Method for preparing masterbatch compositions and their uses

Abstract

The present disclosure relates broadly to methods for preparing high barrier polyolefin compositions and masterbatch compositions that include a synergistic combination of a nucleating agent and a hydrocarbon resin to prepare barrier layers and films having barrier properties suitable for packaging applications.

Description

[Technical field]

[0001]

[0001] The present disclosure relates generally to methods for preparing high barrier polyolefin compositions and masterbatch compositions that may be used to prepare barrier layers and films having barrier properties suitable for packaging applications. Certain aspects disclosed herein relate to methods for preparing masterbatch compositions and the use of such masterbatch compositions to form high barrier polyolefin layers in films. CROSS-REFERENCE TO RELATED APPLICATIONS

[0002]

[0002] This application claims priority to Australian Provisional Patent Application No. 2022900898, filed April 6, 2022, Australian Provisional Patent Application No. 2023900832, filed March 24, 2023, and Australian Provisional Patent Application No. 2023900833, filed March 24, 2023, each of which is incorporated herein by cross-reference in its entirety as if fully set forth. BACKGROUND

[0003]

[0003] Polyolefins, such as polyethylene, high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), metallocene linear low density polyethylene (mLLDPE), very low density linear polyethylene (VLLDPE), ethylene-vinyl acetate (EVA) and plastomers, have a variety of commercial uses.

[0004] Polyethylene is a versatile polymer that possesses a unique combination of properties, such as chemical inertness, toughness, low permeability to water vapor and oxygen, and formability.

[0005]

[0005] High density polyethylene (HDPE) is commonly used in blown film applications where high resistance to water vapor and oxygen transmission is beneficial, such as cereal box liners and packaging for dry foods.

[0006]

[0006] Water vapor transmission rate (WVTR) and oxygen transmission rate (OTR) are important properties of barrier films. These properties reflect the amount of water vapor and oxygen, respectively, that can pass through the film. Generally, for films used in many food packaging, it is desirable for the film to exhibit low values ​​of WVTR and / or OTR.

[0007]

[0007] Best-in-class HDPE blown film grades are approximately 3.0-3.6 g / m at 40 micron gauge. 2 / day. Since WVTR is also a function of film thickness, this is approximately 2.4 to 2.9 g / m2 at 50 micron gauge. 2 / day will be transitioned.

[0008]

[0008] WVTR at a particular gauge is a property that is a function of not only the intrinsic properties of HDPE but also how it is processed into a film. The addition of hydrocarbon resins (HCR) mixed into polyolefins, such as polypropylene and polyethylene, has been used to improve barrier resistance. In the prior art, it is generally taught and accepted that a relatively high concentration of HCR, at least about 10% to 20% w / w, is required in a typical film to achieve suitable WVTR performance, i.e., about a 30% reduction in WVTR. For example, EP2520615, WO2010 / 104628 and US2012 / 0107542 disclose that a concentration of HCR greater than 10% w / w is required to produce the desired barrier and mechanical properties in the barrier layers exemplified therein. Due to the relatively high cost of HCR, the inclusion of high concentrations of HCR in a barrier film significantly increases the overall production cost. It would therefore be advantageous and desirable to be able to achieve suitable barrier properties using less HCR. Furthermore, high concentrations of HCR (e.g., concentrations greater than 10% w / w) can significantly deteriorate the mechanical properties of useful films, such as toughness and tear resistance, and can adversely affect the suitability of the film for use in packaging or in contact with food products.

[0009] In contrast to WVTR, processability is an inherent property of the material / resin, not the film. Poor processability not only leads to difficulties in making blown films from the resin, but the mechanical properties of the film, such as tear strength and puncture resistance, may also be adversely affected.

[0010]

[0010] Nucleating agents facilitate and broadly promote the formation of crystals during processing. The result is smaller crystals which, when well dispersed, achieve a more challenging path for gas molecules to pass through the resin. When a typical HDPE film is effectively nucleated, the WVTR can be reduced by about 25%-30%. However, there are difficulties associated with effectively introducing and homogenizing the nucleating agent into the HDPE, for example, due to poor compatibility and / or particle agglomeration.

[0011]

[0011] It is known that the combination of a hydrocarbon resin and a nucleating agent, when added together to a polymer composition (e.g., polyethylene), provides an additive or cumulative effect in terms of improving the barrier properties of the resulting barrier layer. However, the prior art demonstrates that significant improvements are only reached at relatively high hydrocarbon resin concentrations, typically greater than about 10% in the polymer composition. Moreover, the improvements from the combination of a hydrocarbon resin and a nucleating agent have been shown to be limited to additive or cumulative effects rather than "synergistic" effects. This is consistent with the theorization that the hydrocarbon resin and the nucleating agent impart improvements in the amorphous and crystalline phases of the polymer composition, respectively. In this regard, it is generally understood and accepted by those skilled in the art that the hydrocarbon resin and the nucleating agent essentially work independently of each other. Therefore, most advances in this field have focused on finding new forms of hydrocarbon resins, nucleating agents, introducing different additives, tailoring the physical properties of the polymer substrate and its blends, etc., as well as finding an effective balance of the aforementioned with the aim of lowering costs while maintaining reasonable barrier properties.

[0012] As mentioned above, approaches to improve the effectiveness of nucleation involve narrowing the molecular weight distribution of the polymer and limiting the degree of long chain branching. By changing the molecular weight distribution in the polymer so that a very low molecular weight fraction is blended with a high molecular weight fraction in a specific ratio, the capacity of the resin for effective nucleation can be improved such that the WVTR can be reduced by as much as 40-50%. In another approach, blends of HDPE polymers with low and high melt flow indexes and nucleating agents have been shown to be effective in lowering the WVTR by about 20%-40%. However, there is a limit to how much the barrier properties can be improved by the addition of higher melt index or lower molecular weight polymers without adversely affecting the processability and mechanical properties of the film, especially the puncture and tear resistance. It would be advantageous and desirable to be able to achieve suitable processability, mechanical properties and barrier properties using a wider range of film components, such as lower melt index and wider molecular weight range polymers.

[0013] There have been a number of other approaches to improve the water vapor barrier of HDPE-based films. For example, layers of HDPE can be laminated or coextruded with other layer materials to form multi-layer HDPE-based films with improved water vapor barrier properties. However, the formation of multi-layer films typically entails higher costs, and such films generally have low recyclability. In particular, the use of different types of materials in multi-layer films can limit the ability to recycle the film due to the resulting adverse environmental impact. Monolayer films of HDPE can also be prepared, and the water vapor barrier of the monolayer film can be improved by increasing its thickness, but this has the significant disadvantage of adding weight and cost to the packaging formed with these films.

[0014] There is a need for improved methods of preparing barrier films having suitable barrier properties, such as high resistance to water vapor and oxygen transmission, balanced with robust film properties. There is also a need for methods of preparing barrier films having suitable barrier properties using lower amounts of HCR and broader specifications of component polymers.

[0015] The present invention generally relates to a method for preparing a film having improved barrier properties.

[0016]

[0016] Aspects of the invention disclosed herein broadly relate to methods for preparing masterbatch compositions comprising a nucleating agent, a hydrocarbon resin, or both a nucleating agent and a hydrocarbon resin, and a polyolefin, preferably polyethylene, more preferably high density polyethylene (HDPE), and the use of such masterbatch compositions to prepare high barrier polyolefin (HBP) layers, such as HBP barrier layers, in films. Other aspects disclosed herein relate to the use of masterbatch technology to prepare high barrier polyolefin (HBP) compositions, and the use of HBP compositions to prepare high barrier polyolefin (HBP) layers in high density polyethylene films.

[0017] More specifically, the present invention relates to a method for preparing a mixture comprising a synergistic combination of a nucleating agent and a hydrocarbon resin in a polyolefin, such as polyethylene, more preferably high density polyethylene (HDPE). Such a synergistic mixture allows relatively low concentrations of the hydrocarbon resin to be used, preferably below the threshold concentration considered essential in the prior art, while still achieving acceptable (or in some cases improved) barrier properties. In a preferred embodiment, the synergistic combination and processing of the hydrocarbon resin and nucleating agent achieves suitable or improved barrier properties balanced with good mechanical properties and processability.

[0018]

[0018] In a preferred embodiment, the polyolefin is selected from the group consisting of polyethylene, high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), metallocene linear low density polyethylene (mLLDPE), very low density linear polyethylene (VLLDPE), ethylene-vinyl acetate (EVA) and plastomers, more preferably high density polyethylene (HDPE).

[0019] In one aspect, the present invention provides a method for preparing a high barrier polyolefin masterbatch, comprising the steps of: a) melt mixing a nucleating agent into polyethylene to form a nucleating agent masterbatch; b) melt mixing a hydrocarbon resin into polyethylene to form a hydrocarbon resin masterbatch; c) melt mixing the nucleating agent masterbatch of step a) with the hydrocarbon resin masterbatch of step b) to form a homogeneous high barrier polyolefin masterbatch. The present invention provides a method comprising:

[0020]

[0020] In one embodiment, the barrier performance of the high barrier film prepared from the high barrier polyolefin masterbatch is greater than the barrier performance based on the additive effect of the nucleating agent and the hydrocarbon resin, where the additive effect is preferably based on the effect of each additive when applied individually or when used or processed independently of other additives.

[0021] In another aspect, the present invention provides a method for preparing a nucleating agent masterbatch, comprising the steps of: melt blending the nucleating agent into the polyethylene, wherein the melt blending is sufficient to produce a homogenous nucleating agent masterbatch; A method is provided.

[0022] In another aspect, the present invention provides a method for preparing a hydrocarbon resin masterbatch, comprising the steps of: melt blending a hydrocarbon resin into polyethylene, wherein the melt blending is sufficient to produce a homogenous hydrocarbon resin masterbatch; A method is provided.

[0023] In another aspect, the present invention provides a method for preparing a high barrier polyolefin masterbatch, comprising the steps of: melt mixing a nucleating agent masterbatch as disclosed herein with a hydrocarbon resin masterbatch as disclosed herein; wherein the melt mixing step is sufficient to produce a homogeneous high barrier polyolefin masterbatch; A method is provided.

[0024] In another aspect, the present invention provides a method for preparing a high barrier polyolefin masterbatch, comprising the steps of: melt blending a nucleating agent mixture and a hydrocarbon resin with a polyethylene, wherein the nucleating agent mixture comprises a nucleating agent and a polyolefin, and wherein the melt blending is sufficient to produce a homogenous high barrier polyolefin masterbatch; A method is provided.

[0025]

[0025] In preferred embodiments of the methods disclosed herein for preparing the NA MB, HCR MB, HBP MB, HBP composition or barrier layer, any one or more of the melt mixing steps sufficient to produce homogeneity are carried out in a twin screw compounder or a single screw compounder, preferably a twin screw compounder.

[0026]

[0026] In preferred embodiments of the methods disclosed herein for preparing the NA MB, HCR MB, HBP MB, HBP composition or barrier layer, each melt mixing step is carried out for a residence time sufficient to produce a substantially homogeneous blend.

[0027] In one or more preferred embodiments, the twin screw extruder has the barrel zone temperatures set to provide a constant melt temperature of about 150-220°C.

[0028] In one or more preferred embodiments, the inventive method disclosed herein for preparing the NA MB, HCR MB, HBP MB, HBP composition or barrier layer further comprises the step of adding one or more optional additives. Representative optional additives include antacid metal salts, and antioxidants (including primary and secondary antioxidants), flame retardants, lubricants, UV stabilizers, antistatic agents, processing aids, and the like. If desired, such additives may be added to the extruder and melt compounded into the relevant NA MB, HCR MB, HBP MB, HBP composition or barrier layer.

[0029] In various embodiments of the invention disclosed herein, the nucleating agent is present in the nucleating agent masterbatch or HBP masterbatch in an amount of from about 0.1% to about 30% w / w, or from about 0.2% to about 25% w / w, or from about 0.3% to about 25% w / w, or from about 0.2% to about 15% w / w, or from about 0.3% to about 20% w / w, or from about 0.3% to about 15% w / w, or from about 0.5% to about 20% w / w, or from about 0.5% to about 15% w / w, or from about 0.5% to about 10%.

[0030] In various embodiments of the invention disclosed herein, the hydrocarbon resin is present in the hydrocarbon resin masterbatch or HBP masterbatch in an amount of from about 5% to about 80% w / w, or from about 2.5% to about 80% w / w, or from about 2.5% to about 70% w / w, or from about 2.5% to about 60% w / w, or from about 10% to about 70% w / w, or from about 15% to about 65% w / w, or from about 20% to about 60% w / w, or from about 5% to about 50% w / w, or from about 7.5% to about 45% w / w, or from about 10% to about 40% w / w, or from about 30% to about 50% w / w, or from about 25% to about 55% w / w.

[0031]

[0031] In another embodiment, the nucleating agent is present in the high barrier polyolefin masterbatch in an amount of from about 0.2% to about 25% w / w, and the hydrocarbon resin is present in the high barrier polyolefin masterbatch in an amount of from about 2.5% to about 70% w / w.

[0032] In one or more embodiments of the methods described herein for preparing the HCR MB, HBP MB, HBP composition or barrier layer, the hydrocarbon resin has a weight average molecular weight lower than polyethylene. Preferably, the hydrocarbon resin is derived from a crude olefin feed selected from the group consisting of a C5 olefin feedstream, a C9 olefin feedstream, a terpene olefin, norbornene, pure monomer, and combinations thereof. Preferably, the hydrocarbon resin is a hydrogenated hydrocarbon resin or a cyclic olefin copolymer.

[0033] In one or more embodiments of the methods described herein for preparing a NA MB, HBP MB, HBP composition, or barrier layer, the nucleating agent is organic or inorganic. Preferably, the nucleating agent comprises a metal salt. Preferably, the nucleating agent comprises a metal hydrophthalate, a metal bicycloheptanedicarboxylate, a branched alkylphosphonic acid, or a combination thereof. Preferably, the nucleating agent comprises a metal hydrophthalate. Preferably, the nucleating agent comprises a metal hexahydrophthalate.

[0034] In another aspect, the present invention provides a kit comprising a nucleating agent masterbatch as described herein and a hydrocarbon resin or a hydrocarbon resin masterbatch as described herein, The nucleating agent is present in the nucleating agent masterbatch in an amount of about 0.1% to about 30% w / w; The hydrocarbon resin is present in the hydrocarbon resin masterbatch in an amount of about 5% to about 80% w / w. Provide a kit.

[0035] In another aspect, the present invention provides a kit comprising a nucleating agent mixture as described herein and a hydrocarbon resin masterbatch as described herein, The hydrocarbon resin is present in the hydrocarbon resin masterbatch in an amount of about 5% to about 80% w / w. Provide a kit.

[0036] In another aspect, the present invention provides a high barrier polyolefin masterbatch produced by the process as described herein.

[0037] Another aspect of the invention disclosed herein is To form a high barrier polyolefin composition, a kit as described herein, or A high barrier polyolefin masterbatch as described herein The use of blending the nucleating agent masterbatch and the hydrocarbon resin or hydrocarbon resin masterbatch as described herein with a bulk polyolefin; or blending a nucleating agent mixture and a hydrocarbon resin masterbatch as described herein with a bulk polyolefin; or blending a high barrier polyolefin masterbatch as described herein with a bulk polyolefin. Including, regarding use.

[0038]

[0038] Preferably the bulk polyolefin is bulk polyethylene, such as bulk HDPE.

[0039] In another aspect, the present invention provides a high barrier polyolefin composition produced in accordance with the invention disclosed herein, the high barrier polyolefin composition comprising: a nucleating agent in an amount of about 0.01% to about 1% w / w; a hydrocarbon resin in an amount of about 0.1% to about 10% w / w; The present invention provides a high barrier polyolefin composition comprising:

[0040] In various embodiments of the invention disclosed herein, the nucleating agent and the hydrocarbon resin are present in the HBP masterbatch, or kit, or HBP composition, or barrier layer in a ratio of about 1:4 to about 1:200, preferably about 1:7 to about 1:150, more preferably about 1:10 to about 1:100, and even more preferably about 1:15 to about 1:50. In preferred embodiments, the nucleating agent and the hydrocarbon resin are present in a ratio of about 1:4 to about 1:200. Preferably, the nucleating agent and the hydrocarbon resin are present in a ratio of about 1:10 to about 1:100.

[0041] In a preferred embodiment, either or both of the HDPE and bulk HDPE have a viscosity of about 0.94 to about 0.97 g / cm 3 has a density of

[0042]

[0042] In a preferred embodiment, the HDPE has a melt flow index of about 0.08 to 40.0 g / 10 min, preferably about 0.08 to 10.0 g / 10 min.

[0043] In another aspect, the present invention provides a barrier layer formed from the high barrier polyolefin composition as described herein.

[0044]

[0044] In a preferred embodiment, the nucleating agent is present in the barrier layer in an amount of about 0.01% to about 1% w / w, preferably about 0.02% to about 0.7% w / w, preferably about 0.03% to about 0.5% w / w, preferably about 0.03% to about 0.2% w / w, or preferably about 0.05% to about 0.2% w / w.

[0045]

[0045] In a preferred embodiment, the hydrocarbon resin is present in the barrier layer in an amount of from about 0.1% to about 10% w / w, preferably from about 0.2% to about 9% w / w, preferably from about 0.3% to about 8% w / w, preferably from about 0.5% to about 7% w / w, preferably from about 0.5% to about 6% w / w, preferably from about 0.5% to about 5% w / w, preferably from about 0.5% to about 4% w / w, preferably from about 0.7% to about 3% w / w, or preferably from about 1% to about 2% w / w.

[0046] In another aspect, the invention provides a film comprising a barrier layer as described herein, the film having a water vapor transmission rate as measured by ASTM F 1249-20 that is reduced by at least about 10% compared to a film of comparable thickness that does not include a barrier layer as described herein. In preferred embodiments, the film has a water vapor transmission rate as measured by ASTM F 1249-20 that is reduced by at least about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, or about 80% compared to a film of comparable thickness that does not include a barrier layer of the invention. In some embodiments, the film is a multilayer or monolayer film.

[0047] In another aspect, the invention provides a method for reducing the water vapor transmission rate of a film, the method comprising incorporating a barrier layer as described herein into a film, wherein the film has a water vapor transmission rate as measured by ASTM F 1249-20 that is reduced by at least about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, or about 80% compared to a film of comparable thickness not having a barrier layer as described herein.

[0048] In another aspect, the present invention is a method for reducing the water vapor and oxygen permeability of a polyethylene film, the method comprising: melt mixing a blend comprising polyethylene and 10% by weight or less of a composition, wherein the composition comprises: a nucleating agent masterbatch comprising a nucleating agent homogeneously dispersed in a polyolefin; and Hydrocarbon resin masterbatch containing a hydrocarbon resin homogeneously dispersed in a polyolefin is formed by mixing wherein the hydrocarbon resin masterbatch and the nucleating agent masterbatch are combined in a ratio of about 1:5 to about 60:1; A method is provided.

[0049] In another aspect, the present invention is a method for reducing the water vapor and oxygen transmission rates of a polyethylene film, the method comprising: melt mixing a blend comprising 90% by weight or more of a polyethylene and 10% by weight or less of a composition, wherein the composition comprises: a nucleating agent masterbatch comprising a nucleating agent homogeneously dispersed in a polyolefin; and Hydrocarbon resins having a lower molecular weight than that of polyethylene is formed by mixing wherein the hydrocarbon resin and the nucleating agent masterbatch are combined in a ratio of about 1:5 to about 60:1; A method is provided.

[0050] In another aspect, the present invention is a method for reducing the water vapor and oxygen transmission rates of a polyethylene film, the method comprising: melt mixing a blend comprising 90% by weight or more of a polyethylene and 10% by weight or less of a composition, the composition comprising: a nucleating agent homogeneously dispersed in the polyolefin; and Hydrocarbon resin masterbatch containing a hydrocarbon resin homogeneously dispersed in a polyolefin Including, wherein the hydrocarbon resin masterbatch and the nucleating agent are combined in a ratio of about 5:1 to about 150:1; A method is provided.

[0051] In another aspect, the present invention provides a composition prepared by melt mixing a nucleating agent masterbatch comprising a nucleating agent homogeneously dispersed in a polyolefin; and a hydrocarbon resin, wherein the hydrocarbon resin and the nucleating agent masterbatch are combined in a ratio of from about 1:5 to about 60:1.

[0052]

[0052] In preferred embodiments, the present invention provides a synergistic effect between the nucleating agent and the hydrocarbon resin that is at least 5% greater than the additive effect of the nucleating agent and the hydrocarbon resin, preferably at least 10% greater, 15% greater, 20% greater, 25% greater, 30% greater, 35% greater, 40% greater, 45% greater, or 50% greater. [Brief description of the drawings]

[0053] [Figure 1] FIG. 1 is a graph showing water vapor transmission rate (WVTR) normalized to thickness for films according to embodiments of the present invention and comparative films produced using alternative methods, as described in Table 1. [Diagram 2]

[0054] Figure 2 shows schematic diagrams of non-limiting embodiments of the present invention: (a) use of a melt mixer to blend a polyolefin and a nucleating agent (NA) mixture to produce a nucleating agent masterbatch (NA MB); (b) use of a melt mixer to blend a polyolefin and a hydrocarbon resin (HCR) to produce a hydrocarbon resin masterbatch (HCR MB); (c) use of a melt mixer to blend the NA MB of Figure 2(a) and the HCR MB of Figure 2(b) to produce a high barrier polyolefin masterbatch (HBP MB); (d) use of a melt mixer to blend an NA mixture, HCR and a polyolefin to produce a high barrier polyolefin masterbatch (HBP MB). [Diagram 3]

[0055] FIG. 3 is a schematic diagram of an embodiment of the invention in which a melt mixer is used to blend HBP MB and bulk HDPE to produce a high barrier polyolefin (HBP) composition. [Figure 4]

[0056] FIG. 4 is a schematic diagram of an embodiment of the invention in which a melt mixer is used to blend NA MB, HCR or HCR MB and bulk HDPE to produce a HBP composition suitable for forming a barrier layer. [Diagram 5]

[0057] 5 shows an exemplary melt mixer in the form of a twin screw extruder that may be used to prepare any one or more of the masterbatch and HBP compositions as described herein. As shown, the ingredients to be melt mixed may be fed via port 1. HCR ingredients may be added via a side arm feeder via ports 2 and 3. The exhaust of volatiles or gaseous materials is optionally directed via ports 4 and 5. [Figure 6]

[0058] FIG. 6 is a graph showing the effect of different mixing methods on water vapor transmission rate while using the same amount of nucleating agent and hydrocarbon resin. Detailed Description

[0054] definition

[0059] As used herein, the singular forms "a," "an," and "the" designate both the singular and the plural, unless expressly stated to designate only the singular.

[0055]

[0060] As used herein, the use of the term "about" and ranges in general, whether or not qualified by the term about, means that the figures being understood are not limited to the exact figures set forth herein, but are intended to refer to values ​​that are substantially within the range recited but do not depart from the scope of the present invention. As used herein, "about" will be understood by those of skill in the art to allow for small or insubstantial variations, reflecting an appropriate level of precision according to the context in which it is used. If there are uses of the term that are not clear to those of skill in the art given the context in which it is used, "about" will mean up to plus or minus 10% of the particular term.

[0056]

[0061] The term "barrier," as used herein with respect to a material, e.g., a layer, indicates that the material controls the permeation of one or more molecules or compounds, which may be gaseous, vapor or liquid, including, but not limited to, oxygen and water vapor.

[0057]

[0062] As used herein, the terms "comprises," "comprising," "includes," "including," or similar terms are intended to mean a non-exclusive inclusion of a method, process, system, product, composition, or apparatus that includes a list of integers, such that the method, process, system, product, composition, or apparatus does not include only those integers, but may also include other integers that are not listed.

[0058]

[0063] As used herein, the term "consisting of" is an exclusive term and means consisting only of.

[0059]

[0064] As used herein, the term "consisting essentially of" means that integers other than those recited may be included that do not materially alter or affect the properties or function of the method, process, system, product, composition, or apparatus.

[0060]

[0065] All percentages (%) referred to herein are weight percentages (w / w) unless otherwise indicated.

[0061]

[0066] Polymer molecular weights referred to herein are weight average molecular weights (MW) unless otherwise indicated.

[0062]

[0067] As used herein, the term "masterbatch" refers to a concentrate or premix composition of a particular additive or mixture of additives in which the component is dispersed (preferably to achieve a substantially homogeneous dispersion) within a carrier material. In the context of this specification, the carrier material is a polyolefin.

[0063]

[0068] As used herein, the term "polyolefin" refers to a polymer of an olefin monomer. Polyolefins may be homopolymers or copolymers. A "homopolymer" polyolefin refers to a polymer that consists essentially of olefins (i.e., at least 90% by weight, preferably at least 95% by weight, more preferably at least 97% by weight), and thus a homopolymer preferably comprises predominantly said olefin. A "copolymer" polyolefin refers to a polymer formed from the copolymerization of one olefin and at least one other olefin. Non-limiting examples of polyolefins include polyethylene, high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), metallocene linear low density polyethylene (mLLDPE), very low density linear polyethylene (VLLDPE), ethylene-vinyl acetate (EVA), and plastomers.

[0064]

[0069] As used herein, the term "bulk high density polyethylene" ("bulk HDPE") refers to the HDPE with which the masterbatch composition is mixed to form the HBP composition.

[0065]

[0070] As used herein, the term "HBP composition" includes a nucleating agent and a hydrocarbon resin and refers to a mixture produced when bulk HDPE is blended or mixed with an HBP masterbatch, or a nucleating masterbatch and a hydrocarbon resin masterbatch composition.

[0066]

[0071] As used herein, the term "film" may refer to a substantially planar material of any thickness. In some embodiments, a film as described herein can be a substantially planar material having an average thickness of about 500 μm or less, for example, about 10 μm to about 500 μm, preferably about 20 μm to about 200 μm, or about 25 μm to about 100 μm, or about 30 μm to about 80 μm, or about 35 μm to about 70 μm, or about 40 μm to about 60 μm. The film of the present invention can be, for example, a monolayer or multilayer film in the form of a substantially planar sheet or fabric. Films of the present invention in the form of non-planar configurations or shapes are also contemplated, for example, the film may include one or more layers in an article formed by a molding process, for example, blow molding or injection molding. Injection molding may be used to prepare parts and casings, for example, caulking guns and sealant cartridges, as well as blow molding containers, for example, bottles.

[0067]

[0072] As used herein, the term "layer" refers to a discontinuous film component having a substantially uniform composition. In a monolayer film, the terms "film" and "layer" would be synonymous. A "layer" or "barrier layer" may be in the form of a non-planar arrangement or shape.

[0068]

[0073] As used herein, the term "multilayer" refers to multiple layers in a single film structure. The layers may be bonded together by any conventional means known in the art (e.g., coextrusion, lamination, coating, or a combination thereof).

[0069]

[0074] As used herein, the term "substantially" means to a large or significant degree, mostly, or mostly. That is, the term substantially is used to qualify that a parameter, measurement, condition, or feature may have slight variations such as not being absolute or being slightly less than 100% (e.g., 90%, 95%, 98%, 99%), or may have slight, insignificant variations.

[0070]

[0075] As used herein, the term "synergistic effect" refers to an effect or result produced by two or more components that is greater than the additive effect of each individual component when used separately. For example, a synergistic combination of a hydrocarbon resin and a nucleating agent when used to prepare a barrier layer in accordance with the invention disclosed herein improves the barrier properties of the barrier layer to an extent that is greater than the sum or cumulative effect of the improvements that result from or can be attributed to the use of the hydrocarbon resin and the nucleating agent.

[0071]

[0076] As used herein, the term "melt compounding" or "melt mixing" refers to a process in which two or more components are blended to form a compound or composition, typically in which one or more of the following properties are modified in the resulting compound or composition: stiffness, puncture or tear resistance, rheological properties such as melt flow index, melt flow ratio, complex viscosity, processability, flowability, crystallinity, permeability, porosity, etc. These properties may be measured or analyzed directly or indirectly during the melt compounding or melt mixing process, which will be appreciated by those skilled in the art, allowing for adjustment of blending parameters (e.g., residence time, temperature, mixing energy intensity, specific energy input, throughput rate, etc.) during blending to reach desired properties, or blending to be stopped once the desired properties are obtained.

[0072]

[0077] As used herein, the term "homogeneous" refers to a composition in which the components are substantially evenly distributed throughout the composition.Homogeneity may also refer to the dispersion or distribution of components in different phases, such as crystalline and amorphous phases, as well as the interfaces and interactions between different phases.Preferably, homogeneity is achieved by dynamic melt mixing, shear and extensional mixing achieved through techniques such as twin-screw compounding, single-screw compounding, two-roll milling, and the like. Abbreviation

[0078] The following abbreviations used throughout this specification have the following meanings:

[0079] "NA" refers to "nucleating agent."

[0073]

[0080] "MB" stands for "master batch."

[0074]

[0081] "HCR" refers to "hydrocarbon resin."

[0075]

[0082] "HHCR" refers to "hydrogenated hydrocarbon resin."

[0076]

[0083] "HBP" stands for "high barrier polyolefin."

[0077]

[0084] "HDPE" stands for "high density polyethylene."

[0078]

[0085] "MFI" stands for "Melt Flow Index."

[0079]

[0086] "MFR" stands for "Melt Flow Ratio."

[0080]

[0087] "OTR" stands for "oxygen transmission rate."

[0081]

[0088] "WVTR" stands for "water vapor transmission rate." Description of the Aspects

[0089] The present invention generally relates to a method for preparing a film having barrier properties.The present invention is premised on the surprising finding that polyolefins, such as polyethylenes, containing a mixture of a nucleating agent and a relatively low concentration of a hydrocarbon resin (especially below the threshold concentration considered essential in the prior art) can achieve suitable or improved barrier properties balanced with good mechanical properties and processability.

[0082]

[0090] In particular, it has been found that the hydrocarbon resin and the nucleating agent may act synergistically to improve the barrier properties of a barrier layer containing these components, including any one or more of the properties described herein, such as water vapor transmission rate, oxygen transmission rate, rheological properties, processability, etc. That is, the combination of a hydrocarbon resin and a nucleating agent in accordance with the present invention may improve the barrier properties of a barrier layer to a greater extent than the sum or cumulative effect of the hydrocarbon resin and the nucleating agent.

[0083]

[0091] The synergistic effect has surprisingly been found by modifying the blending parameters of the melt compounding or melt mixing process when blending a hydrocarbon resin with a polyolefin, blending a nucleating agent with a polyolefin, blending a hydrocarbon resin and a nucleating agent together with a polyolefin, or blending a masterbatch containing both a hydrocarbon resin and a nucleating agent with a bulk resin, or with two separate masterbatches, i.e., a nucleating agent masterbatch and a hydrocarbon resin masterbatch. In a preferred embodiment, the synergistic effect is realized by blending a masterbatch containing a nucleating agent and a hydrocarbon resin, or two separate masterbatches containing a hydrocarbon resin and a nucleating agent, respectively, with a bulk resin. In a preferred embodiment, one or more blending parameters, such as residence time, temperature, mixing energy intensity, specific energy input, and throughput rate, may be modified to achieve a sufficiently homogenous dispersion between the hydrocarbon resin and the nucleating agent to impart the synergistic effect. Preferably, modifying the residence time of the melt compounding or melt mixing process allows for the formation of a sufficiently homogenous dispersion to impart the synergistic effect.

[0084]

[0092] Without wishing to be limited by any theory, it is believed that a hydrocarbon resin (preferably a hydrogenated hydrocarbon resin) dispersed in a polyolefin, such as polyethylene, preferably HDPE, can help make the amorphous phase of the polyolefin less permeable to elements such as oxygen and water vapor, while enhancing the dispersion of the crystalline phase within the polymer by modifying the rheological properties of the polymer to make it more suitable for melt relaxation during extrusion and molding processes which promotes enhanced barrier properties if the resin is effectively nucleated. Thus, in this manner, the hydrocarbon resin can enhance the action of the nucleating agent in the polyolefin, thus further reducing oxygen and / or water vapor permeation beyond additive or cumulative effects, i.e., helping to create a synergistic effect. Based on the conventional understanding that the hydrocarbon resin is limited to being dispersed in and affecting the amorphous phase, thereby limiting any effect on the crystalline phase and the nucleating agent dispersed therein, the present invention provides unexpected results demonstrating a synergistic effect not taught or suggested in the prior art.

[0085]

[0093] A person skilled in the art can use routine techniques to identify when an appropriate degree of homogeneity has been achieved, for example, by measuring one or more of the physical properties of the composition during or after the melt compounding or melt mixing process.In addition, a person skilled in the art can modify one or more of the blending parameters to achieve sufficient homogeneity in the composition to impart the synergistic effects of the present invention.Exemplary parameters include, for example, residence time, mixing energy input, melt temperature, and mixing time, among others.A person skilled in the art will understand how parameters such as mixing energy input, melt temperature, and mixing time correlate with achieving homogeneity in a melt mixer.

[0086]

[0094] In implementing the present invention, one skilled in the art may take samples at relevant intervals during the blending / mixing process to determine whether the blending / mixing parameters (e.g., residence time) are sufficient to impart the desired synergistic effect. For example, one skilled in the art may compare the WVTR of films prepared from samples taken during the blending process to determine whether a desired threshold value of a property has been achieved. If not, the blending process may be continued until subsequent samples confirm that the desired property (e.g., WVTR, OTR, rheology, etc.) has been achieved. Preferably, the mixing / blending process will be continued until samples indicate that the WVTR and / or OTR reflect a synergistic effect rather than an additive effect that may be due to NA and HCR.

[0087]

[0095] Preferred embodiments disclosed herein are directed to the use of defined ratios and / or amounts of nucleating agent and hydrocarbon resin, in some embodiments, the synergistic effect is at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% greater than the cumulative effect of the hydrocarbon resin and nucleating agent when used separately.

[0088]

[0096] Advantageously, the method of preparing the masterbatch composition may facilitate substantially homogeneous dispersion of the nucleating agent while using reduced amounts or concentrations of hydrocarbon resin (e.g., HCR concentration less than 10% w / w) to achieve improved barrier film properties, such as lower WVTR, balanced with good mechanical properties, such as puncture and tear resistance, when using said masterbatch composition. This is in contrast to the conventional understanding in the art that relatively high concentrations of HCR, at least about 10%-20% w / w, are required to achieve suitable WVTR performance in a typical film, such as about a 30% reduction in WVTR.

[0089]

[0097] In a preferred embodiment, the present invention relates to a method for preparing a masterbatch composition comprising a substantially homogeneous blend of component raw materials. In a further embodiment, the present invention relates to the use of such a masterbatch composition to form a high barrier polyolefin (HBP) composition, and to the use of the HBP composition to form an HBP layer in a polyolefin film.

[0090]

[0098] Masterbatch technology is a particularly effective technique for preparing high barrier polyolefin (HBP) layers according to the present invention. Advantageously, the use of masterbatch technology to prepare barrier layers in films may provide one or more benefits, such as improved dispersion of the nucleating agent and / or hydrocarbon resin in the polyolefin, such as HDPE, improving the crystallinity characteristics of the resulting barrier layer, and facilitating the effectiveness of the compounding, melt mixing, and / or extrusion process.

[0091]

[0099] In a preferred embodiment, the method of preparing the masterbatch composition as described herein may provide for efficient and substantially homogeneous nucleation of polyolefins, such as HDPE, even when a hydrocarbon resin is introduced at the same time. In a further embodiment, a method is provided for preparing a masterbatch composition containing both a nucleating agent and a hydrocarbon resin at the same time, or separate nucleating agent masterbatches and hydrocarbon masterbatches used simultaneously or sequentially. Such a method may balance the required amount of each component while maintaining suitable processability requirements in such masterbatches. When such a masterbatch is used to form a barrier layer, a film containing the barrier layer may achieve significantly improved barrier properties while retaining good mechanical properties.

[0092]

[0100] Thus, in a preferred embodiment, the method of preparing such masterbatches and their use in the method of preparing barrier layers and films can provide overall cost feasibility during production. Advantageously, an embodiment of the present invention provides components blended in selected amounts or ratios that can achieve a substantially homogeneous or uniform dispersion of the hydrocarbon resin and nucleating agent in a polyolefin, such as HDPE. In a further embodiment, the method of preparing such masterbatches and their use in preparing barrier layers can advantageously reduce the amount of hydrocarbon resin required to provide the desired barrier layer resistance, especially in terms of WVTR, while still retaining good mechanical properties, such as puncture and tear resistance. The reduction in the amount and concentration of the hydrocarbon resin can reduce the overall manufacturing costs, which provides a significant commercial advantage.

[0093]

[0101] Tear strength (in the machine and transverse directions) is the ability of a film to withstand the extension of a defect or tear in the film. It is an important property in many film applications. Due to orientation effects, poor films may have an undesirable tendency to tear easily when a defect or tear is initiated in the film. Tear strength, or more specifically tear propagation strength, is commonly measured in both the machine and transverse directions with the aid of a pendulum in the Elmendorf test. This test measures the energy required to propagate a tear formed as a small tear in a film sample.

[0094]

[0102] Puncture resistance involves the ability of a film to resist damage and puncture from protruding and sharp structures that tend to induce high stress areas in the material. This property is typically measured by the puncture energy, which is a measure of the maximum force or energy required to penetrate the material. This type of biaxial stress is found in packaging films that have rigid protrusions, such as when packaging pelletized dry foods, such as cereals and pet foods, and frozen vegetables.

[0095]

[0103] Other embodiments disclosed herein advantageously allow hydrocarbon resins to be used in reduced amounts (e.g., less than 10% w / w) than previously considered necessary in the prior art, while still maintaining or improving the resulting barrier layer properties.

[0096]

[0104] In a preferred embodiment, the method according to the present invention improves the dispersion of the nucleating agent and / or hydrocarbon resin in the masterbatch composition and / or together with the bulk HDPE in the resulting high barrier polyolefin composition, thereby improving the crystallinity characteristics of the resulting barrier layer.

[0097]

[0105] In a preferred embodiment, the process of the present invention may include extended residence time in a melt mixer comprising a twin screw extruder or a single screw extruder.

[0098]

[0106] In one or more embodiments, the present invention utilizes an effective method of melt mixing or blending one or more of the hydrocarbon resin, nucleating agent, HCR MB, NA MB, or HBP MB with bulk HDPE. In a preferred embodiment, masterbatch technology may be used to produce a substantially homogeneous or uniform dispersion of the hydrocarbon resin and / or nucleating agent in polyolefin, such as HDPE. In a preferred embodiment, masterbatch technology may be used to produce a substantially homogeneous or uniform dispersion of the hydrocarbon resin and / or nucleating agent in bulk HDPE in the resulting high barrier polyolefin composition to produce a barrier layer. The use of masterbatch technology according to the present invention unexpectedly allows barrier films with reduced WVTR to be produced that contain relatively low concentrations of hydrocarbon resin.

[0099]

[0107] Advantageously, when preparing a barrier layer for use in a film made using the master composition, the method for preparing the master batch composition as described herein provides a barrier layer having a coating density of about 4 g / m or less in the film, measured at about 38° C. and 90% external relative humidity. 2 It can provide a water vapor transmission rate of 100 / day.

[0100]

[0108] In one or more embodiments, a suitable HBP composition for forming a barrier layer may be prepared by melt compounding HCR MB and NA MB into bulk HDPE in a suitable extrusion device to form the HBP composition. The amount of HCR MB and NA MB may be selected to achieve a desired ratio of HCR and NA in the barrier layer. The extrusion device may include a single pass or a multi-pass extruder, preferably a single pass extruder. In a preferred embodiment, the extrusion device is a twin screw extruder.

[0101]

[0109] By mixing the nucleating agent and / or the hydrocarbon resin with a polyolefin, such as HDPE, to form a masterbatch, the nucleating agent or the hydrocarbon resin, respectively, can be directly incorporated during processing. Thus, the use of a masterbatch eliminates the need for a separate compounding step to incorporate the nucleating agent or the hydrocarbon resin into the bulk HDPE. Due to economic considerations, it is preferred to achieve the desired concentration of HCR and / or NA in the masterbatch without compromising the ability of the masterbatch to be uniformly blended into the bulk HDPE during the melt mixing and / or extrusion process. In a preferred embodiment, it is desirable to achieve the highest possible HCR content in the masterbatch while still balancing the desired properties and cost of the resulting HBP composition.

[0102]

[0110] Nucleating agents are known to be generally difficult to disperse directly in HDPE due to their relatively poor miscibility. The use of masterbatch technology to pre-disperse nucleating agents as concentrates in carrier resins, such as polyolefins, such as HDPE, to produce a substantially homogeneous dispersion of nucleating agents in the masterbatch is a further advantage of the present invention, especially when the nucleating agent masterbatch is co-blended with a hydrocarbon resin masterbatch to form an HBP masterbatch, which can then be subsequently blended with bulk HDPE to form a HBP composition useful for forming a barrier layer or a film containing a barrier layer. Advantageously, the use of a masterbatch can allow a small amount of NA to be dispersed in a carrier resin in a convenient and controllable manner. Masterbatch Technology

[0111] The term "masterbatch," as used herein with respect to a nucleating agent (NA) or a hydrocarbon resin (HCR), or a combination of NA and HCR, refers to a composition that contains a relatively high concentration of NA, HCR, or a combination of NA and HCR in a polyolefin resin, preferably a polyethylene resin, more preferably HDPE.

[0103]

[0112] Typically, the hydrocarbon resin masterbatch (HCR MB) may comprise from about 5% to about 80% w / w, or from about 2.5% to about 80% w / w, or from about 2.5% to about 70% w / w, or from about 2.5% to about 60% w / w, or from about 10% to about 70% w / w, or from about 15% to about 65% w / w, or from about 20% to about 60% w / w, or from about 5% to about 50% w / w, or from about 7.5% to about 45% w / w, or from about 10% to about 40% w / w, or from about 30% to about 50% w / w, or from about 25% to about 55% w / w of HCR, the remainder being a polyolefin resin and optionally one or more conventional additives as described herein.

[0104]

[0113] Typically, the nucleating agent masterbatch (NA MB) may contain from about 0.1% to about 30% w / w, or from about 0.2% to about 25% w / w, or from about 0.3% to about 25% w / w, or from about 0.2% to about 15% w / w, or from about 0.3% to about 20% w / w, or from about 0.3% to about 15% w / w, or from about 0.5% to about 20% w / w, or from about 0.5% to about 10%, or from about 0.3% to about 10% w / w of nucleating agent, with the remainder being polyolefin resin and optionally one or more conventional additives as described herein.

[0105]

[0114] Depending on scale, an appropriate amount (e.g., some or all) of the NA MB and / or HCR MB may be blended with the bulk HDPE to obtain the desired amount or concentration of nucleating agent and / or hydrocarbon resin in the resulting HBP masterbatch or HBP composition.

[0106]

[0115] An advantage of the present invention is that it may allow for the addition of small amounts of nucleating agents and / or hydrocarbon resins to bulk HDPE during the extrusion process in a manner that provides homogeneous mixing, preferably resulting in improved barrier properties. Thus, an embodiment of the present invention is A process for preparing a high barrier polyolefin masterbatch (HBP MB) composition comprising a nucleating agent and a hydrocarbon resin in a polyolefin carrier, preferably a HDPE resin; A process for preparing a nucleator masterbatch (NA MB) comprising a nucleator in a polyolefin carrier, preferably a HDPE resin, and a hydrocarbon resin masterbatch (HCR MB) comprising a hydrocarbon resin in a polyolefin carrier, preferably a HDPE resin; A method for preparing an HBP MB composition formed by melt blending NA MB and HCR MB as described herein, or by melt blending NA and HCR with a polyolefin carrier, preferably HDPE resin. wherein the method provides a substantially homogeneous dispersion of the components in the resulting masterbatch. It concerns the method.

[0107]

[0116] The masterbatch compositions prepared according to these methods may be blended with the bulk HDPE resin used to form the barrier layer, and thus the polyolefin carrier in the masterbatch composition is also blended with the bulk HDPE resin.

[0108]

[0117] In a preferred embodiment, the polyolefin carrier is selected to provide a resultant viscosity in the masterbatch composition that is lower than or close to the viscosity of the bulk HDPE, preferably to facilitate blending between the masterbatch composition and the bulk HDPE.

[0109]

[0118] In another embodiment, the polyolefin carrier in the nucleating agent masterbatch has a lower viscosity than that of bulk HDPE. In a further embodiment, the polyolefin carrier in the nucleating agent masterbatch is HDPE with a higher MFI than that of bulk HDPE.

[0110]

[0119] In another embodiment, the polyolefin carrier in the hydrocarbon resin masterbatch has a viscosity higher than or similar to that of bulk HDPE. In a further embodiment, the polyolefin carrier in the hydrocarbon resin masterbatch is HDPE with a MFI lower than or similar to that of bulk HDPE.

[0111]

[0120] Delivery of the nucleating agent and the hydrocarbon resin via a masterbatch can be particularly advantageous since it can promote a more uniform dispersion of the desired amount of the nucleating agent and / or the hydrocarbon resin in the final HBP composition. In addition, delivery of the nucleating agent and / or the hydrocarbon resin via a masterbatch may also advantageously improve the crystallinity characteristics of the resulting barrier layer. Delivery of the nucleating agent and / or the hydrocarbon resin via a masterbatch may also advantageously promote the effectiveness of the compounding, melt mixing and / or extrusion process to form the barrier layer while retaining good mechanical properties. In a preferred embodiment, the inventors have developed a method for preparing a masterbatch composition and a method for using such a prepared masterbatch to form a barrier layer having one or more advantageous properties. For example, improved processability, mechanical properties, such as stiffness, due to the relatively low levels of HCR used, lowered production costs. NA Masterbatch

[0121] Further aspects of the present invention relate to a method for preparing a nucleating agent masterbatch (NA MB) and to the resulting NA MB.

[0112]

[0122] Preferably, the method provides a substantially homogeneous distribution of the components in the resulting masterbatch.

[0113]

[0123] In one more preferred embodiment, the nucleating agent masterbatch comprises from about 0.1% to about 30% w / w, or from about 0.2% to about 25% w / w, or from about 0.2% to about 15% w / w, or from about 0.3% to about 25% w / w, or from about 0.3% to about 20% w / w, for example from about 5% to about 15% nucleating agent.

[0114]

[0124] In one or more embodiments, the nucleating agent masterbatch is from about 0.1% w / w to about 1% w / w, or from about 1% w / w to about 3% w / w, or from about 3% w / w to about 5% w / w, or from about 5% w / w to about 7% w / w, or from about 7% w / w to about 8% w / w, or from about 8% w / w to about 10% w / w, or from about 10% w / w to about 12% w / w, or or from about 12% w / w to about 14% w / w, or from about 14% w / w to about 16% w / w, or from about 16% w / w to about 18% w / w, or from about 18% w / w to about 20% w / w, or from about 20% w / w to about 22% w / w, or from about 22% w / w to about 25% w / w, or from about 25% w / w to about 30% w / w of nucleating agent.

[0115]

[0125] In another aspect, the present invention relates to a method comprising blending a nucleating agent mixture comprising a nucleating agent with a polyolefin carrier, preferably polyethylene, to form a nucleating agent masterbatch. More preferably, the polyethylene is high density polyethylene (HDPE).

[0116]

[0126] Preferably, the nucleating agent mixture comprises a nucleating agent and a polyolefin, preferably polyethylene. The polyethylene may be a polyethylene powder. In a preferred embodiment, the nucleating agent may be dry blended with the polyethylene powder to form the nucleating agent mixture.

[0117]

[0127] Preferably, the nucleating agent mixture includes one or more additional components as described herein.

[0118]

[0128] Another aspect of the present invention relates to a nucleating agent masterbatch produced by the method as described herein.

[0119]

[0129] Preferably, the nucleating agent masterbatch includes one or more additional ingredients as described herein.

[0120]

[0130] A representative embodiment is illustrated in FIG. 2(a). HCR Masterbatch

[0131] In another aspect, the present invention relates to a process for preparing a hydrocarbon resin masterbatch (HCR MB) and to the obtained HCR MB.

[0121]

[0132] In one or more preferred embodiments, the present invention relates to a process that involves blending a hydrocarbon resin with a polyolefin carrier, preferably high density polyethylene (HDPE), to form a hydrocarbon resin masterbatch.

[0122]

[0133] Preferably, the method provides a substantially homogeneous distribution of the components in the resulting masterbatch.

[0123]

[0134] In one or more preferred embodiments, the hydrocarbon resin masterbatch comprises from about 5% to about 80% w / w, preferably from about 10% to about 70% w / w, more preferably from about 20% to about 60% w / w, and even more preferably from about 30% to about 50% w / w of hydrocarbon resin.

[0124]

[0135] In one or more embodiments, the hydrocarbon resin masterbatch is from about 5% w / w to about 10% w / w, or from about 10% w / w to about 15% w / w, or from about 15% w / w to about 20% w / w, or from about 20% w / w to about 25% w / w, or from about 25% w / w to about 30% w / w, or from about 30% w / w to about 35% w / w, or from about 35% w / w to about 40% w / w. or about 40% w / w to about 45% w / w, or about 45% w / w to about 50% w / w, or about 50% w / w to about 55% w / w, or about 55% w / w to about 60% w / w, or about 60% w / w to about 65% w / w, or about 65% w / w to about 70% w / w, or about 70% w / w to about 80% w / w of the hydrocarbon resin.

[0125]

[0136] Preferably, the hydrocarbon resin masterbatch includes one or more additional ingredients as described herein.

[0126]

[0137] Another aspect of the present invention relates to a hydrocarbon resin masterbatch produced by the method as described herein.

[0127]

[0138] An exemplary embodiment of this aspect is illustrated in FIG. 2(b). HBP Masterbatch

[0139] In a further aspect, the present invention relates to a method for preparing a high barrier polyolefin (HBP) masterbatch composition, which may be used to form a barrier layer in a film.

[0128]

[0140] HBP Masterbatch (HBP MB) refers to a concentrated composition comprising a nucleating agent and a hydrocarbon resin dispersed in a polyolefin carrier, preferably polyethylene. More preferably, the polyethylene is high density polyethylene (HDPE). In one embodiment, the HBP MB may be produced by blending an NA MB or a NA mixture with an HCR MB or HCR. In another embodiment, the HBP MB may be produced by blending NA and HCR with HDPE.

[0129]

[0141] In various embodiments, the HBP masterbatch comprises one or more nucleating agents, preferably one nucleating agent, one or more hydrocarbon resins, preferably one hydrocarbon resin, with the remainder of the HBP masterbatch composition comprising a polyolefin carrier, preferably polyethylene, more preferably HDPE, and optionally one or more conventional additives, as described herein.

[0130]

[0142] Preferably, the nucleating agent is present in the HBP masterbatch in an amount of from about 0.1% to about 30% w / w, or from about 0.2% to about 25% w / w, or from about 0.3% to about 25% w / w, or from about 0.2% to about 15% w / w, or from about 0.3% to about 20% w / w, or from about 0.3% to about 15% w / w, or from about 0.5% to about 20% w / w, or from about 0.5% to about 10%, or from about 0.3% to about 10% w / w.

[0131]

[0143] Preferably, the HCR is present in the HBP masterbatch in an amount of from about 5% to about 80% w / w, or from about 2.5% to about 80% w / w, or from about 2.5% to about 70% w / w, or from about 2.5% to about 60% w / w, or from about 10% to about 70% w / w, or from about 15% to about 65% w / w, or from about 20% to about 60% w / w, or from about 5% to about 50% w / w, or from about 7.5% to about 45% w / w, or from about 10% to about 40% w / w, or from about 30% to about 50% w / w, or from about 25% to about 55% w / w.

[0132]

[0144] In one or more embodiments, the HBP masterbatch may contain from about 0.2% w / w to about 2% w / w, or from about 2% w / w to about 4% w / w, or from about 4% w / w to about 6% w / w, or from about 6% w / w to about 8% w / w, or from about 8% w / w to about 10% w / w, or from about 10% w / w to about 12% w / w, or from about 12% w / w to about 14% w / w, or from about 14% w / w to about 16% w / w, or from about 16% w / w to about 18% w / w, or from about 18% w / w to about 20% w / w, or from about 20% w / w to about 22% w / w, or from about 22% w / w to about 25% w / w of nucleating agent.

[0133]

[0145] In one or more embodiments, the HBP masterbatch may comprise from about 2.5% w / w to about 5% w / w, or from about 5% w / w to about 10% w / w, or from about 10% w / w to about 15% w / w, or from about 15% w / w to about 20% w / w, or from about 20% w / w to about 25% w / w, or from about 25% w / w to about 30% w / w, or from about 30% w / w to about 35% w / w, or from about 35% w / w to about 40% w / w, or from about 40% w / w to about 45% w / w, or from about 45% w / w to about 50% w / w, or from about 50% w / w to about 60% w / w, or from about 60% w / w to about 70% w / w of the hydrocarbon resin.

[0134]

[0146] In one aspect, the present invention provides a method for producing a high barrier polyolefin masterbatch (HBP MB) comprising a nucleating agent (NA) and a hydrocarbon resin (HCR), the method comprising: (a) blending a nucleating agent mixture comprising a nucleating agent with a first polyolefin to form a nucleating agent masterbatch (NA MB); (b) blending a hydrocarbon resin into a second polyolefin to form a hydrocarbon resin masterbatch (HCR MB); (c) blending the nucleating agent masterbatch and the hydrocarbon resin masterbatch to form the HBP MB; The present invention relates to a method comprising the steps of:

[0135]

[0147] In another aspect, the present invention provides a method for producing a high barrier polyolefin masterbatch (HBP MB) comprising a nucleating agent (NA) and a hydrocarbon resin (HCR), the method comprising: The present invention relates to a process comprising blending a nucleating agent masterbatch or a nucleating agent mixture with a hydrocarbon resin or a hydrocarbon resin masterbatch, and optionally a polyolefin, such as a polyethylene, for example HDPE, to form a high barrier polyolefin masterbatch (HBP MB).

[0136]

[0148] Preferably, the first polyolefin is polyethylene, more preferably HDPE.

[0137]

[0149] Preferably, the second polyolefin is polyethylene, more preferably HDPE.

[0138]

[0150] Steps (a) and (b) may be performed in any order.

[0139]

[0151] An exemplary embodiment of this aspect of the invention is illustrated in Figures 2(a)-2(c).

[0140]

[0152] In one or more embodiments, the ratio of the nucleating agent masterbatch to the hydrocarbon resin masterbatch is from about 10:1 to about 1:100, or from about 25:4 to about 1:80, or from about 50:9 to about 1:70, or from about 5:1 to about 1:60, or from about 5:1 to about 1:50. Preferably, the ratio of the nucleating agent masterbatch to the hydrocarbon resin masterbatch is from about 5:1 to about 1:60, or from about 5:1 to about 1:50.

[0141]

[0153] In another aspect, the present invention provides a method for producing a high barrier polyolefin masterbatch (HBP MB) comprising a nucleating agent (NA) and a hydrocarbon resin (HCR), the method comprising: The method includes blending (i) a nucleating agent mixture comprising a nucleating agent, (ii) a hydrocarbon resin, and (iii) a polyolefin to form an HBP MB.

[0142]

[0154] Preferably, the polyolefin is polyethylene, more preferably HDPE.

[0143]

[0155] An exemplary embodiment of this aspect of the invention is illustrated in FIG. 2(d).

[0144]

[0156] In some embodiments of the above aspects, the nucleating agent and the hydrocarbon resin are present in the masterbatch in a ratio of about 1:4 to about 1:200, preferably about 1:7 to about 1:150, and more preferably about 1:10 to about 1:100 or about 1:15 to about 1:50.

[0145]

[0157] In a preferred embodiment, the nucleating agent mixture comprises a nucleating agent and a polyolefin carrier, preferably polyethylene. The polyethylene may be a polyethylene powder. In a preferred embodiment, the nucleating agent is dry blended with the polyethylene powder to form the nucleating agent mixture.

[0146]

[0158] The first and second polyolefins may be the same or different. In some embodiments, the first and second polyolefins may have the same or different MFI. In some embodiments, the first and second polyolefins may have the same or different density. In some embodiments, the first and / or second polyolefin is polyethylene, preferably HDPE, where the HDPE is the same or different. In some embodiments, the first and second polyolefin is polyethylene, preferably HDPE, where each HDPE has the same or different MFI. In some embodiments, the first and second polyolefin is polyethylene, preferably HDPE, where each HDPE has the same or different density. In a preferred embodiment, the first polyolefin, preferably polyethylene, more preferably HDPE, has a higher melt index than the second polyolefin, preferably polyethylene, more preferably HDPE.

[0147]

[0159] In another embodiment, the HBP masterbatch may be produced by blending a nucleating agent masterbatch (NA MB) and a hydrocarbon resin or hydrocarbon resin masterbatch (HCR MB) as described herein.

[0148]

[0160] Aspects of the invention also relate to high barrier polyolefin masterbatches (HBP MB) produced by the methods described herein.

[0149]

[0161] Preferably, the method as described herein provides a substantially homogeneous dispersion of the nucleating agent and the hydrocarbon resin in the resulting masterbatch, preferably wherein the homogeneity is sufficient to provide a synergistic effect between the nucleating agent and the hydrocarbon resin. Preferably, the HBP masterbatch comprises a synergistic combination of nucleating agent and hydrocarbon resin.

[0150]

[0162] In a preferred embodiment, the blending comprises melt mixing. Preferably, the melt mixing is carried out for a period of time, e.g., residence time, sufficient to produce a substantially homogeneous dispersion.

[0151]

[0163] In a preferred embodiment, the blending is carried out using an extruder, such as a twin screw extruder. Masterbatch Preparation

[0164] Masterbatches according to the present invention, including NA MB, HCR MB, and HBP MB, may be prepared using the methods as disclosed herein. General techniques and equipment for preparing masterbatches are known to those skilled in the art and are also described, for example, in WO00 / 56806 (Eastman), the entire contents of which are incorporated herein by cross-reference.

[0152]

[0165] In a preferred embodiment, the masterbatch is formed by melt compounding. In one embodiment, the nucleating agent and the hydrocarbon resin may be melt compounded in a polyolefin carrier, such as polyethylene, preferably HDPE, to prepare the HBP masterbatch. Melt compounding techniques may be used to prepare the barrier layer, for example, by melt compounding the HBP masterbatch and bulk HDPE.

[0153]

[0166] In a preferred embodiment, melt blending is the technique used for masterbatch preparation because it advantageously enhances effective dispersion of the nucleating agent and the hydrocarbon resin in the polyolefin carrier, such as polyethylene, preferably HDPE. Substantially uniform dispersion of the nucleating agent and the hydrocarbon resin in the polyolefin carrier is preferred because the inventors have surprisingly found that proper dispersion, preferably uniform or homogeneous dispersion, of the nucleating agent and the hydrocarbon resin in the polyolefin promotes desirable barrier properties. Also surprisingly, the inventors have found that improved desirable barrier properties may be achieved with a low percentage of the hydrocarbon resin. In another embodiment, dry blending may be used for masterbatch preparation.

[0154]

[0167] Preferably, the method as described herein provides a substantially homogeneous dispersion of the nucleating agent and the hydrocarbon resin in the resulting masterbatch, preferably wherein the homogeneity is sufficient to provide a synergistic effect between the nucleating agent and the hydrocarbon resin.

[0155]

[0168] In one or more embodiments, the masterbatch may be formed by melt compounding a selected amount of nucleating agent and / or hydrocarbon resin in a polyolefin carrier, such as polyethylene, preferably HDPE, in a single pass or multi-pass extruder, preferably a twin screw extruder. In an exemplary embodiment, the twin screw extruder has barrel zone temperatures set to provide a constant melt temperature of about 150-220°C. HBP composition

[0169] In another aspect, the present invention relates to a method for producing a high barrier polyolefin (HBP) composition comprising a combination of a nucleating agent and a hydrocarbon resin, the method comprising blending a nucleating agent (NA), a hydrocarbon resin (HCR) and a polyolefin carrier, such as polyethylene, preferably HDPE, to form a substantially homogeneous dispersion using a masterbatch composition as described herein, preferably wherein the homogeneity is sufficient to provide a synergistic effect between the nucleating agent and the hydrocarbon resin. Preferably, the HBP composition comprises a synergistic combination of a nucleating agent and a hydrocarbon resin.

[0156]

[0170] Preferably, the HBP composition includes one or more additional ingredients as described herein.

[0157]

[0171] Various embodiments of this aspect are illustrated in Figures 2-5.

[0158]

[0172] The resulting HBP composition produced according to the embodiments disclosed herein may then be processed to form a barrier layer. Techniques for forming the barrier layer are described herein. In one embodiment, the barrier layer is formed by extrusion. Suitable extrusion techniques are known in the art, and representative techniques are described herein.

[0159]

[0173] In one or more embodiments, blending may be accomplished by melt compounding (e.g., melt mixing) the respective components to blend the components together. Melt compounding may be accomplished using techniques and equipment known to those skilled in the art, such as an extruder or other suitable blending equipment. The extruder may be a twin screw extruder or a single screw extruder. Preferably, the extruder is a twin screw extruder.

[0160]

[0174] In one or more embodiments, suitable amounts or ratios of the nucleating agent masterbatch and the hydrocarbon resin masterbatch may be blended with the bulk HDPE by melt compounding. By blending the NA masterbatch and the HCR masterbatch with the bulk HDPE, the desired amount of the nucleating agent and the hydrocarbon resin may be introduced into the HBP composition for melt compounding with the bulk HDPE. The NA masterbatch may be introduced into the bulk HDPE before or after the HCR masterbatch. Alternatively, the NA masterbatch and the HCR masterbatch may be introduced into the bulk HDPE simultaneously at the same or different rates.

[0161]

[0175] According to embodiments as described herein, a desired amount or proportion of nucleating agent and hydrocarbon resin may be introduced into the HBP composition for melt compounding with bulk HDPE by adding (e.g., blending) an HBP masterbatch containing the nucleating agent and hydrocarbon resin with the bulk HDPE.

[0162]

[0176] In one or more embodiments, the present invention provides a method for producing a high barrier polyolefin (HBP) composition, the method comprising: (a) blending a mixture including a nucleating agent into a first polyolefin to form a nucleating agent masterbatch (NA MB); (b) blending a hydrocarbon resin into a second polyolefin to form a hydrocarbon resin masterbatch (HCR MB); (c) blending the nucleating agent masterbatch and the hydrocarbon resin masterbatch to form a high barrier polyolefin masterbatch (HBP MB); (d) blending the high barrier polyolefin masterbatch (HBP MB) and bulk HDPE to form a high barrier polyolefin (HBP) composition; The present invention relates to a method comprising the steps of:

[0163]

[0177] In one or more embodiments, the present invention provides a method for producing a high barrier polyolefin (HBP) composition, the method comprising: (a) blending a nucleating agent masterbatch or a nucleating agent mixture with a hydrocarbon resin or a hydrocarbon resin masterbatch, and optionally a polyolefin, such as a polyethylene, e.g., HDPE, to form a high barrier polyolefin masterbatch (HBP MB); (b) blending the high barrier polyolefin masterbatch (HBP MB) and bulk HDPE to form a high barrier polyolefin (HBP) composition; The present invention relates to a method comprising the steps of:

[0164]

[0178] Preferably, the method as described herein provides a substantially homogeneous dispersion of the nucleating agent and the hydrocarbon resin in the HBP MB, preferably wherein the homogeneity is sufficient to provide a synergistic effect between the nucleating agent and the hydrocarbon resin.

[0165]

[0179] Representative embodiments are illustrated in FIGS.

[0166]

[0180] In one or more embodiments, the present invention provides a method for producing a high barrier polyolefin (HBP) composition, the method comprising: (a) blending a mixture including a nucleating agent into a first polyolefin to form a nucleating agent masterbatch (NA MB); (b) blending a hydrocarbon resin into a second polyolefin to form a hydrocarbon resin masterbatch (HCR MB); (c) blending the nucleating agent masterbatch, the hydrocarbon resin masterbatch and the bulk HDPE to form a high barrier polyolefin (HBP) composition; The present invention relates to a method comprising the steps of:

[0167]

[0181] Preferably, the first polyolefin is polyethylene, more preferably HDPE.

[0168]

[0182] Preferably, the second polyolefin is polyethylene, more preferably HDPE.

[0169]

[0183] Preferably, the method as described herein provides a substantially homogeneous dispersion of the nucleating agent and the hydrocarbon resin in the HBP composition, preferably wherein the homogeneity is sufficient to provide a synergistic effect between the nucleating agent and the hydrocarbon resin.

[0170]

[0184] Representative embodiments are illustrated in FIGS. 2(a), 2(b) and 4.

[0171]

[0185] One of ordinary skill in the art would be able to readily determine the appropriate amounts of each masterbatch and bulk HDPE to be blended together to produce an HBP composition having the desired amount or concentration of nucleating agent and hydrocarbon resin, taking into account the concentrations of these components in each masterbatch composition. In one or more embodiments, the amount of nucleating agent masterbatch may be in the range of about 0.04% to about 30% w / w of the HBP composition, and the amount of hydrocarbon resin masterbatch may be in the range of about 0.14% to about 70% w / w of the HBP composition.

[0172]

[0186] In one or more embodiments, the HBP composition is from about 0.04% w / w to about 0.1% w / w, or from about 0.1% w / w to about 0.5% w / w, or from about 0.5% w / w to about 1% w / w, or from about 1% w / w to about 3% w / w, or from about 3% w / w to about 5% w / w, or from about 5% w / w to about 7% w / w, or from about 7% w / w to about 8% w / w, or from about 8% w / w to about 10% w / w, or The nucleating agent masterbatch may comprise from 10% w / w to about 12% w / w, or from about 12% w / w to about 14% w / w, or from about 14% w / w to about 16% w / w, or from about 16% w / w to about 18% w / w, or from about 18% w / w to about 20% w / w, or from about 20% w / w to about 22% w / w, or from about 22% w / w to about 25% w / w, or from about 25% w / w to about 30% w / w.

[0173]

[0187] In one or more embodiments, the HBP composition is from about 0.14% w / w to about 1% w / w, or from about 1% w / w to about 5% w / w, or from about 5% w / w to about 10% w / w, or from about 1% w / w to about 10% w / w, or from about 10% w / w to about 20% w / w, from about 20% w / w to about 25% w / w, or from about 25% w / w to about 30% w / w, or from about 30% w / w to about 35% w / w. or about 35% w / w to about 40% w / w, or about 40% w / w to about 45% w / w, or about 45% w / w to about 50% w / w, or about 50% w / w to about 55% w / w, or about 55% w / w to about 60% w / w, or about 60% w / w to about 65% w / w, or about 65% w / w to about 70% w / w of the hydrocarbon resin masterbatch.

[0174]

[0188] In one or more embodiments, a nucleating agent masterbatch or mixture of nucleating agents and a hydrocarbon resin or a hydrocarbon resin masterbatch is blended with bulk HDPE to produce an HBP composition having a desired or suitable amount and distribution of nucleating agent and hydrocarbon resin dispersed within the HBP composition, particularly to achieve a synergistic effect.

[0175]

[0189] In one or more embodiments, a suitable amount of the HBP masterbatch may be blended with bulk HDPE by melt compounding. In one or more embodiments, an amount of the HBP masterbatch in the range of about 0.2% to about 75% w / w may be combined with a desired amount of bulk HDPE resin to produce an HBP composition having a desired amount or ratio and distribution of nucleating agent and hydrocarbon resin.

[0176]

[0190] In one or more embodiments, the HBP composition comprises from about 0.2% w / w to about 2% w / w, or from about 2% w / w to about 4% w / w, or from about 4% w / w to about 6% w / w, or from about 6% w / w to about 8% w / w, or from about 8% w / w to about 10% w / w, or from about 10% w / w to about 12% w / w, or from about 12% w / w to about 14% w / w, or from about 14% w / w to about 16% w / w, or from about 16% w / w to about 18% w / w, or from about 18% w / w to about 20% w / w, or from about 20% w / w to about 22% w / w, or from about 20% w / w to about 22% w / w. The HBP masterbatch may comprise from 2% w / w to about 25% w / w, or from about 25% w / w to about 30% w / w, or from about 30% w / w to about 35% w / w, or from about 35% w / w to about 40% w / w, or from about 40% w / w to about 45% w / w, or from about 45% w / w to about 50% w / w, or from about 50% w / w to about 55% w / w, or from about 55% w / w to about 60% w / w, or from about 60% w / w to about 65% w / w, or from about 65% w / w to about 70% w / w, or from about 70% w / w to about 75% w / w.

[0177]

[0191] In one embodiment, the amount of HBP masterbatch blended with the bulk HDPE resin is about 7% by weight, based on the total weight of the masterbatch composition and HDPE.

[0178]

[0192] In another preferred embodiment, the nucleating agent masterbatch comprises from about 0.1% to about 30% w / w of nucleating agent.

[0179]

[0193] In one or more embodiments, the nucleating agent masterbatch is from about 0.1% w / w to about 1% w / w, or from about 1% w / w to about 3% w / w, or from about 3% w / w to about 5% w / w, or from about 5% w / w to about 7% w / w, or from about 7% w / w to about 8% w / w, or from about 8% w / w to about 10% w / w, or from about 10% w / w to about 12% w / w, or or from about 12% w / w to about 14% w / w, or from about 14% w / w to about 16% w / w, or from about 16% w / w to about 18% w / w, or from about 18% w / w to about 20% w / w, or from about 20% w / w to about 22% w / w, or from about 22% w / w to about 25% w / w, or from about 25% w / w to about 30% w / w of nucleating agent.

[0180]

[0194] In another preferred embodiment, the hydrocarbon resin masterbatch comprises from about 5% to about 80% w / w of hydrocarbon resin.

[0181]

[0195] In one or more embodiments, the hydrocarbon resin masterbatch is from about 5% w / w to about 10% w / w, or from about 10% w / w to about 15% w / w, or from about 15% w / w to about 20% w / w, or from about 20% w / w to about 25% w / w, or from about 25% w / w to about 30% w / w, or from about 30% w / w to about 35% w / w, or from about 35% w / w to about 40% w / w. or about 40% w / w to about 45% w / w, or about 45% w / w to about 50% w / w, or about 50% w / w to about 55% w / w, or about 55% w / w to about 60% w / w, or about 60% w / w to about 65% w / w, or about 65% w / w to about 70% w / w, or about 70% w / w to about 80% w / w of the hydrocarbon resin.

[0182]

[0196] In one or more embodiments, the ratio of the nucleating agent masterbatch to the hydrocarbon resin masterbatch is from about 10:1 to about 1:100, or from about 25:4 to about 1:80, or from about 50:9 to about 1:70, or from about 5:1 to about 1:60, or from about 5:1 to about 1:50.

[0183]

[0197] Preferably, the nucleating agent mixture comprises a nucleating agent and polyethylene. The polyethylene may be a polyethylene powder. In a preferred embodiment, the nucleating agent is dry blended with the polyethylene powder to form the nucleating agent mixture.

[0184]

[0198] In a preferred embodiment, the polyolefin is polyethylene, preferably high density polyethylene (HDPE). Thus, in one or more embodiments, the bulk HDPE that is melt blended with the nucleating agent masterbatch and the hydrocarbon resin masterbatch, with the hydrocarbon resin and nucleating agent mixture, or with the nucleating agent masterbatch and the hydrocarbon resin to form the HBP composition may be the same or different from the HDPE contained in each masterbatch composition. It is generally preferred that the polyolefin, preferably HDPE, in the masterbatch composition is essentially linear without long chain branching. In a preferred embodiment, the polyolefin, preferably HDPE, in the masterbatch composition is of the same type or grade as the bulk HDPE that is blended with the masterbatch composition to form the HBP composition, since this can avoid or minimize the risk of incompatibility issues or dilution or deterioration of the properties of the barrier layer that may result from the use of a different type or grade of HDPE resin. Preferably, the polyolefin, preferably HDPE, in the masterbatch composition, and the bulk HDPE are essentially linear without long chain branching. Hydrocarbon Resin

[0199] Hydrocarbon resins (HCRs) useful in the present invention include low molecular weight materials derived from cyclic olefin copolymers or crude olefin feeds produced in petroleum cracking processes. Examples of these crude olefin feeds include light olefin fractions having an average carbon number of 5 carbon atoms per olefin molecule (C5 feed), or having an average of 6-9 carbon atoms per olefin molecule. Hydrocarbon resins produced from olefin streams rich in dicyclopentadiene (DCPD), from terpene olefins, such as limonene derived from citrus products, or derived from the polymerization of one or more pure monomer feeds selected from the group consisting of styrene, alpha-methylstyrene, 4-methylstyrene, norbornene, and vinyltoluene, may also be utilized.

[0185]

[0200] In one or more embodiments, the hydrocarbon resin has a lower weight average molecular weight (MW) than polyethylene. In some embodiments, the hydrocarbon resin has a weight average molecular weight (MW) of about 5,000 daltons or less, preferably about 2,000 daltons or less, more preferably about 1,000 daltons or less, and most preferably wherein the hydrocarbon resin has a weight average molecular weight of about 400 to about 800 daltons.

[0186]

[0201] The MW of a resin can be determined using techniques known to those of skill in the art, including, for example, size exclusion chromatography (SEC) using polystyrene as a standard.

[0187]

[0202] In some embodiments, the hydrocarbon resin is aliphatic in character to aid its compatibility with polyolefin carriers, preferably where the polyolefin is HDPE. Aliphatic hydrocarbon resins can be prepared by copolymerization with other unsaturated monomers, such as ethylene, or by converting hydrocarbon resins having unsaturated character by catalytic hydrogenation. By hydrogenation, the remaining unsaturated olefinic and / or aromatic groups in the hydrocarbon resin are converted to saturated species by reduction with hydrogen. The hydrogenation reaction can be carried out under a variety of conditions, examples of which are at temperatures ranging from about 150° C. to about 320° C., using hydrogen pressures of about 50 to about 2,000 psi, and in the presence of a catalyst, such as Ni metal-loaded carbon black.

[0188]

[0203] In a preferred embodiment, the hydrocarbon resins described herein may be hydrogenated hydrocarbon resins (HHCRs) or cyclic olefin copolymers. Such hydrogenated hydrocarbon resins may be partially or fully hydrogenated. In one embodiment, hydrogenated resins with low residual unsaturation may be desired. For example, a preferred type of hydrogenated hydrocarbon resin may have more than about 80%, preferably more than about 90%, and even more preferably more than about 95% of the residual olefinic and / or aromatic groups hydrogenated.

[0189]

[0204] In one or more embodiments, the hydrocarbon resin comprises a hydrogenated hydrocarbon resin selected from the group consisting of hydrogenated C5 resin, C9 resin, norbornene ethylene copolymer resin, hydrogenated aromatic resin, and hydrogenated dicyclopentadiene resin, or any combination thereof.

[0190]

[0205] Representative examples of hydrocarbon resins are those derived from the polymerization of crude C5 and / or C9 feedstocks, which are hydrogenated. C5 feedstocks are olefin streams produced during petroleum cracking that are composed of hydrocarbon olefin components with about 5 carbon atoms per molecule. Examples of olefins found in C5 feeds include, but are not limited to, trans-1,3-pentadiene, cis-1,3-pentadiene, 2-methyl-2-butene, cyclopentadiene, cyclopentene, and dicyclopentadiene. C9 feedstocks are olefin streams produced during petroleum cracking that are composed of hydrocarbon olefin components with about 9 carbon atoms per molecule. Examples of olefins found in C9 feeds include, but are not limited to, styrene, α-methylstyrene, indene, various methyl-substituted indenes, 4-methylstyrene, β-methylstyrene, and ethylstyrene.

[0191]

[0206] In one embodiment, the hydrocarbon resin comprises a hydrogenated C5 hydrocarbon resin, a hydrogenated C9 hydrocarbon resin, or a norbornene ethylene copolymer resin.

[0192]

[0207] In another embodiment, the hydrocarbon resin comprises a hydrogenated C5 / C9 hydrocarbon resin. Such resins may be produced using techniques known in the art, for example, by copolymerizing C5 and C9 feedstocks and hydrogenating the resulting resin, or by blending hydrogenated resins derived from such feedstocks.

[0193]

[0208] Another example of a hydrocarbon resin suitable for use in accordance with the present invention is a resin derived from the polymerization of an olefin feed rich in dicyclopentadiene (DCPD). Hydrocarbon resins rich in DCPD can be produced by thermally polymerizing an olefin stream containing from about 50% to about 100% DCPD at a temperature in the range of about 200° C. to about 325° C. to produce a resin product that can be hydrogenated to form a fully saturated material. In another embodiment, the hydrocarbon resin may comprise a hydrogenated dicyclopentadiene resin.

[0194]

[0209] Another example of a hydrocarbon resin that can be utilized in accordance with the present invention is a resin derived from the polymerization of pure monomers, such as styrene, alpha-methylstyrene, 4-methylstyrene, vinyltoluene, or any combination of these or similar pure monomeric feedstocks. The product produced by this polymerization is aromatic in character, but may be converted to an aliphatic resin by catalytic hydrogenation via a process similar to that described above. In another embodiment, the hydrocarbon resin may include a hydrogenated aromatic resin, or a cyclic olefin copolymer.

[0195]

[0210] In another example, hydrocarbon resins suitable for use in accordance with the present invention may be derived from the polymerization of terpene olefins, such as α-pinene, β-pinene, or d-limonene. These resins are aliphatic based materials and hydrogenation is generally not required to achieve the aliphatic character.

[0196]

[0211] Thus, in one or more embodiments, the hydrocarbon resin is selected from the group consisting of hydrogenated C5 resins, hydrogenated C9 resins, norbornene ethylene copolymer resins, hydrogenated aromatic resins, hydrogenated dicyclopentadiene resins, and combinations thereof.

[0197]

[0212] Preferably, hydrogenated hydrocarbon resins suitable for use in the present invention have a low softening point, preferably less than 180° C. The low softening point can help promote the compatibility of the resin and its interaction with the polyolefin in which it is dispersed, where the polyolefin is preferably HDPE.

[0198]

[0213] The softening point of the hydrogenated hydrocarbon resin may be determined using methods and techniques known to those skilled in the art. An exemplary method for measuring the softening point of a resin is the ring and ball method described in ASTM E28.

[0199]

[0214] In one or more embodiments, the hydrogenated hydrocarbon resin has a softening point, measured according to ASTM E28, of less than about 160° C., preferably less than about 150° C., more preferably less than about 140° C., and preferably about 124° C.

[0200]

[0215] In a preferred embodiment, the hydrocarbon resin is a hydrogenated hydrocarbon resin, and preferably the hydrogenated hydrocarbon resin has a softening point of less than about 140° C., measured according to ASTM E28.

[0201]

[0216] A range of commercially available hydrogenated hydrocarbon resins may be suitable for use in accordance with the present invention. Non-limiting representative examples of commercially available hydrogenated hydrocarbon resins include Picotac 1115, Eastotac™ H-100W, H-115W, H-130W and H-142W; Regalite™ R1090 and R1125 (available from Eastman Chemical Company); Alcon P100, Alcon P125, Alcon P140 (available from Arakawa Chemical Industries, Ltd., Japan); Bitner LH3115, LH3100, DH1100, DH1120, LH3100W and LH2100W (available from Qingdao Bater Chemical Co., Ltd); Fuculia FD-100, Fuculia FD-120 (available from UPM Sun-Tack); Oppera™ and Escorez™ resins (available from ExxonMobil Chemical Company); the HCR-D100 series of hydrogenated DCPD resins (available from Puyang Tiancheng Chemical Company); Regalrez™ hydrocarbon resins (available from Eastman Chemical Company); and Clearon P series resins (available from Yasuhara Chemical Co., Ltd., Japan).

[0202]

[0217] Examples of commercially available hydrogenated hydrocarbon resins that may be particularly useful in accordance with embodiments of the present invention include Escorez™ 5320, Escorez™ 5340, Topas® 8007F-04, Oppera™ PR100N, and Oppera™ PR120.

[0203]

[0218] An advantage of one or more embodiments of the present invention is that relatively small amounts of hydrocarbon resins may be incorporated into the barrier layer of the films of the present invention. Advantageously, it has been found that small amounts of hydrocarbon resins, particularly hydrogenated hydrocarbon resins, can be blended with a nucleating agent and bulk HDPE to achieve substantial improvements in barrier properties, particularly WVTR.

[0204]

[0219] In one or more embodiments, the hydrocarbon resin may be present in the barrier layer in an amount of from about 0.1% to about 10% by weight, based on the total weight of the components of the barrier layer. In certain embodiments, the barrier layer includes from 0.5% to about 7% by weight, preferably from 1% to about 4% by weight, of a hydrocarbon resin. Preferably, the hydrocarbon resin is a hydrogenated hydrocarbon resin. Nucleating Agent

[0220] Nucleating agents are additives that form nuclei in a polymer melt which, upon solidification from the molten state, promote crystal growth and the formation of small but numerous crystalline domains in the polymer.

[0205]

[0221] Any suitable and effective nucleating agent may be used according to the present invention. The preferred nucleating agent is compatible with the polyolefin carrier and dispersible in the polyolefin, preferably, where the polyolefin is polyethylene, preferably HDPE. The polyolefin-compatible, preferably HDPE-compatible nucleating agent may be inorganic or organic. A combination of two or more nucleating agents may be used. In a preferred embodiment, a single nucleating agent is used.

[0206]

[0222] Inorganic nucleating agent can be nanoscale particulate inorganic material.The examples of inorganic nucleating agent include but are not limited to calcium carbonate, talc, barium sulfate, silicon dioxide, carbon particles such as expanded graphite or carbon nanotubes, polyhedral oligomeric silsesquioxane (POSS), nanoclay such as halloysite and montmorillonite, silicate minerals such as vermiculite, and combinations thereof.

[0207]

[0223] The organic nucleating agent may be any suitable organic material. Examples of organic nucleating agents include, but are not limited to, metal salts of carboxylates, such as metal salts of benzoates, metal salts of phthalates, metal salts of hydrophthalates and metal salts of bicycloheptanedicarboxylates; phosphates; anthracenes; zinc monoglycerolates; benzoates; organic derivatives of dibenzylidene sorbitol; sorbitol acetals; metal salts of branched alkylphosphonic acids; cyclic organic phosphate metal salts; and combinations thereof.

[0208]

[0224] Other examples of nucleating agents are known to those of skill in the art and are described, for example, in WO2022 / 226247, WO2022 / 226249 and WO2022 / 226250 (Milliken), the entire contents of which are incorporated herein by cross-reference.

[0209]

[0225] In one or more embodiments, the nucleating agent is selected from a metal hydrophthalate, a metal bicycloheptanedicarboxylate, or a combination thereof. In one embodiment, the metal hydrophthalate is a metal hexahydrophthalate or a metal heptahydrophthalate. In one embodiment, the nucleating agent is preferably a metal hexahydrophthalate.

[0210]

[0226] Metal salts of nucleating agents include, but are not limited to, zinc, magnesium, sodium and calcium salts, and mixtures of such metal salts.

[0211]

[0227] In one embodiment, the nucleating agent is bicyclo[2,2,1]heptane-2,3-dicarboxylic acid disodium salt, which is commercially available from Milliken under the trade name Hyperform® HPN-68L. In another preferred embodiment, the nucleating agent is hexahydrophthalic acid calcium salt, which is commercially available from Milliken under the trade name Hyperform® HPN-20E. Combinations of these nucleating agents may also be used.

[0212]

[0228] The nucleating agent may be present in the barrier layer in an effective amount, and generally may be present in an amount of about 0.01% to about 1% by weight, based on the total weight of the components in the barrier layer. In one embodiment, the nucleating agent is present in the barrier layer in an amount of about 0.03% to about 0.5% by weight. In certain embodiments, the nucleating agent may be present in the barrier layer in an amount of about 0.05% to about 0.2% by weight, or about 0.075% to about 0.125% by weight. High Density Polyethylene (HDPE)

[0229] High density polyethylene (HDPE) is the preferred embodiment of the polyethylene, which is the preferred embodiment of the polyolefin carrier used in the masterbatch compositions as disclosed herein.

[0213]

[0230] HDPE is also the resin with which the masterbatch composition is mixed to form the HBP composition. In this context, HDPE is referred to as bulk HDPE.

[0214]

[0231] HDPE is a class of polyethylene in which the generally linear polymer has a low level of branching in the polymer chain. As a result of its regular structure, HDPE is a highly crystalline material. Preferably, the HDPE is selected from those suitable for forming layers and films.

[0215]

[0232] In some preferred embodiments, the HDPE is "substantially linear", meaning that it is essentially free of long chain branching and has a relatively narrow molecular weight distribution. Long chain branching can be measured by NMR, 3D-GPC, and rheology.

[0216]

[0233] In one or more embodiments, the HDPE useful according to the present invention may be a homopolymer or copolymer of ethylene. Accordingly, the terms "high density polyethylene" and "HDPE" are used herein to denote homopolymers of ethylene and copolymers of ethylene.

[0217]

[0234] The term "ethylene homopolymer" refers to an ethylene polymer that consists essentially of (i.e., at least 90% by weight, preferably at least 95% by weight, more preferably at least 97% by weight) ethylene; thus, a polyethylene homopolymer preferably comprises predominantly ethylene monomers.

[0218]

[0235] The term "ethylene copolymer" refers to a polymer formed from the copolymerization of ethylene and at least one comonomer. Preferably, the comonomer is at least one alpha-olefin. The alpha-olefin comonomer may contain 3 to 20 carbon atoms, preferably 4 to 8 carbon atoms. In some embodiments, the alpha-olefin comonomer is selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, and mixtures thereof. In one preference, the alpha-olefin comonomer may be selected from the group consisting of C4, C5, and C6 alkenes, and mixtures thereof, preferably selected from the group consisting of 1-butene, 1-pentene, 1-hexene, and mixtures thereof.

[0219]

[0236] In one or more embodiments, HDPE suitable for use in accordance with the present invention has a viscosity of about 0.94 to about 0.97 g / cm at 23° C. 3 The density of HDPE can be determined by one of ordinary skill in the art using known techniques. Exemplary techniques are described in ASTM D792. Density is a measure of HDPE crystallinity, where higher density relates to higher levels of crystallinity developed by the polymer.

[0220]

[0237] In a preferred embodiment, the HDPE (including, for example, bulk HDPE) has a modulus of at least about 0.940 g / cm at 23° C., measured according to ASTM D792. 3 In one embodiment, the HDPE has a density of about 0.95 to about 0.965 g / cm at 23° C., measured according to ASTM D792. 3 The material may have a density in the range of

[0221]

[0238] Bulk HDPE may have a melt flow index (MFI) in the range of about 0.08 to 40.0 g / 10 min at 190°C and 2.16 kg, measured according to ISO 1133. The melt flow index (MFI) provides an indication of the flowability and processability of the HDPE resin and is related to the viscosity of the HDPE in its molten state. The MFI may also be related to the average molecular weight of the polymer chains in the HDPE resin. A lower melt index at a defined load and temperature indicates a higher viscosity and a higher average molecular weight for the HDPE. In one or more preferred embodiments, the HDPE has an MFI, measured according to ISO 1133, at 190° C. and 2.16 kg in the range of about 0.08 to 20.0 g / 10 min, or about 0.10 to 10 g / 10 min, or about 0.10 to 4 g / 10 min, or about 0.5 to 3 g / 10 min, or about 0.8 to 2.0 g / 10 min.

[0222]

[0239] In one or more embodiments, the MFI of the HDPE, when used as the polyolefin carrier in one or more of the relevant masterbatches, is the same as or different from the MFI of the bulk HDPE. In a preferred embodiment, the HDPE in the nucleating agent masterbatch has an MFI higher than that of the bulk HDPE. In a preferred embodiment, the HDPE in the hydrocarbon resin masterbatch has an MFI lower than or similar to that of the bulk HDPE.

[0223]

[0240] Polyethylene generally consists of a mixture of polymer molecules having a distribution of different molecular weights, which can be represented graphically by a molecular weight distribution curve. In one or more embodiments, the HDPE may have a weight average molecular weight in the range of about 5,000 to 5,000,000 g / mol.

[0224]

[0241] In some embodiments, the ratio of viscosities of HDPE measured at two different shear rates may be used to provide an indication of the breadth of the molecular weight distribution for HDPE. In some cases, the ratio of the MFI measured under standard conditions at 190° C. and a load of 21.6 kg to the MFI measured under the same conditions and a load of 2.16 kg (e.g., MFI = 1.025 kg / mole) may be used to provide an indication of the breadth of the molecular weight distribution for HDPE. 21 The melt flow index ratio (MFR), which is the melt flow index ratio (MFR / MI2), can provide an indication of the breadth of the molecular weight distribution. In some embodiments of the invention, the bulk HDPE has an MI of less than 100, preferably less than 70, and more preferably less than 60. 21 / MI2 melt flow index ratio (MFR). In some embodiments, the MFR of the resin is less than 50, more preferably less than 45.

[0225]

[0242] In one or more embodiments, the HDPE comprises at least one polyethylene polymer, and may comprise a blend of two or more polyethylene polymers, such as a blend of a polyethylene copolymer and a polyethylene homopolymer, or a blend of two or more polyethylene homopolymers or copolymers of different molecular weights and / or compositions.

[0226]

[0243] In accordance with embodiments of the present invention, the HDPE described herein may optionally contain one or more other additives. Representative examples of additives include antioxidants (including primary and secondary antioxidants), antacid metal salts, flame retardants, lubricants, UV stabilizers, antistatic agents, processing aids, etc. If desired, such additives may be added to the extruder and melt compounded into the relevant masterbatch or HBP composition.

[0227]

[0244] For the avoidance of doubt, for each respective embodiment described herein, the nucleating agent, hydrocarbon resin and polyolefin, preferably polyethylene, more preferably HDPE, may be selected from any one of those described herein. Barrier Layer

[0245] In another aspect, the invention relates to a method for producing a barrier layer, the method comprising forming the barrier layer from an HBP composition as described herein. Additional aspects of the invention also relate to barrier layers produced by such methods.

[0228]

[0246] In a preferred embodiment, the HBP composition is extruded to form the barrier layer.

[0229]

[0247] In another aspect, the present invention provides a barrier layer produced by a method as described herein.

[0230]

[0248] In another aspect, the invention relates to a method for preparing a barrier layer for use in a film, the method comprising blending an HBP masterbatch comprising a synergistic combination of a nucleating agent, a hydrocarbon resin, and a polyolefin with bulk HDPE to form an HBP composition; and forming a barrier layer from the resulting blended HBP composition, wherein the polyolefin is preferably polyethylene, more preferably HDPE.

[0231]

[0249] In another embodiment, the HBP composition may be formed by blending a nucleating agent masterbatch, a polyolefin and a hydrocarbon resin without the use of a hydrocarbon resin masterbatch, where the polyolefin is preferably polyethylene, more preferably HDPE.

[0232]

[0250] A further aspect of the invention relates to a method for producing a barrier layer for a film, the method comprising: (a) melt mixing a nucleating agent masterbatch into bulk HDPE; (b) simultaneously or sequentially melt mixing a hydrocarbon resin masterbatch into the bulk HDPE of step (a) to form an HBP composition; and (c) forming a barrier layer from the HBP composition. In one embodiment, the nucleating agent masterbatch may be blended into the bulk HDPE in an amount of from about 0.04% w / w to about 30% w / w of the barrier layer, preferably from about 0.1% w / w to about 10% w / w. In one embodiment, the hydrocarbon resin masterbatch may be blended into the bulk HDPE in an amount of from about 0.14% w / w to about 70% w / w of the barrier layer, preferably from about 0.5% w / w to about 25% w / w. Barrier Film

[0251] The barrier layers described herein may be incorporated within and form part of a film. A film according to the present invention incorporates a barrier layer as described herein.

[0233]

[0252] Thus, in another aspect, the present invention relates to a method of reducing the water vapor transmission rate of a film, the method comprising incorporating a barrier layer as described herein into the film. Preferably, the film has a water vapor transmission rate of about 4 g / m or less, measured at about 38° C. and 90% external relative humidity. 2 / day water vapor transmission rate.

[0234]

[0253] As used herein, the term "film" may refer to a substantially planar material of any thickness. In some embodiments, a film as described herein can be a substantially planar material having an average thickness of about 500 μm or less, for example, about 10 μm to about 500 μm, preferably about 20 μm to about 200 μm, or about 25 μm to about 100 μm, or about 30 μm to about 80 μm, or about 35 μm to about 70 μm, or about 40 μm to about 60 μm. Films in the form of non-planar configurations or shapes are also contemplated, for example, a film may include one or more layers in an article formed by blow molding or injection molding.

[0235]

[0254] A film including a barrier layer may be a monolayer (ie, single-layer) film consisting of only the barrier layer, which is generally in the form of a substantially planar sheet.

[0236]

[0255] Alternatively, the film may be a multilayer film, in which the barrier layer is a component of the film along with other layers. Thus, the term "multilayer" refers to multiple layers in a single film structure. The layers may be combined together by any conventional means known in the art, for example, by coextrusion, lamination, or a combination thereof. The multilayer film described in this application may include as many layers as desired, for example, at least three, four, five or more film layers. At least one of the layers in the multilayer film is a barrier layer as described herein. The barrier layer may be sandwiched between other layers of the multilayer film. For example, the multilayer film may include three layers, and the barrier layer may be the central core layer of the multilayer film.

[0237]

[0256] Other layers in the multilayer film may comprise or be composed of conventional materials suitable for films for packaging applications, including other oxygen and / or water vapor barrier materials.

[0238]

[0257] The films of the present invention may be oriented or non-oriented films.

[0239]

[0258] Oriented films may be molecularly oriented in the machine direction (LD) and / or in the transverse (i.e., cross) direction (TD). Orientation of the film in either or both directions may be achieved by any suitable technique, such as by the well-known bubble and / or tenter processes.

[0240]

[0259] The films of the present invention advantageously exhibit one or more favorable barrier properties, including low water vapor transmission rate and / or oxygen transmission rate. For a particular film, the trends of water vapor and oxygen transmission rate may be correlated. Thus, a film that exhibits low water vapor transmission rate would be expected to exhibit a correspondingly low oxygen transmission rate.

[0241]

[0260] In one or more embodiments, the films according to the present invention have a film hardness of about 4 g / m or less measured at about 38° C. and 90% external relative humidity. 2 The test temperature may be within ±10% of 38°C (100°F).

[0242]

[0261] Water vapor transmission rate (WVTR) is the steady-state rate at which water vapor will permeate through a film under specified conditions. WVTR is expressed in g / m 2 / day (i.e., 24 hours), and is usually expressed at conditions of about 38°C and 90% relative humidity. WVTR can increase with humidity, and with increasing temperature or pressure. A suitable method for determining WVTR is described in ASTM E3. In one embodiment, WVTR is determined using a film having a thickness of about 40 μm or greater.

[0243]

[0262] In one or more embodiments, the barrier layer may be primarily responsible for imparting desirable WVTR properties to the film.

[0244]

[0263] In some embodiments, the barrier layer itself has a surface area of ​​about 4 g / m or less measured at about 38° C. and 90% external relative humidity. 2For example, in an embodiment in which the film is a monolayer film, the barrier layer itself may have a water vapor transmission rate of about 4 g / m or less when the film has a thickness of about 40 μm to about 60 μm, as measured at about 38° C. and 90% external relative humidity. 2 / day water vapor transmission rate.

[0245]

[0264] In embodiments where the film is a multilayer film, preferably when the film has a thickness of about 40 μm to about 60 μm, the film has a viscosity of about 4 g / m or less measured at about 38° C. and 90% external relative humidity. 2 / day, approximately 3.5g or less / m 2 / day, preferably about 3g or less / m 2 / day, preferably about 2.5 g / m or less 2 / day, preferably about 2.0 g / m or less 2 / day, preferably about 1.5 g / m or less 2 / day, preferably about 1.0 g / m or less 2 / day, preferably about 0.5 g / m or less 2 / day water vapor transmission rate.

[0246]

[0265] In accordance with the present invention, the barrier film may have a low oxygen transmission rate (OTR). The OTR is the steady state rate at which oxygen will permeate through a film at specified conditions. The OTR is expressed in cc / m 2 OTR is usually expressed per day (i.e., 24 hours) and at conditions of 23° C. and 0% relative humidity. Higher values ​​of OTR can be observed in high humidity environments and can increase with increasing temperature and pressure. In one embodiment, the films of the present invention have an OTR of 1,000 cc / cm or less, determined using a film having a thickness of about 40 μm or more. 2 The OTR may have an OTR of 100 / day. The OTR may be determined using methods known to those skilled in the art. A suitable method for determining the OTR is described in ASTM D3985.

[0247]

[0266] Advantageously, the barrier layers described herein can control oxygen and / or water vapor permeation. In one embodiment, the barrier layers can inhibit or reduce oxygen and / or water vapor permeation. Thus, films including the barrier layers may exhibit lower WVTR and / or OTR values ​​than those of conventional films.

[0248]

[0267] According to an embodiment of the present invention, a barrier layer may be formed from the HBP composition as defined herein. In one or more embodiments, the HBP composition and the resulting barrier layer include one or more polyolefins, preferably HDPE, one or more nucleating agents, and one or more hydrocarbon resins. Preferably, the HBP composition and the barrier layer include one nucleating agent and one hydrocarbon resin. Conventional techniques for forming polymer layers and films can be used to prepare the barrier layer from the HBP composition.

[0249]

[0268] Techniques for preparing barrier layers are known to those skilled in the art. According to one embodiment, the barrier layer may be formed by extruding a melt compounded HBP composition, which includes a synergistic blend of a nucleating agent and a hydrocarbon resin dispersed in a polyolefin, preferably HDPE, to form a substantially planar sheet or fabric. This may involve, for example, extrusion of the molten HBP composition through a slit die onto a casting roll, and then drawing the extruded blend to the desired sheet thickness while in the molten state.

[0250]

[0269] In alternative embodiments, the barrier layer may be prepared using a cast film process or a blown film process. Other film fabrication techniques suitable for making polymeric films or layers may also be used (e.g., tenter frame).

[0251]

[0270] In the blown film process, the HBP composition, which includes a synergistic blend of nucleating agent and hydrocarbon resin dispersed within HDPE, may be extruded through an annular die to form a cylindrical tube, which is then expanded using internal air pressure inside the tube of molten polymeric material to form a layer of a desired thickness.

[0252]

[0271] Some suitable film extrusion techniques are also described in a technical guide entitled "Film Extrusion and Conversion," published by Qenos Pty Ltd (published July 2015), the contents of which are incorporated herein by reference.

[0253]

[0272] In some aspects, the method of preparing the thermoplastic composition of the present invention comprises: (a) adding a high barrier polyolefin composition as described herein to an apparatus, the apparatus including a die and a mold, the mold having an interior surface defining a shape of a molded article; (b) melting the composition by heating, where the heating is sufficient to melt the composition and extrude it through a die; (c) forming a molten mass (also referred to as a parison) from the extruded composition; (d) capturing the mass in a mold; (e) expanding the extruded mass with a pressurized fluid to force the mass to conform to an interior surface of the mold, thereby producing a shaped article; (f) cooling the shaped article to at least partially solidify the composition; (g) obtaining the molded article from the mold; Includes.

[0254]

[0273] The above mentioned compositions may be any embodiment of the composition of the present invention. Preferably, the apparatus is any suitable extrusion blow molding apparatus, such as a continuous extrusion blow molding apparatus, such as a rotary wheel extrusion blow molding apparatus and a shuttle extrusion blow molding apparatus, and an intermittent extrusion blow molding apparatus, such as a reciprocating screw extrusion blow molding apparatus and an accumulator head extrusion blow molding apparatus. Preferably, the apparatus includes a die through which the plasticized (molten) composition is extruded to form a parison. Preferably, the apparatus also includes a mold having a mold cavity. Preferably, the shape of the molded article is defined by the mold cavity or the interior surface of the mold cavity. Preferably, the exterior surface of the molded article is defined by the interior surface of the mold cavity.

[0255]

[0274] In some aspects, a method for producing a film from a thermoplastic composition of the present invention comprises: (a) adding a high barrier polyolefin composition as described herein to an apparatus, the apparatus comprising: a die having an annular die orifice adapted to extrude a tube; means for injecting pressurized fluid into the tube exiting the annular die orifice; and Means for stretching and collecting tubes and (b) melting the composition by heating, where the heating is sufficient to melt the composition and extrude it through a die; (c) forming a tube by extruding the molten composition through the annular die orifice exiting the annular die orifice in a first direction, the tube having a diameter and a length; (d) inflating the tube by injecting a pressurized fluid into it to increase its diameter while simultaneously stretching the tube in a first direction to increase its length to produce a film; (e) cooling the film to solidify the composition; (f) obtaining a film; Includes.

[0256]

[0275] In one or more embodiments, the incorporation of a barrier layer into a film may reduce the water vapor transmission rate (WVTR) of the film by at least 10%, at least 20%, at least 40%, or at least 60% over a comparable film of comparable thickness that either does not have a barrier layer or has a barrier layer that is not prepared using the HBP composition as described herein (e.g., a barrier layer that does not include a synergistic combination of a nucleating agent and a hydrocarbon resin substantially homogeneously dispersed within the barrier composition). Thus, the barrier layer according to the present invention allows for films to be obtained that exhibit a greater reduction in WVTR when compared to the WVTR of the comparable film.

[0257]

[0276] A comparative film as described herein may be a film that includes or consists of a barrier layer formed of bulk HDPE resin alone, with no nucleating agent or hydrocarbon resin contained or dispersed therein.

[0258]

[0277] In one or more embodiments, the incorporation of a barrier layer into the film may reduce the oxygen transmission rate (OTR) of the film by at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, or at least 60% over a comparable film of comparable thickness that either does not have a barrier layer or has a barrier layer that is not prepared with an HBP composition as described herein (e.g., a barrier layer that does not include a nucleating agent and a hydrocarbon resin substantially homogeneously dispersed within the barrier composition). Thus, the barrier layer according to the present invention allows for films to be obtained that exhibit a greater reduction in OTR when compared to the OTR of the comparative film.

[0259]

[0278] Thus, the inventors have surprisingly discovered that reduced WVTR may be realized by blending bulk HDPE with a nucleating agent and a hydrocarbon resin via a polyolefin carrier to form an HBP composition, and forming a barrier layer from the HBP composition, via the use of a masterbatch composition according to embodiments disclosed herein.

[0260]

[0279] The effects observed with the relatively small amounts of hydrocarbon resin and nucleating agent utilized are unexpected.

[0261]

[0280] A further advantage of the present invention is that the nucleating agent and hydrocarbon resin (preferably hydrogenated hydrocarbon resin) may be used with many different types of polyolefins, including those traditionally considered to be less responsive to nucleation, such as polyethylene, preferably HDPE, and thus improved barrier properties may be advantageously imparted to a wider range of polyolefins, including but not limited to polyethylene and HDPE.

[0262]

[0281] The improved films described herein are valuable in packaging applications where a low rate of water vapor and / or oxygen transmission may be desired to help increase the shelf life of the packaged material while retaining good mechanical properties such as puncture and tear resistance. The improved barrier properties, in turn, can allow the thickness of the barrier layer and the film containing the barrier layer to be reduced, thereby providing cost savings in addition to environmental benefits.

[0263]

[0282] The invention will now be described with reference to the following examples, however, it should be understood that the examples are provided as an illustration of the invention and that they are in no way a limitation on the scope of the invention.

[0264] Example 1: Effect of method on synergy material:

[0283] The following materials were used in the examples below: HDPE(b) - Qenos Alkatane HDF895 - High density polyethylene homopolymer: 0.8MI2, 58MFR, 0.962g / cm 3 Density of NA -Milliken Hyperfoam 20E - 66.6% cyclohexanedicarboxylic acid, calcium salt (1:1) and 33.3% zinc stearate [ALLENS Note: Check] HCR -Hydrogenated alicyclic hydrocarbon resin: softening point 124℃, Mn 400, Mw 700 [ALLENS note: please check] Experiments using industry standard operating procedures

[0284] Table 1 shows some early experiments by the inventors, all carried out in a twin screw extruder, which did not use the method of the present invention, but rather used industry standard operating procedures.

[0265]

[0285] Compound 1: If the effects (in terms of WVTR increase) of films containing (a) 2% HCR and (b) 0.1% NA are summed, the expected additive WVTR is (c) 39%. The WVTR of a film containing both 2% HCR and 0.1% NA gives a WVTR increase of 36%.

[0266]

[0286] Compound 2: If the effects (in terms of WVTR increase) of films containing (a) 2% HCR and (b) 0.1% NA are summed, the expected additive WVTR is (c) 34%. The WVTR of a film containing both 2% HCR and 0.1% NA gives a WVTR increase of 38%.

[0267]

[0287] These results indicate that when industry standard operating procedures are used, WVTR improvements are at best equivalent to an additive effect, indicating that no synergistic effects are observed.

[0268] [Table 1]

[0269] Effect on WVTR using different methods

[0288] FIG. 6 shows that using different methods to prepare the masterbatches produces different results, even when the same type of extruder is used. Comparison Film: (a) No HCR or NA used in film (b) 2% HCR only (c) 0.1% NA only Films with the same NA and HCR amounts prepared according to different methods: (d) 0.1% NA + 2% HCR (SSC) - single screw extruder compound; single pass (e) 0.1%NA+2%HCR(TSC) pass 1-twin screw extruder compound; single pass (f) 0.1% NA + 2% HCR (TSC) pass 2-twin screw extruder compound; 2 passes (g) 0.1% NA + 2% HCR (TSC) pass 3-Twin screw extruder compound; 3 passes (h) 0.1% NA + 2% HCR (TSC) - Twin screw extruder compound; single pass, using the process of the present invention

[0289] The results indicate that the poorest results were obtained in the single screw extruder (d). A single pass in the twin screw extruder (e) produced a film with a similar additive effect, while increasing passes (f) and (g) gave higher WVTR performance in the resulting film.

[0270]

[0290] However, by using the method of the present invention (h) while maintaining the same amount of NA and HCR, substantially higher WVTRs are obtained, far greater than the expected additive effect, indicating that a synergistic effect may be obtained.

[0271] Example 2: Comparative Films and Films of the Invention material:

[0291] The following materials were used in the examples below: HDPE(a) - Qenos Alkatane HD0195FX - High density polyethylene homopolymer: 1.4MI2, 45MFR, 0.955g / cm 3 Density of HDPE(b) - Qenos Alkatan HDF895 - High density polyethylene homopolymer: 0.8MI2, 58MFR, 0.962g / cm 3 Density of HDPE(c) - Qenos Alkatan HDF995X - High density polyethylene homopolymer: 0.9MI2, 70MFR, 0.965g / cm 3 Density of HDPE(d) - Qenos Alkatan GF7660 - High density polyethylene copolymer: 0.3MI2, 120MFR, 0.959g / cm 3 Density of HDPE(e) - Qenos Alkatan HD1090 - High density polyethylene copolymer: 10MI2, 0.956g / cm 3 Density of NA-Milliken Hyperfoam 20E - 66.6% cyclohexanedicarboxylic acid, calcium salt (1:1) and 33.3% zinc stearate HCR-Hydrogenated alicyclic hydrocarbon resin: Softening point 124℃, Mn400, Mw700

[0272] [Table 2-1]

[0273] [Table 2-2]

[0274] [Table 2-3]

[0275] [Table 2-4]

[0276] Method for Producing HDPE Compositions for Forming Barrier Films Method 1: C1~C15

[0292] Selected HDPE resins were doped with the specified amounts of nucleating agent (NA) and hydrocarbon resin (HCR) additives as follows: C1: None C2: 1% HCR (33% HCR MB used) C3: 3% HCR (33% HCR MB used) C4: 0.1% NA (using 20% ​​NA MB) C5: None C6: 0.1% NA (20% NA MB used) C7: None C8: 1% HCR (50% HCR MB used) C9: 2% HCR (50% HCR MB used) C10: 0.1% NA (20% NA MB used) C11: None C12: 0.1% NA (20% NA MB used) C13: 4% HCR (using 60% HCR MB) C14: None C15: 0.1% NA (20% NA MB used) The resulting composition was melt blended in a twin screw extruder and then blown for film formation. Method 2: S1, S2, S5, S6, S7 and S8

[0293] Selected HDPE resins were doped with the specified amounts of nucleating agent (NA) and hydrocarbon resin (HCR) additives as follows: S1: 0.1% NA (20% NA MB used) + 1% HCR (33% HCR MB used); NA MB and HCR MB were used in a ratio of 1:7 S2: 0.1% NA (20% NA MB used) + 3% HCR (33% HCR MB used); NA MB and HCR MB were used in a ratio of 1:18 S5: 0.1% NA (using 20% ​​NA MB) + 1% HCR (using 33% HCR MB) S6: 0.1% NA (20% NA MB used) + 2% HCR (33% HCR MB used); NA MB and HCR MB were used in a ratio of 2:25 S7: 0.1% NA (20% NA MB used) + 4% HCR (60% HCR MB used); NA MB and HCR MB were used in a ratio of 2:27 S8: 0.1% NA (using 20% ​​NA MB) + 4% HCR (using 60% HCR MB)

[0294] The resulting composition was melt blended in a twin screw extruder and then blown for film formation. Method 3: S3 and S4

[0295] The specified amounts of NA, HCR and HDPE were melt mixed in a twin screw extruder to produce HBP MB [HBP MB with 2.5% NA + 50% HCR + 47.5% HDPE w / w]. HBP MB was mixed with bulk HDPE in a twin screw extruder to produce the HBP composition. S3: 0.05% NA + 1% HCR (2% HBP MB used) S4: 0.1% NA + 2% HCR (using 4% HBP MB)

[0296] The resulting composition was then blown for film formation.

[0277]

[0297] The barrier layer compositions are summarized in Table 2. Synergy

[0298] The following table shows the synergy based on comparing (a) the actual WVTR observed from the combination of hydrocarbon resin and nucleating agent in the inventive samples and (b) the expected additive WVTR calculated by adding the WVTRs of the hydrocarbon resin and nucleating agent when used separately in the comparative films. Column (c) shows the difference between (a) and (b) and indicates the value of the synergy.

[0278] [Table 3]

[0279]

[0299] The above examples show that in all inventive examples, the observed synergy resulted in an increase of more than 5% over the expected additive WVTR. General Method for Film Formation :

[0300] Films were produced from the HDPE blends and the comparative HDPE blends using a blown film extrusion process on a blown film line. Films containing only bulk HDPE resin (i.e., no added nucleating agent or hydrocarbon resin) were also prepared for comparison.

[0280]

[0301] Using the blown film process, HDPE was melted and then extruded vertically upward through an annular die to obtain a tube of controlled diameter and thickness. The extruded melt was air-cooled near the die through a cooling ring, and the film tube was inflated into a bubble of the required diameter by air introduced through the center of the die mandrel. The film was pulled through a pair of nip rollers to contain a volume of expanding air within the bubble formed between the nip rollers and the die. The bubble was then collapsed in a collapse frame and flattened through nip rollers to form a lay-flat film that could be rolled up either as a tubular film or by slitting into a sheet film.

[0281]

[0302] The films were formed by blown film extrusion using the following process parameters: Film gauge: 40~50μm Blow-up ratio (BUR): 2.5 Frost line height: 300mm (low) or 800mm (high) Lay flat width: 40~45cm Zone temperature: 190℃ max. 20 Screw speed: 300 rpm WVTR Test:

[0303] The formed films were evaluated for WVTR at a temperature of about 38° C. and an external relative humidity of about 90% according to test method ASTM E398-20 using a Permatran-W model 1 / 50G manufactured by Mocon.

[0282]

[0304] The improvement in WVTR (i.e., reduced water vapor transmission) was determined by evaluating the difference in WVTR obtained for a film prepared using only bulk HDPE resin and a film formed using the HDPE blend. The improvement may be expressed as a change in WVTR (ΔWVTR) using the following equation:

[0283]

number

[0284]

[0305] From the above results, it can be seen that films formed from HBP compositions containing (i) 0.1% NA + 1-3% HCR using Method 2 (i.e., Samples S1 and S2); and (ii) 0.05-0.1% NA + 1-2% HCR using Method 3 (i.e., S3 and S4) provided significantly improved barrier results over the comparative films, balanced with good film mechanical properties. OTR Testing:

[0306] The formed films were evaluated for OTR using an Oxtran 2 / 22 from Mocon according to test method ASTM D3985-05 at a temperature of about 23° C. and an external relative humidity of about 0%.

[0285]

[0307] The improvement in OTR (i.e., reduction in oxygen transmission) was determined by evaluating the difference in OTR obtained for a film prepared using only bulk HDPE resin and a film formed using the HDPE blend. The improvement may be expressed as a change in OTR (ΔOTR) using the following equation:

[0286]

number

[0287]

[0308] The examples provided herein demonstrate that one or more embodiments of the barrier layers and films prepared by the methods of the present invention may provide a useful alternative to barrier layers and films known in the art, or, in particularly preferred embodiments, one or more advantages, such as one or more of the following: Improved balance of mechanical properties, e.g. stiffness, or puncture and tear resistance; Lower production costs, for example, due to the relatively low levels of hydrocarbon resins used; Improved processability; improving the homogeneous dispersion of the nucleating agent or hydrocarbon resin; providing a synergistic combination of a nucleating agent and a hydrocarbon resin; improving the crystalline characteristics of the resulting barrier layer; Facilitating the effectiveness of compounding, melt mixing and / or extrusion processes; Allowing for the addition of small or precise amounts of nucleating agents and / or hydrocarbon resins to bulk HDPE; Improved barrier film properties, e.g., lower WVTR or OTR; and Allowing for a reduction in the thickness of the barrier layer or film while retaining one or more of the above properties.

[0288]

[0309] For the avoidance of doubt, any reference to or discussion of any document, statute, or article of knowledge in this specification is included solely for the purpose of providing a context for the present invention, and no suggestion or representation is being made that any of these matters, or any combination thereof, formed part of the common general knowledge at the priority date, or were known to be relevant to attempting to solve any problems to which this specification pertains.

[0289]

[0310] It should be understood that various other modifications and / or alterations may be made without departing from the spirit of the invention as outlined herein.

Claims

1. A method for preparing a high-barrier polyolefin masterbatch, a) A step of melting and mixing a nucleating agent into polyethylene to form a nucleating agent masterbatch; b) A step of melting and mixing hydrocarbon resin into polyethylene to form a hydrocarbon resin masterbatch; c) A step of melt-mixing the nucleating agent masterbatch from step a) with the hydrocarbon resin masterbatch from step b) to produce a homogeneous high-barrier polyolefin masterbatch. Methods that include...

2. A method for preparing a high-barrier polyolefin masterbatch, The process includes melt-mixing a nucleating agent mixture and a hydrocarbon resin with polyethylene. Here, the nucleating agent mixture comprises a nucleating agent and a polyolefin, Here, the melting and mixing step is sufficient to produce a homogeneous high-barrier polyolefin masterbatch. method.

3. The method according to claim 1 or 2, wherein one or more of the melting and mixing steps include a residence time sufficient to produce a uniform dispersion of the nucleating agent and the hydrocarbon resin.

4. The nucleating agent masterbatch; The hydrocarbon resin masterbatch; or The aforementioned high-barrier polyolefin masterbatch One or more of the melting and mixing steps for forming the The process further includes adding one or more additives. The method according to claim 1 or 2.

5. The nucleating agent is present in the high-barrier polyolefin masterbatch in an amount of about 0.2% to about 15% w / w; The hydrocarbon resin is present in the high-barrier polyolefin masterbatch in an amount of approximately 2.5% to approximately 80% w / w. The method according to claim 1 or 2.

6. The method according to claim 1 or 2, wherein the polyethylene is HDPE.

7. The method according to claim 1 or 2, wherein the hydrocarbon resin has a lower weight-average molecular weight than the polyethylene.

8. The method according to claim 1 or 2, wherein the hydrocarbon resin is a cyclic olefin copolymer or hydrocarbon resin derived from a crude olefin feed selected from the group consisting of C5 olefin feedstreams, C9 olefin feedstreams, terpene olefins, norbornene, pure monomers, and combinations thereof.

9. The method according to claim 1 or 2, wherein the nucleating agent comprises a metal salt.

10. The method according to claim 1 or 2, wherein the nucleating agent comprises a branched alkylphosphonic acid, a metal hydrophthalate, a metal bicycloheptanedicarboxylate, or a combination thereof.

11. A high-barrier polyolefin masterbatch produced by the method described in claim 1 or 2.

12. A method for producing a high-barrier polyolefin composition, comprising the step of blending the high-barrier polyolefin masterbatch described in Claim 11 with a bulk polyolefin.

13. A high-barrier polyolefin composition produced by the method described in Claim 12.

14. A nucleating agent in an amount of about 0.01% to about 1% w / w; Hydrocarbon resin in an amount of approximately 0.1% to approximately 10% w / w A high-barrier polyolefin composition according to claim 13, comprising:

15. A method for producing a high-barrier polyolefin composition, The process includes blending the nucleating agent masterbatch and the hydrocarbon resin masterbatch according to claim 1 with a bulk polyolefin, Here, the nucleating agent is present in the nucleating agent masterbatch in an amount of about 0.1% to about 30% w / w; The hydrocarbon resin is present in the hydrocarbon resin masterbatch in an amount of approximately 5% to approximately 80% w / w. Here, the high-barrier polyolefin composition is With the nucleating agent in an amount of 0.01% to 1% w / w; The hydrocarbon resin in an amount of 0.1% to 7% w / w and Methods that include...

16. A method for producing a high-barrier polyolefin composition, The process includes blending the nucleating agent mixture according to claim 2 and the hydrocarbon resin masterbatch according to claim 1 with a bulk polyolefin, Here, the hydrocarbon resin is present in the hydrocarbon resin masterbatch in an amount of approximately 5% to approximately 80% w / w. Here, the high-barrier polyolefin composition is With the nucleating agent in an amount of 0.01% to 1% w / w; The hydrocarbon resin in an amount of 0.1% to 7% w / w and Methods that include...

17. The method according to claim 12, 15, or 16, wherein the high-barrier polyolefin composition comprises 0.5% to 7%, 0.5% to 6%, 0.5% to 5%, and 0.5% to 4% w / w of hydrocarbon resin.

18. The method according to claim 12, 15, or 16, wherein the nucleating agent and the hydrocarbon resin are present in the high-barrier polyolefin composition in a ratio of about 1:4 to about 1:

200.

19. A method for reducing the water vapor permeability and oxygen permeability of a polyethylene film, wherein the method comprises incorporating a barrier layer into the film, the barrier layer being a) Mixing a nucleating agent masterbatch containing a nucleating agent uniformly dispersed in polyolefin with a hydrocarbon resin masterbatch containing a hydrocarbon resin uniformly dispersed in polyolefin to form a high-barrier polyolefin masterbatch; Here, the hydrocarbon resin masterbatch and the nucleating agent masterbatch are in a ratio of approximately 1:5 to approximately 50:

1. b) Melt-mixing bulk polyethylene with the high-barrier polyolefin masterbatch in an amount of 10% by weight or less of portion (a) to form a high-barrier polyolefin composition; c) Forming a barrier layer from the high-barrier polyolefin composition; Formed by, A method wherein the water vapor permeability and oxygen permeability of the film are less than those of an equivalent film without the barrier layer.

20. A method for reducing the water vapor permeability and oxygen permeability of a polyethylene film, wherein the method includes incorporating a barrier layer into the film, and the barrier layer is a) Forming a high-barrier polyolefin composition by melt-mixing bulk polyethylene in an amount of 90% by weight or more with a nucleating agent masterbatch and a hydrocarbon resin masterbatch; Here, the nucleating agent masterbatch comprises a nucleating agent uniformly dispersed in a polyolefin, and the hydrocarbon resin masterbatch comprises a hydrocarbon resin uniformly dispersed in a polyolefin. Here, the hydrocarbon resin masterbatch and the nucleating agent masterbatch are in a ratio of approximately 1:5 to approximately 50:

1. b) Forming a barrier layer from the high-barrier polyolefin composition; Formed by, A method wherein the water vapor permeability and oxygen permeability of the film are less than those of an equivalent film without the barrier layer.

21. A method for reducing the water vapor permeability and oxygen permeability of a polyethylene film, wherein the method comprises incorporating a barrier layer into the film, and the barrier layer is a) Mixing a nucleating agent masterbatch containing a nucleating agent uniformly dispersed in a polyolefin with a hydrocarbon resin having a molecular weight lower than that of polyethylene to form a high-barrier polyolefin masterbatch; Here, the hydrocarbon resin and the nucleating agent masterbatch are combined in a ratio of approximately 1:5 to approximately 60:

1. b) Forming a high-barrier polyolefin composition by melt-mixing 90% by weight or more of bulk polyethylene with 10% by weight or less of the high-barrier polyolefin masterbatch of part (a); c) Forming a barrier layer from the high-barrier polyolefin composition; Formed by, A method wherein the water vapor permeability and oxygen permeability of the film are less than those of an equivalent film without the barrier layer.

22. A method for reducing the water vapor permeability and oxygen permeability of a polyethylene film, wherein the method comprises incorporating a barrier layer into the film, and the barrier layer is a) Forming a high-barrier polyolefin composition by melt-mixing bulk polyethylene in an amount of 90% by weight or more with a nucleating agent masterbatch and a hydrocarbon resin; Here, the nucleating agent masterbatch comprises a nucleating agent uniformly dispersed in a polyolefin, Here, the hydrocarbon resin and the nucleating agent masterbatch are combined in a ratio of approximately 1:5 to approximately 60:

1. b) Forming a barrier layer from the high-barrier polyolefin composition; Formed by, A method wherein the water vapor permeability and oxygen permeability of the film are less than those of an equivalent film without the barrier layer.

23. A method for reducing the water vapor permeability and oxygen permeability of a polyethylene film, wherein the method comprises incorporating a barrier layer into the film, the barrier layer being a) Mixing a nucleating agent mixture containing a nucleating agent uniformly dispersed in a polyolefin with a hydrocarbon resin masterbatch containing a hydrocarbon resin uniformly dispersed in a polyolefin to form a high-barrier polyolefin masterbatch; Here, the hydrocarbon resin masterbatch and the nucleating agent are combined in a ratio of approximately 5:1 to approximately 150:

1. b) Forming a high-barrier polyolefin composition by melt-mixing 90% by weight or more of bulk polyethylene with 10% by weight or less of the high-barrier polyolefin masterbatch of part (a); c) Forming a barrier layer from the high-barrier polyolefin composition; Formed by, A method wherein the water vapor permeability and oxygen permeability of the film are less than those of an equivalent film without the barrier layer.

24. A method for reducing the water vapor permeability and oxygen permeability of a polyethylene film, wherein the method comprises incorporating a barrier layer into the film, the barrier layer being a) Forming a high-barrier polyolefin composition by melt-mixing bulk polyethylene in an amount of 90% by weight or more with a nucleating agent mixture and a hydrocarbon resin masterbatch; Here, the nucleating agent mixture comprises a nucleating agent uniformly dispersed in a polyolefin, and the hydrocarbon resin masterbatch comprises a hydrocarbon resin uniformly dispersed in a polyolefin. Here, the hydrocarbon resin masterbatch and the nucleating agent are combined in a ratio of approximately 5:1 to approximately 150:

1. b) Forming a barrier layer from the high-barrier polyolefin composition; Formed by, A method wherein the water vapor permeability and oxygen permeability of the film are less than those of an equivalent film without the barrier layer.

25. The method according to any one of claims 19 to 24, wherein the polyolefin in any one or more of the nucleating masterbatch, the hydrocarbon resin masterbatch, and the nucleating agent mixture is polyethylene.

26. The method according to any one of claims 19 to 24, wherein the polyolefin in one or more of the nucleating masterbatch, the hydrocarbon resin masterbatch, and the nucleating agent mixture is the same or different.

27. ​​The method according to any one of claims 1 to 10, 12, 15, or 16, or the method according to any one of claims 19 to 24, wherein one or more of the mixing step, the melting and mixing step, and / or the blending step are performed in a twin-screw compounding machine.

28. A method for producing a high-barrier polyolefin composition, A method comprising the step of blending a nucleating agent masterbatch according to claim 1 and a hydrocarbon resin masterbatch according to claim 1 with a bulk polyolefin to form a homogeneous polyolefin composition in which the nucleating agent and the hydrocarbon resin are uniformly dispersed.

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