, B / A / B / A / B / A / B, B / A / B / A / B / A / B / A / B, etc.).

[0222] In development modes, a 1.5 mil multilayer blown film structure will have a maximum Dynatup load of > 5.0 lb, or > 5.5 lb.

[0223] In development modes, a 1.5 mil multilayer blown film structure will have a maximum Dynatup load of 4.5 to 9.0 lb, or 5.0 to 8.5 lb, or 5.0 to 8.0 lb, or 5.0 to 7.0 lb.

[0224] In the development embodiments, a 1.5 mil multilayer blown film structure will have a maximum Dynatup load of > 5.0 lb, or > 5.5 lb, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0225] In development modes, a 1.5 mil multilayer blown film structure will have a maximum Dynatup load of 4.5 to 9.0 lb, or 5.0 to Petition 870240100454, dated 11 / 26 / 2024, p. 55 / 169 47 / 76 8.5 lb, or 5.0 to 8.0 lb, or 5.0 to 7.0 lb, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0226] In development modes, a 2 mil multilayer blown film structure will have a maximum Dynatup load of > 5.5 lb, or > 6.0 lb, or > 6.5 lb or > 7.0 lb.

[0227] In development modes, a 2 mil multilayer blown film structure will have a maximum Dynatup load of 5.5 to 10.0 lb, or 6.0 to 9.5 lb, or 6.5 to 9.0 lb.

[0228] In the development embodiments, a 2 mil multilayer blown film structure will have a maximum Dynatup load of > 5.5 lb, or > 6.0 lb, or > 6.5 lb or > 7.0 lb, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0229] In the development embodiments, a 2 mil multilayer blown film structure will have a maximum Dynatup load of 5.5 to 10.0 lb, or 6.0 to 9.5 lb, or 6.5 to 9.0 lb, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0230] In one embodiment of the development, the maximum Dynatup load of an all-polyethylene multilayer film structure is increased by arranging adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene in strictly alternating layers (i.e., film structures of the type: A / B / A..., such Petition 870240100454, dated 11 / 26 / 2024, page 56 / 169 48 / 76 such as A / B / A, A / B / A / B / A, A / B / A / B / A / B / A, A / B / A / B / A / B / A / B / A, etc.; or film structures of the type B / A / B..., such as B / A / B, B / A / B / A / B, B / A / B / A / B / A / B, B / A / B / A / B / A / B / A / B, etc.).

[0231] In the development modalities, a 1.5 mil multilayer blown film structure will have a secant modulus at 1% in the machine direction (MD) of > 400 MPa, or > 450 MPa, or > 500 MPa.

[0232] In the development modalities, a 1.5 mil multilayer blown film structure will have a secant modulus at 1% in the machine direction (MD) of 400 MPa to 700 MPa, or 450 to 650 MPa, or 500 to 650 MPa.

[0233] In the development embodiments, a 1.5 mil multilayer blown film structure will have a drying modulus at 1% in the machine direction (MD) of > 400 MPa, or > 450 MPa, or > 500 MPa, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0234] In the development embodiments, a 1.5 mil multilayer blown film structure will have a drying modulus at 1% in the machine direction (MD) of 400 MPa to 700 MPa, or 450 to 650 MPa, or 500 to 650 MPa, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0235] In the development modalities, a 2 mil multilayer blown film structure will have a secant modulus at 1% in the machine direction (MD) of > 400 MPa, or > 450 MPa, or > 500 MPa.

[0236] In the development modalities, a 2 mil multilayer blown film structure will have a secant modulus at 1% in the machine direction (MD) of 400 MPa to 700 MPa, or 450 to 650 MPa, or 500 to 650 MPa.

[0237] In the modes of revelation, a blown film structure Petition 870240100454, dated 11 / 26 / 2024, page 57 / 169 49 / 76 multilayer 2 mil will have a secant modulus at 1% in the machine direction (MD) of > 400 MPa, or > 450 MPa, or > 500 MPa, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0238] In the development embodiments, a 2 mil multilayer blown film structure will have a drying modulus at 1% in the machine direction (MD) of 400 MPa to 700 MPa, or 450 to 650 MPa, or 500 to 650 MPa, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0239] In the development modalities, a 1.5 mil multilayer blown film structure will have a secant modulus at 1% in the transverse direction (TD) of > 500 MPa, or > 550 MPa, or > 600 MPa, or £ 650 MPa, or > 700 MPa.

[0240] In the development modalities, a 1.5 mil multilayer blown film structure will have a secant modulus at 1% in the transverse direction (TD) of 500 MPa to 900 MPa, or 550 to 900 MPa, or 550 to 850 MPa, or 600 to 850 MPa, or 600 to 800 MPa.

[0241] In the embodiments of the development, a 1.5 mil multilayer blown film structure will have a secant modulus at 1% in the transverse direction (TD) of z 500 MPa, or > 550 MPa, or > 600 MPa, or £ 650 MPa, or > 700 MPa, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0242] In the development modalities, a 1.5 mil multilayer blown film structure will have a secant modulus at 1% in the transverse direction (TD) of 500 MPa to 900 MPa, or 550 to 900 MPa, or 550 to 850 MPa, or 600 to Petition 870240100454, dated 11 / 26 / 2024, pp. 58 / 169 50 / 76 850 MPa, or 600 to 800 MPa, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0243] In the development modalities, a 2 mil multilayer blown film structure will have a secant modulus at 1% in the transverse direction (TD) of > 500 MPa, or > 550 MPa, or > 600 MPa, or > 650 MPa, or > 700 MPa.

[0244] In the development modalities, a 2 mil multilayer blown film structure will have a secant modulus at 1% in the transverse direction (TD) of 500 MPa to 900 MPa, or 550 to 900 MPa, or 550 to 850 MPa, or 600 to 850 MPa, or 600 to 800 MPa.

[0245] In the embodiments of the development, a 2 mil multilayer blown film structure will have a secant modulus at 1% in the transverse direction (TD) of > 500 MPa, or > 550 MPa, or > 600 MPa, or £ 650 MPa, or £ 700 MPa, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0246] In the development embodiments, a 2 mil multilayer blown film structure will have a secant modulus at 1% in the transverse direction (TD) of 500 MPa to 900 MPa, or 550 to 900 MPa, or 550 to 850 MPa, or 600 to 850 MPa, or 600 to 800 MPa, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0247] In development modalities, a 1.5 mil multilayer blown film structure will have an oxygen transmission rate (OTR) of < 100 cm3 per 100 inches2 per 24 hours, or < 80 cm3 per 100 inches2 per 24 hours, Petition 870240100454, dated 11 / 26 / 2024, pp. 59 / 169 51 / 76 or < 75 cm3 per 100 inches2 per 24 hours, or < 70 cm3 per 100 inches2 per 24 hours.

[0248] In development modes, a 1.5 mil multilayer blown film structure will have an oxygen transmission rate (OTR) of 35 to 100 cm3 per 100 inches2 per 24 hours, or 40 to 80 cm3 per 100 inches2 per 24 hours, or 50 to 75 cm3 per 100 inches2 per 24 hours.

[0249] In the development embodiments, a 1.5 mil multilayer blown film structure will have an oxygen transmission rate (OTR) of < 100 cm3 per 100 inches2 per 24 hours, or < 80 cm3 per 100 inches2 per 24 hours, or < 75 cm3 per 100 inches2 per 24 hours, or < 70 cm3 per 100 inches2 per 24 hours, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0250] In the development embodiments, a 1.5 mil multilayer blown film structure will have an oxygen transmission rate (OTR) of 35 to 100 cm3 per 100 inches2 per 24 hours, or 40 to 80 cm3 per 100 inches2 per 24 hours, or 50 to 75 cm3 per 100 inches2 per 24 hours, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0251] In development modalities, a 2 mil multilayer blown film structure will have an oxygen transmission rate (OTR) of 100 cm3 per 100 inches2 per 24 hours, or < 75 cm3 per 100 inches2 per 24 hours, or < 60 cm3 per 100 inches2 per 24 hours, or < 50 cm3 per 100 inches2 per 24 hours.

[0252] In the modes of revelation, a blown film structure Petition 870240100454, dated 11 / 26 / 2024, pp. 60 / 169 52 / 76 multilayer 2 mil panels will have an oxygen transmission rate (OTR) of 25 to 100 cm3 per 100 inches2 per 24 hours, or 25 to 75 cm3 per 100 inches2 per 24 hours, or 25 to 60 cm3 per 100 inches2 per 24 hours, or 30 to 75 cm3 per 100 inches2 per 24 hours, or 30 to 60 cm3 per 100 inches2 per 24 hours, or 25 to 50 cm3 per 100 inches2 per 24 hours.

[0253] In the development embodiments, a 2 mil multilayer blown film structure will have an oxygen transmission rate (OTR) of < 100 cm3 per 100 inches2 per 24 hours, or < 75 cm3 per 100 inches2 per 24 hours, or < 60 cm3 per 100 inches2 per 24 hours, or < 50 cm3 per 100 inches2 per 24 hours, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0254] In the development embodiments, a 2 mil multilayer blown film structure will have an oxygen transmission rate (OTR) of 25 to 100 cm3 per 100 inches2 per 24 hours, or 25 to 75 cm3 per 100 inches2 per 24 hours, or 25 to 60 cm3 per 100 inches2 per 24 hours, or 30 to 75 cm3 per 100 inches2 per 24 hours, or 30 to 60 cm3 per 100 inches2 per 24 hours, or 25 to 50 cm3 per 100 inches2 per 24 hours, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0255] In the development modalities, a 1.5 mil multilayer blown film structure will have a water vapor transmission rate (WVTR) of < 0.2400 grams per 100 inches2 per 24 hours, or < 0.2200 grams per 100 inches2 per 24 hours, or < 0.2000 grams per 100 inches2 per 24 hours, or < 0.1800 grams per 100 inches2 per 24 hours. Petition 870240100454, dated 11 / 26 / 2024, pp. 61 / 169 53 / 76

[0256] In development modalities, a 1.5 mil multilayer blown film structure will have a water vapor transmission rate (WVTR) of 0.1000 to 0.2400 grams per 100 inches2 per 24 hours, or 0.1000 to 0.2000 grams per 100 inches2 per 24 hours, or 0.1200 to 0.1800 grams per 100 inches2 per 24 hours, or 0.1400 to 0.2000 grams per 100 inches2 per 24 hours, or 0.1400 to 0.1800 grams per 100 inches2 per 24 hours.

[0257] In the development embodiments, a 1.5 mil multilayer blown film structure will have a water vapor transmission rate (WVTR) of < 0.2400 grams per 100 inches² per 24 hours, or < 0.2200 grams per 100 inches² per 24 hours, or < 0.2000 grams per 100 inches² per 24 hours, or < 0.1800 grams per 100 inches² per 24 hours, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0258] In the development embodiments, a 1.5 mil multilayer blown film structure will have a water vapor transmission rate (WVTR) of 0.1000 to 0.2400 grams per 100 inches² per 24 hours, or 0.1000 to 0.2000 grams per 100 inches² per 24 hours, or 0.1200 to 0.1800 grams per 100 inches² per 24 hours, or 0.1400 to 0.2000 grams per 100 inches² per 24 hours, or 0.1400 to 0.1800 grams per 100 inches² per 24 hours, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the structure a follow: A / B / A / B / A / B / A / B / A.

[0259] In development modalities, a 2 mil multilayer blown film structure will have a water vapor transmission rate (WVTR) of < 0.2000 grams per 100 inches² per 24 hours, or < 0.1800 grams per 100 inches² per 24 hours, or < 0.1600 grams per 100 inches² per 24 hours, or < Petition 870240100454, dated 11 / 26 / 2024, pp. 62 / 169 54 / 76 0.1400 grams per 100 cubic inches per 24 hours, or < 0.1200 grams per 100 cubic inches per 24 hours.

[0260] In development modes, a 2 mil multilayer blown film structure will have a water vapor transmission rate (WVTR) of 0.0400 to 0.2000 grams per 100 inches2 per 24 hours, or 0.0600 to 0.1800 grams per 100 inches2 per 24 hours, or 0.0600 to 0.1400 grams per 100 inches2 per 24 hours, or 0.0800 to 0.1400 grams per 100 inches2 per 24 hours.

[0261] In the development embodiments, a 2 mil multilayer blown film structure will have a water vapor transmission rate (WVTR) of < 0.2000 grams per 100 inches2 per 24 hours, or < 0.1800 grams per 100 inches2 per 24 hours, or < 0.1600 grams per 100 inches2 per 24 hours, or < 0.1400 grams per 100 inches2 per 24 hours, or < 0.1200 grams per 100 inches2 per 24 hours, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0262] In the development embodiments, a 2 mil multilayer blown film structure will have a water vapor transmission rate (WVTR) of 0.0400 to 0.2000 grams per 100 inches² per 24 hours, or 0.0600 to 0.1800 grams per 100 inches² per 24 hours, or 0.0600 to 0.1400 grams per 100 inches² per 24 hours, or 0.0800 to 0.1400 grams per 100 inches² per 24 hours, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0263] In the modes of revelation, a blown film structure Petition 870240100454, dated 11 / 26 / 2024, pp. 63 / 169 55 / 76 multilayer 1.5 mil sheets will have a machine direction (MD) radius of curvature greater than 5 mm, or greater than 10 mm, or greater than 15 mm, or greater than 25 mm, or approximately no machine direction waviness.

[0264] In development modalities, a 1.5 mil multilayer blown film structure will have a radius of curvature in the transverse direction (TD) greater than 5 mm, or greater than 10 mm, or greater than 15 mm, or greater than 25 mm, or approximately no transverse direction waviness.

[0265] In the development embodiments, a 1.5 mil multilayer blown film structure will have a machine-direction (MD) radius of curvature greater than 5 mm, or greater than 10 mm, or greater than 15 mm, or greater than 25 mm, or approximately no machine-direction waviness, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0266] In the development embodiments, a 1.5 mil multilayer blown film structure will have a radius of curvature in the transverse direction (TD) greater than 5 mm, or greater than 10 mm, or greater than 15 mm, or greater than 25 mm, or approximately no transverse direction waviness, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0267] In development modalities, a 2 mil multilayer blown film structure will have a machine-direction (MD) radius of curvature greater than 5 mm, or greater than 10 mm, or greater than 15 mm, or greater than 25 mm, or approximately no machine-direction undulations.

[0268] In development modalities, a 2 mil multilayer blown film structure will have a larger radius of curvature in the transverse direction (TD). Petition 870240100454, dated 11 / 26 / 2024, pp. 64 / 169 56 / 76 that is 5 mm, or greater than 10 mm, or greater than 15 mm, or greater than 25 mm, or approximately will not have undulations in the transverse direction.

[0269] In the development embodiments, a 2 mil multilayer blown film structure will have a machine-direction (MD) radius of curvature greater than 5 mm, or greater than 10 mm, or greater than 15 mm, or greater than 25 mm, or approximately no machine-direction waviness, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0270] In the development embodiments, a 2 mil multilayer blown film structure will have a radius of curvature in the transverse direction (TD) greater than 5 mm, or greater than 10 mm, or greater than 15 mm, or greater than 25 mm, or approximately no transverse direction waviness, provided that the film structure has nine alternating and adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene, arranged in the following structure: A / B / A / B / A / B / A / B / A.

[0271] In one embodiment of the development, the ripple properties of an all-polyethylene multilayer film structure are improved (i.e., one or more of the bend radii in MD and TD are increased or approximately no ripples occur in one or more MD and TD directions) by arranging adjacent film layers of two different polyethylene polymers: (A) a linear low-density polyethylene and (B) a high-density polyethylene in strictly alternating layers (i.e., film structures of the type: A / B / A..., such as A / B / A, A / B / A / B / A, A / B / A / B / A / B / A, A / B / A / B / A / B / A / B / A, etc.; or film structures of the type B / A / B..., such as B / A / B, B / A / B / A / B, B / A / B / A / B / A / B, B / A / B / A / B / A / B / A / B, etc.).

[0272] The following examples are presented for the purpose of illustrating selected modalities of this disclosure; it being understood that the examples Petition 870240100454, dated 11 / 26 / 2024, pp. 65 / 169 57 / 76 presented do not limit the claims presented. Examples General Testing Procedures

[0273] Before testing, each polymer specimen was conditioned for at least 24 hours at 23 ±2 °C and 50 ±10% relative humidity, and a subsequent test was conducted at 23 ±2 °C and 50 ±10% relative humidity. In this document, the term “ASTM conditions” refers to a laboratory maintained at 23 ±2 °C and 50 ±10% relative humidity; and the specimens to be tested were conditioned for at least 24 hours in that laboratory before testing. ASTM refers to the American Society for Testing and Materials. Density

[0274] Polymer densities were determined using ASTM D79213 (November 1, 2013). Merger Index

[0275] The polymer melt index was determined using ASTM D1238 (August 1, 2013). The melt indices, I2, Ie, I10, and I21 were measured at 190 °C, using weights of 2.16 kg, 6.48 kg, 10 kg, and 21.6 kg, respectively. Conventional Size Exclusion Chromatography (SEC)

[0276] Polymer sample solutions (1 to 3 mg / mL) were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) and spinning it on a wheel for 4 hours at 150°C in an oven. An antioxidant (2,6-di-tert-butyl-4-methylphenol (BHT)) was added to the mixture to stabilize the polymer against oxidative degradation. The BHT concentration was 250 ppm. The polymer solutions were chromatographed at 140°C in a PL 220 high-temperature chromatography unit equipped with four SHODEX™ columns (HT803, HT804, HT805, and HT806) using TCB as the mobile phase at a flow rate of 1.0 mL / minute, with a differential refractive index (DRI) as the concentration detector. BHT was Petition 870240100454, dated 11 / 26 / 2024, pp. 66 / 169 58 / 76 was added to the mobile phase at a concentration of 250 ppm to protect the GPC columns against oxidative degradation. The sample injection volume was 200 pL. The GPC columns were calibrated with narrow-distribution polystyrene standards. Polystyrene molecular weights were converted to polyethylene molecular weights using the Mark-Houwink equation, as described in the ASTM D6474-12 standard test method (December 2012). The raw GPC data were processed with CIRRUS® GPC software to produce molar mass averages (Mn, Mw, Mz) and molar mass distribution (e.g., Polydispersity, Mw / Mn). In polyethylene technology, a commonly used term equivalent to SEC is GPC, i.e., Gel Permeation Chromatography. Dart Impact

[0277] The impact resistance of the film dart was determined using ASTM Method D1709-09 A (May 1, 2009). In this disclosure, the dart impact test employed a dart with a hemispherical head 1.5 inches (38 mm) in diameter. Drilling

[0278] Film “penetration,” or “slow perforation,” which is the energy (J / mm) required to break the film, was determined using ASTM D5748-95 (originally adopted in 1995, re-approved in 2012). Tensile Properties

[0279] The following film tensile properties were determined using ASTM D882-12 (August 1, 2012): tensile rupture strength (MPa), elongation at break (%), tensile yield strength (MPa), tensile yield elongation (%), and film stiffness or total energy at break (lb / in3). Tensile properties were measured in the machine direction (MD) and in the transverse direction (TD) of the blown films. Film Module Petition 870240100454, dated 11 / 26 / 2024, pp. 67 / 169 59 / 76

[0280] The secant modulus is a measure of film stiffness. The secant modulus is the slope of a line drawn between two points on the stress-strain curve, that is, the secant line. The first point on the stress-strain curve is the origin, that is, the point corresponding to the origin (the point of zero percent strain and zero stress); and the second point on the stress-strain curve is the point corresponding to a 1% strain; given these two points, the secant modulus at 1% is calculated and expressed in terms of force per unit area (MPa). The secant modulus at 2% is calculated similarly. This method is used to calculate the film modulus because the stress-strain relationship of polyethylene does not follow Hooke's law; that is, the stress-strain behavior of polyethylene is non-linear due to its viscoelastic nature. The secant moduli were measured using a conventional Instron tensile tester equipped with an 889.64 N (200 lbf) load cell.Monolayer film sample strips were cut for testing with the following dimensions: 35.56 centimeters (14 inches) in length, 2.54 centimeters (1 inch) in width, and 1 mil in thickness; ensuring there were no cracks or cuts on the edges of the samples. Film samples were cut in the machine direction (MD) and transverse direction (TD) and tested. ASTM conditions were used to condition the samples. The thickness of each film was precisely measured with a hand micrometer and entered along with the sample name into the Instron software. Samples were loaded into the Instron with a grip separation of 25.4 centimeters (10 inches) pulled at a rate of 2.54 cm / min (1 inch / min) generating the strain-strain curve. Secant moduli at 1% and 2% were calculated using the Instron software. Flexural Properties

[0281] The flexural properties, namely secant and tangent flexural modulus and flexural strength, were determined using ASTM D790-10 (published in April 2010). Petition 870240100454, dated 11 / 26 / 2024, pp. 68 / 169 60 / 76 Optical Properties

[0282] The optical properties of the film were measured as follows: Opacity, ASTM D1003-13 (November 15, 2013), and; Gloss, ASTM D2457-13 (April 1, 2013). Dynatup Impact

[0283] An instrumented impact test was performed on a machine referred to as a DYNATUP® Impact Tester purchased from Illinois Test Works Inc., Santa Barbara, California, USA; individuals skilled in the art often refer to this test as a Dynatup impact test. The testing was completed according to the following procedure. Test samples are prepared by cutting strips approximately 5 inches (12.7 cm) wide and approximately 6 inches (15.2 cm) long from a roll of blown film; the film was approximately 1 mil thick. Prior to testing, the thickness of each sample was precisely measured with a hand micrometer and recorded. ASTM conditions were employed. Test samples were mounted on the DYNATUP 9250 Impact Testing machine / drop tower using the pneumatic clamp. A DYNATUP #1 impact head, 0.5 inch (1.3 cm) in diameter, was attached to the crosshead using a supplied Allen screw.Before testing, the crosshead is raised to a height such that the film impact velocity is 10.9 ± 0.1 ft / s. A weight was added to the crosshead so that: 1) the deceleration of the crosshead, or the deceleration of the impact head, was no more than 20% from the start of the test to the peak load point; and 2) the impact head should penetrate through the specimen. If the impact head does not penetrate through the film, an additional weight is added to the crosshead to increase the impact velocity. During each test, the DYNATUP Impulse Data Acquisition Software collected the experimental data (load (lb) versus time). At least 5 film samples are tested and the software reports the following average values: “Maximum Load (Max). Petition 870240100454, dated 11 / 26 / 2024, pp. 69 / 169 61 / 76 “Dynatup Energy (lb)”, the highest load measured during the impact test; “Total Dynatup Energy (ft lb)”, the area under the load curve from the start of the test to the end of the test (sample puncture); and “Total Dynatup Energy at Max Load (ft lb)”, the area under the load curve from the start of the test to the point of maximum load. Water Vapor Transmission Rate

[0284] The Water Vapor Transmission Rate (“WVTR”, expressed as grams of water vapor transmitted per 100 square inches of film per day at a specified film thickness (mils), or g / 100 in2 / day) was measured according to ASTM F1249-90 with a MOCON® permatron developed by Modern Controls Inc. under conditions of 100°F (37.8°C) and 100% relative humidity. A control (comparative) experiment was conducted using a single low melt index HDPE resin having a melt index, I2 of approximately 0.95 grams / 10 minutes, a density of 0.9575 g / cm3 and a molecular weight distribution, Mw / Mn, of 3.51 (an ethylene homopolymer designated SCLAIR® 19C, available from NOVA Chemicals Corporation, Calgary, Alberta, Canada). The WVTR test was run in duplicate and the average WVTR was reported. Oxygen Transmission Rate (OTR)

[0285] The Oxygen Transmission Rate (OTR), expressed as cm3 of oxygen transmitted per 100 square inches of film per day at a specified film thickness (mils), or cm3 / 100 in2 / day) was measured on film samples (4 inches x 4 inches) at 0% relative humidity and 23°C using a MOCON® OH-TRAN® Model 2 / 21T System. OTR testing was performed in duplicate and the average oxygen permeation rate was determined at a steady state. Film Ripple

[0286] The film ripple is characterized substantially as reported in US Patent No. 8,709,611 by cutting a 2-inch x 2-inch “X” in each film frame, where the two cuts of the X are perpendicular. Petition 870240100454, dated 11 / 26 / 2024, pp. 70 / 169 62 / 76 Each cut is oriented at a 45-degree angle in both the machine and transverse directions. The two cuts produce four triangles, which are then free to curl. The X-axis is oriented so that two of the triangles curl only in the machine direction of the film, and two of the triangles curl only in the transverse direction. The films are mounted on a rigid substrate and allowed to curl for 20 hours. After 20 hours, the curl direction (toward or away from the inside or outside of the film) is noted, and the radii of curvature of the curl in both the machine and transverse directions are measured. A larger radius of curvature in this measurement indicates less curl. When the films curl by an amount greater than 90 degrees, the radius of curvature is measured directly. When the films curl by an amount less than 90 degrees, it is difficult to measure the radius directly.In these cases, the radius of curvature is determined by measuring the distance, / , from the base of the triangle to its free point and the distance, w, from the base of the triangle to the projection of the free point onto the film plane. With these two dimensions, the radius of curvature, r, is calculated numerically using the equation: w / r = sin (II r) Differential Scanning Calorimetry (DSC)

[0287] The primary peak melting point (°C), peak melting temperatures (°C), heat of fusion (J / g), and crystallinity (%) were determined using differential scanning calorimetry (DSC) as follows: the instrument was first calibrated with indium; after calibration, a polymer specimen was equilibrated at 0°C and then the temperature was increased to 200°C at a heating rate of 10°C / min; the melt was held isothermally at 200°C for five minutes; the melt was then cooled to 0°C at a cooling rate of 10°C / min and held at 0°C for five minutes; the specimen was then heated to 200°C at a heating rate of 10°C / min. DSC values, heat of fusion, and crystallinity are reported. Petition 870240100454, dated 11 / 26 / 2024, pp. 71 / 169 63 / 76 from the 2nd heating cycle. Differential Scanning Calorimetry (Modulated DSC)

[0288] Thermal characterization of multilayer films was conducted using Modulated DSC (MDSC) experiments on a TA Q-2000 instrument. Modulated DSC uses two simultaneous heating rates – a linear heating rate that provides information similar to standard DSC, and a sinusoidal or modulated heating rate that allows simultaneous measurement of the sample's thermal capacity. Therefore, resolution and sensitivity are improved for detecting weak transitions. The heating / cooling / heating protocol was used with a heating ramp of 1.25°C / min and a cooling ramp of 10°C / min. The modulation was adjusted to ± 0.20°C every 60 seconds. CRYSTAF / TREF (CTEF)

[0289] The most common distribution of a polymer was measured using a CRYSTAF / TREF 200+ unit equipped with an IR detector, hereinafter referred to as the CTREE. The acronym “TREF” stands for Temperature Elevation Fractionation. The CTREF was supplied by PolymerChar SA (Valencia Technology Park, Gustave Eiffel, 8, Paterna, E-46980 Valencia, Spain). The CTREF was operated in TREF mode, which operates the chemical composition of the polymer sample as a function of elution temperature, the Co / Ho ratio (Copolymer / Homopolymer ratio), and the CDBI (Composition Distribution Amplitude Index), i.e., CDBko and CDBI25. A polymer sample (80 to 100 mg) was placed in the reactor vessel of the CTREF. The reactor vessel was loaded with 35 mL of 1,2,4-trichlorobenzene (TCB), and the polymer was dissolved by heating the solution to 150°C for 2 hours. An aliquot (1.5 mL) of the solution was then loaded onto the CTREF column, which was packed with stainless steel microspheres.The column, loaded with the sample, was allowed to stabilize at 110°C for 45 minutes. The polymer was then crystallized from the solution in the column by reducing the temperature to 30°C at a rate of... Petition 870240100454, dated 11 / 26 / 2024, p. 72 / 169 64 / 76 cooling at 0.09°C / minute. The column was then equilibrated for 30 minutes at 30°C. The crystallized polymer was then eluted from the column with TCB flowing through the column at 0.75 mL / minute, while the column was slowly heated from 30°C to 120°C at a heating rate of 0.25°C / minute. The raw CTREF data were processed using Polymer Char software, an Excel spreadsheet, and internally developed CTREF software. CDBIso was defined as the percentage of polymer whose composition is within 50% of the median comonomer composition; CDBIso was calculated from the composition distribution curve and the normalized cumulative integral of the composition distribution curve, as described in US Patent 5,376,439.Those skilled in the art will understand that a calibration curve is necessary to convert a CTREF elution temperature into comonomer content, that is, the amount of comonomer in the ethylene / α-olefin polymer fraction that elutes at a specific temperature. The generation of such calibration curves is described in the prior art, for example, Wild, et al., J. Polym. Sci., Part B, Polym. Phys., Vol. 20 (3), pages 441-455: fully incorporated herein by reference. CDBI25 as similarly calculated; CDBI25 is defined as the percentage of polymer whose composition is within 25% of the median comonomer composition. At the end of each sample run, the CTREF column was cleaned for 30 minutes; specifically, with the CTREF column temperature at 160°C, TCB flowed (0.5 mL / minute) through the column for 30 minutes. All-Polyethylene Blow Molded Film Structure (Multilayer)

[0290] Multilayer blown films were produced on a commercially available 9-layer blown film line from Brampton Engineering (Brampton ON, Canada). The structure consists of two inventive 9-layer film structures, each having an alternating structure sequence of A / B / A / B / A / B / A / B / A, and an overall thickness of 1.5 mil (Inventive Example 1) or a Petition 870240100454, dated 11 / 26 / 2024, pp. 73 / 169 65 / 76 overall thickness of 2.0 mil (Inventive Example 2), are shown in Table 1. Also shown in Table 1 are the structures of four comparative 9-layer film structures: two of these have a completely block-like structure sequence of B / B / B / B / A / A / A / A / A ​​with an overall thickness of 1.5 mil (Comparative Example 1), or an overall thickness of 2.0 mil (Comparative Example 2); and two of these have a structure sequence that is somewhat random, having alternating block-like portions, B / B / A / B / B / A / B / B / A (Comparative Example 3), and B / A / A / B / A / A / B / A / A (Comparative Example 4), each having an overall thickness of 1.5 mil.

[0291] The properties of nine-layer blown films (having a thickness of 1.5 mil or 2 mil) made as described above are given in Table 2.

[0292] Layers A were made of a linear low-density polyethylene: SCLAIR® FP120-C, an ethylene / 1-octene copolymer available from NOVA Chemicals Corporation having a density of about 0.920 g / cm3 and a melt index, I2, of about 1 g / 10 min. Layers B were made of a high-density polyethylene: SURPASS® HPs167-AB, a high-density ethylene homopolymer available from NOVA Chemicals Corporation having a density of about 0.967 g / cm3 and a melt index, I2, of about 1.20 g / 10 min. Each of the Inventive and Comparative multilayer film structures was designed to contain about 50 percent, by weight, of the SCLAIR® FP120-C material and about 50 percent, by weight, of the SURPASS® HPs167-AB material.

[0293] The multilayer mold technology consisted of a pancake-type mold, a FLEX-STACK Coextrusion (SCD) mold, with flow paths machined on both sides of a plate, the mold tool diameter was 6.3 inches, in this development, an 85-mil mold gap was used consistently, film was produced at a Blow Ratio (BUR) of 2.5 and the line throughput rate was kept constant at 250 lb / h. The specifications of the nine Petition 870240100454, dated 11 / 26 / 2024, pp. 74 / 169 The 66 / 76 extruders were as follows: 1.5-inch diameter screws, 30 / 1 length-to-diameter ratio, 7 polyethylene screws with single passes and Maddox mixers, 2 nylon screws; extruders were air-cooled, equipped with 20-HP motors, and all extruders were equipped with gravimetric mixers. The pressure and compression frame included a Decatex horizontal oscillating conveyor and pearl cooling blades just below the pressure rollers. The line was equipped with a sheet winder and oscillating cutting knives. All mold temperatures were maintained at a constant 480°F (i.e., layer sections, bottom of mandrel, mandrel, inner edge, and outer edge). TABLE 1 Multilayer blown film structure Inventive Example No. 1 Comparative 1 Comparative 3 Comparative 4 Film Structure Width 1.5 mil 1.5 mil 1.5 mil 1.5 mil Film Structure A / B / A / B / A / B / A / B / AB / B / B / B / A / A / A / A / AB / B / A / B / B / A / B / B / AB / A / A / B / A / A / B / A / A Material %, by weight, of the 9-layer structure s Material %, by weight, of the 9-layer structure s Material %, by weight, of the 9-layer structure s Material %, by weight, of the 9-layer structure s Layer 1 (inside the bubble) FP120-C 10 HPs167AB 12.5 HPs167AB 8.33 H Ps 167AB 16.7 Layer 2 HPs167AB 12.5 HPs167AB 12.5 HPs167AB 8.33 FP120-C 8.33 Layer 3 FP120-C 10 HPs167AB 12.5 FP120-C 16.7 FP120-C 8.33 Layer 4 HPs167AB 12.5 HPs167AB 12.5 HPs167AB 8.34 HPs167AB 16.6 Petition 870240100454, dated 11 / 26 / 2024, pp. 75 / 169 67 / 76 Layer 5 FP120-C 10 FP120-C 10 HPs167AB 8.34 FP120-C 8.34 Layer 6 HPs167AB 12.5 FP120-C 10 FP120-C 16.6 FP120-C 8.34 Layer 7 FP120-C 10 FP120-C 10 HPs167AB 8.33 HPs167AB 16.7 Layer 8 HPs167AB 12.5 FP120-C 10 HPs167AB 8.33 FP120-C 8.33 Layer 9 (outside the bubble; the shell layer) FP120-C 10 FP120-C 10 FP120-C 16.7 FP120-C 8.33 TABLE 1 - CONTINUED Multilayer blown film structure Inventive Example No. 2 Comparative 2 Film Structure Width 2.0 mil 2.0 mil Film Structure A / B / A / B / A / B / A / B / AB / B / B / B / A / A / A / A / A ​​Material %, by weight, of the 9-layer structure Material %, by weight, of the 9-layer structure Layer 1 (inside the bubble) FP120-C 10 HPs167-AB 12.5 Layer 2 HPs167-AB 12.5 HPs167-AB 12.5 Layer 3 FP120-C 10 HPs167-AB 12.5 Layer 4 HPs167-AB 12.5 HPs167-AB 12.5 Layer 5 FP120-C 10 FP120-C 10 Layer 6 HPs167-AB 12.5 FP120-C 10 Layer 7 FP120-C 10 FP120-C 10 Layer 8 HPs167-AB 12.5 FP120-C 10 Layer 9 (outside the bubble) FP120-C 10 FP120-C 10 Petition 870240100454, dated 11 / 26 / 2024, pp. 76 / 169 68 / 76 TABLE 2 Multilayer blown film structure Inventive Example No. 1 Comparative 1 Comparative 3 Comparative 4 Film Structure Width 1.5 mil 1.5 mil 1.5 mil 1.5 mil Film Structure A / B / A / B / A / B / A / B / AB / B / B / B / A / A / A / A / AB / B / A / B / B / A / B / B / AB / A / A / B / A / B / A / A / A ​​Opacity (%) 14.38 29.4 29.4 30.07 Brightness at 45° 58 48 47 47 Piercing Energy (J / mm) 64 48 52 59 Dart Impact (g / mil) 105 82 90 97 Maximum Dynatup Load (lb) 5.98 4.81 5.59 5.66 Modulus Sec a 1%MD (MPa) 562 561 550 541 Modulus Sec at 1%TD (MPa) 747 757 714 742 WVTR (g / 100 in² / day) 0.1646 0.1625 0.1654 0.1728 OTR (cm³ / 100 inch² / day) 66.68 61.17 63.01 65.28 Radius of curvature MD (mm) No waviness 2 - - Radius of curvature TD (mm) No waviness 4 - - TABLE 2 - CONTINUED Multilayer blown film structure Inventive Example No. 2 Comparative Example 2 Film Structure Width 2.0 mil 2.0 mil Film Structure A / B / A / B / A / B / A / B / AB / B / B / B / A / A / A / A / A ​​Opacity (%) 17.61 27.6 Petition 870240100454, dated 11 / 26 / 2024, p. 77 / 169 69 / 76 Inventive Example No. 2 Comparative 2 Brightness at 45° 50 47 Drilling Energy (J / mm) 73 64 Dart Impact (g / mil) 106 79 Maximum Dynatup Load (lb) 7.52 6.64 Modulus Sec at 1% - MD (MPa) 533 533 Modulus Sec at 1% - TD (MPa) 720 771 WVTR (g / 100 in² / day) 0.1144 0.1022 OTR (cm³ / 100 in² / day) 42.72 39.55 Radius of curvature MD (mm) No waviness (0) 2 Radius of curvature TD (mm) No waviness (0) 5

[0294] The optical properties (both opacity and brightness) of the 9-layer blown films are presented in Table 2. From the data, it is clear that film structures with a thickness of 1.5 mil or 2 mil and having an alternating arrangement of layers comprising polymers (A) and (B) instead of a block arrangement of layers comprising polymers (A) and (B) have significantly better optical properties. Inventive Example 1 has an opacity that is 54% lower than Comparative Example 1, while Inventive Example 2 has an opacity that is 36% lower than Comparative Example 2. Inventive Example 1 has a brightness value that is 20% higher than Comparative Example 1, while Inventive Example 2 has a brightness value that is 6% higher than Comparative Example 2. Similar improvements in opacity and brightness are observed for Inventive Example 1 compared to Comparative Example 3 and Comparative Example 4.

[0295] Film robustness data are also provided in Table 2. The data show that for both film thicknesses, 1.5 mil and 2 mil, film structures having an alternating arrangement of layers comprising polymers (A) and (B) rather than a block or random arrangement of layers comprising polymers (A) and (B) have improved robustness properties. The Inventive Example Petition 870240100454, dated 11 / 26 / 2024, pp. 78 / 169 Example 70 / 76 has a piercing energy that is 33% greater than Comparative Example 1, 23% greater than Comparative Example 3, and 8% greater than Comparative Example 4, while Inventive Example 2 has a piercing energy that is 14% greater than Comparative Example 2. Similarly, Inventive Examples 1 and 2 both have higher dart impact values ​​than Comparative Examples 1 and 2, by 28% and 34%, respectively. Inventive Example 1 also had better dart impact values ​​than Comparative Examples 3 and 4. Finally, when comparing the Dynatup values ​​of maximum load, it is clear that Inventive Examples 1 and 2 have significantly higher values ​​than Comparative Examples 1 and 2. Inventive Example 1 has a Dynatup value of maximum load that is 24% higher than Comparative Example 1, while Inventive Example 2 has a Dynatup value of maximum load that is 13% higher than Comparative Example 2.Inventive Example 1 also had better Dynatup maximum load values ​​than Comparative Examples 3 and 4.

[0296] To evaluate the stiffness properties of the film structures, the secant modulus at 1% was measured and the data are also presented in Table 2. When the secant modulus at 1% in the machine direction (MD) is considered, there is little difference observed between film structures having an alternating arrangement of layers comprising polymers (A) and (B) and film structures having a block arrangement of layers comprising polymers (A) and (B). At both thicknesses of 1.5 mil and 2 mil, the secant modulus at 1% in the machine direction was essentially the same for Inventive Examples 1 and 2 and Comparative Examples 1 and 2 (562 MPa for a thickness of 1.5 mil and 533 MPa for a thickness of 2 mil).However, when the secant modulus at 1% in the transverse direction (TD) is considered, a small difference was observed between Inventive Examples 1 and 2 and Comparative Examples 1 and 2: in this case, the film structures having an alternating arrangement of layers comprising polymers (A) and (B) instead of. Petition 870240100454, dated 11 / 26 / 2024, pp. 79 / 169 71 / 76 a block arrangement of layers comprising polymers (A) and (B) have only slightly lower stiffness values. Inventive Example 1 has a secant modulus at 1% TD of 747 MPa vs. Comparative Example 1 which has a secant modulus at 1% TD of 757 MPa. Inventive Example 2 has a secant modulus at 1% TD of 720 MPa vs. Comparative Example 2 which has a secant modulus at 1% TD of 771 MPa.

[0297] When considered together, the data in Table 2 show that when a film structure is formulated with strictly alternating and adjacent layers comprising polymers (A) and (B) instead of with a blocky (or random) arrangement of layers comprising polymers (A) and (B), a film structure has significantly improved optical and robustness properties, while not negatively impacting stiffness to a large degree. This results in an improved balance of stiffness, robustness, and optics for the film structure.

[0298] Regarding the water vapor transmission rate (WVTR) and oxygen transmission rate (OTR) data for the film structures, the data in Table 2 show that a film structure having an alternating arrangement of layers comprising polymers (A) and (B) has slightly worse barrier properties than a film structure having a block arrangement of layers comprising polymers (A) and (B). However, the difference is not large, and ranges from 2 to 10% more for Inventive Examples 1 and 2 vs. Comparative Examples 1 and 2 when both WVTR and OTR are considered.

[0299] The waviness direction and radius of curvature in the machine (MD) and transverse (TD) directions of the film structures are given in Table 2. It was clear from a simple visual inspection that the 1.5 mil and 2 mil film structures having an alternating arrangement of layers comprising polymers (A) and (B) did not exhibit significant waviness in either the MD or TD directions, while the 1.5 mil and 2 mil film structures having a block arrangement of Petition 870240100454, dated 11 / 26 / 2024, pp. 80 / 169 72 / 76 layers comprising polymers (A) and (B) showed waviness in both MD and TD directions. In fact, for Inventive Examples 1 and 2, essentially no waviness was observed in the MD and TD directions, while for Comparative Example 1, the MD and TD radii of curvature were 2 mm and 4 mm respectively, and for Comparative Example 2, the MD and TD radii of curvature were 2 mm and 5 mm respectively.

[0300] The modulated DSC profiles (heat flux vs. temperature) for a 1.5 mil film structure having an alternating arrangement of layers comprising polymers (A) and (B), Inventive Example 1, and for a 1.5 mil film structure having a block arrangement of layers comprising polymers (A) and (B), Comparative Example 1, are shown in Figure 1. The profiles are obtained from the modulated DSC final heating cycles. Figure 1 clearly shows the presence of only one single melting peak at 127.8°C for Inventive Example 1, which is a film structure having an alternating arrangement of layers comprising polymers (A) and (B), while two distinct melting peaks are observed, one at 126.0°C and one at 131.1°C, for Comparative Example 1, which is a film structure having a block arrangement of layers comprising polymers (A) and (B).

[0301] Without wishing to dwell on theory, the presence of only one single melting peak for Inventive Example 1 is indicative of co-crystallization behavior occurring at the interface between linear low-density polyethylene (A) and high-density polyethylene (B). With alternating layers comprising polymer (A) and polymer (B), it appears that the layer comprising the higher-density polyethylene is able to nucleate the layer comprising the lower-density polyethylene, resulting in co-crystallization at their interface. This co-crystallization behavior is accentuated in the film structure having strictly alternating layers comprising polymers (A) and (B) because the number of Petition 870240100454, dated 11 / 26 / 2024, page 81 / 169 73 / 76 adjacent interfaces between a lower and higher density polyethylene material are increased (compared to a film structure having a blocked nature) and there are more opportunities for the higher density material to nucleate the lower density material (i.e., co-crystallization effects are accentuated). As a result, a single peak is observed for Inventive Example 1 in Figure 1, while two distinct peaks are observed for Comparative Example 1.

[0302] Because co-crystallization phenomena are believed to be influenced by the melt miscibility (and relative crystallization rates) of the polymers used to produce each layer in a blown film structure (during the blown film process), and because melt miscibility and crystallization rates are believed to be determined, at least in part, by polymer branch content and branch distribution, polymers (A) and (B) were further examined using TREF (temperature elevation elution fractionation) analysis.

[0303] Figure 2 shows the CTREF profiles of polymer (A) which is a linear low-density polyethylene (e.g., SCLAIR FPs120) and polymer (B) which is high-density polyethylene (e.g., SURPASS HPs 167).

[0304] Polymer (B), which is made with a single-site catalyst, has a narrow compositional distribution, with a large elution peak that occurs at a relatively high temperature. Polymer (A), which is made with a multi-site ZieglerNatta catalyst, has a broad compositional distribution, but includes higher-density polymer chains that are eluted at higher temperatures and which, in the CTREF profile, partially overlap with those with higher-density polymer chains present in polymer (B). Without wishing to delve into theory, it seems likely that the partial synergy in the comonomer distribution of polymers (A) and (B) as observed in the CTREF profiles promotes their co-crystallization, which is consistent with the results obtained by modulated DSC, where a peak Petition 870240100454, dated 11 / 26 / 2024, page 82 / 169 74 / 76 unique was observed for the strictly alternating film structure (Inventive Example 1).

[0305] The non-limiting forms of this disclosure include the following:

[0306] Modality A. Multilayer film structure made entirely of polyethylene, wherein the film structure comprises at least five alternating and adjacent layers of: (A) a linear low-density polyethylene having a density of 0.910 g / cm3 to 0.940 g / cm3 and a melt index, I2, of 0.1 to 10 g / 10 min; and (B) a high-density polyethylene having a density of at least 0.945 g / cm3, a melt index, I2, of 0.1 to 10 g / 10 min and comprising 0 to 1 percent, by weight, of a nucleating agent or a mixture of nucleating agents.

[0307] Embodiment B. Film structure, according to Embodiment A wherein a difference in density between linear low-density polyethylene (A) and high-density polyethylene (B) is at least 0.015 g / cm3.

[0308] Embodiment C. Film structure, according to Embodiment A wherein a difference in density between linear low-density polyethylene (A) and high-density polyethylene (B) is at least 0.030 g / cm3.

[0309] Modality D. Film structure, according to Modality A, B, or C, wherein the high-density polyethylene is a polyethylene homopolymer composition, wherein the polyethylene homopolymer composition comprises: (i) 95 to 30 percent by weight of a first ethylene homopolymer having a density of 0.950 to 0.975 g / cm3; and (ii) 5 to 70 percent by weight of a second ethylene homopolymer having a density of 0.950 to 0.975 g / cm3, wherein the ratio of the melt index, I2 of the second homopolymer to Petition 870240100454, dated 11 / 26 / 2024, page 83 / 169 75 / 76 ethylene and the melting index, I2 of the first ethylene homopolymer is at least 10.

[0310] Modality E. Film structure, according to Modality A, B, C, or D, wherein the high-density polyethylene comprises from 100 to 3,000 ppm of the nucleating agent or mixture of nucleating agents.

[0311] Embodiment F. Film structure, according to Embodiment A, B, C, D, or E, wherein the nucleating agent or mixture of nucleating agents comprises a salt of a dicarboxylic acid.

[0312] Mode G. Film structure, according to Mode A, B, C, D, E or F, having five alternating and adjacent layers in the following pattern: A / B / A / B / A.

[0313] Mode H. Film structure, according to Mode A, B, C, D, E or F, having five alternating and adjacent layers in the following pattern: B / A / B / A / B.

[0314] Mode I. Film structure, according to Mode A, B, C, D, E or F, having seven alternating and adjacent layers in the following pattern: A / B / A / B / A / B / A.

[0315] Mode J. Film structure, according to Mode A, B, C, D, E or F, having seven alternating and adjacent layers in the following pattern: B / A / B / A / B / A / B.

[0316] Mode K. Film structure, according to Mode A, B, C, D, E or F, having nine alternating and adjacent layers in the following pattern: A / B / A / B / A / B / A / B / A.

[0317] Mode L. Film structure, according to Mode A, B, C, D, E or F, having nine alternating and adjacent layers in the following pattern: B / A / B / A / B / A / B / A / B.

[0318] Mode M. Film structure, according to Mode A, B, C, D, E or F, having eleven alternating and adjacent layers in the following pattern: Petition 870240100454, dated 11 / 26 / 2024, p. 84 / 169 76 / 76 A / B / A / B / A / B / A / B / A / B / A.

[0319] Mode N. Film structure, according to Mode A, B, C, D, E or F, having eleven alternating and adjacent layers in the following pattern: B / A / B / A / B / A / B / A / B / A / B.

[0320] Embodiment O. Film structure, according to Embodiment A, B, C, D, E or F, wherein the film structure has at least one shell layer comprising (A) a linear low-density polyethylene having a density of 0.910 g / cm3 to 0.940 g / cm3 and a melt index, I2 of 0.1 to 10 g / 10 min. INDUSTRIAL APPLICABILITY

[0321] Multilayer polymer film structures can be adapted for use in various packaging applications. A multilayer film structure made entirely of polyethylene is provided, having good inherent recyclability. Petition 870240100454, dated 11 / 26 / 2024, pp. 85 / 169

Claims

1 / 2 CLAIMS 1. Multilayer film structure made entirely of polyethylene CHARACTERIZED in that the film structure comprises at least five alternating and adjacent layers of: (A) a linear low-density polyethylene having a density, determined using ASTM D792-13, of 0.910 g / cm3 to 0.940 g / cm3 and a melt index, I2, of 0.1 to 10 g / 10 min; and (B) a high-density polyethylene having a density, determined using ASTM D792-13, of at least 0.945 g / cm3, a melt index, I2, of 0.1 to 10 g / 10 min and comprising 0 to 1 percent by weight of a nucleating agent or a mixture of nucleating agents; wherein high-density polyethylene is a polyethylene homopolymer composition, wherein the polyethylene homopolymer composition comprises: (i) 95 to 30 percent by weight of a first ethylene homopolymer having a density of 0.950 to 0.975 g / cm3;and (ii) 5 to 70 percent by weight of a second ethylene homopolymer having a density of 0.950 to 0.975 g / cm3, wherein the ratio of the melt index, I2, of the second ethylene homopolymer to the melt index, I2, of the first ethylene homopolymer is at least 10; and wherein the film structure has five alternating and adjacent layers in the following pattern: A / B / A / B / A; or wherein the film structure has five alternating and adjacent layers in the following pattern: B / A / B / A / B; or wherein the film structure has seven alternating and adjacent layers in the following pattern: A / B / A / B / A / B / A; or wherein the film structure has seven alternating and adjacent layers in Petition 870240100454, dated 11 / 26 / 2024, p. 86 / 169 2 / 2 pattern as follows: B / A / B / A / B / A / B; or where the film structure has nine alternating and adjacent layers in the following pattern: A / B / A / B / A / B / A / B / A; or where the film structure has nine alternating and adjacent layers in the following pattern: B / A / B / A / B / A / B / A / B;or wherein the film structure has eleven alternating and adjacent layers in the following pattern: A / B / A / B / A / B / A / B / A / B / A; or wherein the film structure has eleven alternating and adjacent layers in the following pattern: B / A / B / A / B / A / B / A / B / A / B.

2. Film structure, according to claim 1, CHARACTERIZED in that the difference in density between linear low-density polyethylene (A) and high-density polyethylene (B) is at least 0.015 g / cm3.

3. Film structure, according to claim 1, CHARACTERIZED in that the difference in density between linear low-density polyethylene (A) and high-density polyethylene (B) is at least 0.030 g / cm3.

4. Film structure, according to claim 3, CHARACTERIZED in that the high-density polyethylene comprises from 100 to 3000 ppm of the nucleating agent or a mixture of nucleating agents.

5. Film structure according to claim 4, CHARACTERIZED in that the nucleating agent or mixture of nucleating agents comprises a salt of a dicarboxylic acid compound.

6. Film structure according to claim 1, CHARACTERIZED in that the film structure has at least one shell layer comprising (A) a linear low-density polyethylene having a density of 0.910 g / cm3 to 0.940 g / cm3 and a melt index, I2, of 0.1 to 10 g / 10 min. Petition 870240100454, dated 11 / 26 / 2024, p. 87 / 169

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