Metalized multilayer films
A multilayer film with a polyethylene core and polypropylene outer layers retains surface energy post-metallization, addressing the issue of high fatty acid content and enhancing adhesion for improved laminating and printing performance.
Patent Information
- Application Number
- PCT/CN2024/096747
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2024-05-31
- Publication Date
- 2025-12-04
AI Technical Summary
Metallized polyolefin films often fail to retain surface energy after metallization due to high fatty acid and fatty acid salt content, leading to poor performance in laminating or printing processes.
A multilayer film structure comprising a core layer of polyethylene with a high fatty acid and fatty acid salt content, flanked by outer layers of polypropylene and polyethylene, allows the film to retain surface energy post-metallization, enhancing adhesion and performance in subsequent processes.
The multilayer film design maintains surface energy and improves adhesion of the metal layer, enabling better laminating and printing capabilities despite high fatty acid and fatty acid salt content in the polyethylene composition.
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Figure CN2024096747_04122025_PF_FP_ABST
Abstract
Description
METALIZED MULTILAYER FILMSTECHNICAL FIELD
[0001] Embodiments described herein generally relate to multilayer films and, more specifically, to multilayer films comprising a metal layer.BACKGROUND
[0002] Polyolefin films may be used in various applications, including use as a packaging material. In some applications, packaging films should exhibit good barrier properties against moisture and / or oxygen to protect the contents of the package. While plastic packaging materials offer toughness, lighter weight and a level of design flexibility that glass and metal cannot meet, most plastics, including particularly polyolefins, have a permeability to oxygen and water vapor that make them unacceptable by themselves as a packaging material. One approach to provide improved barrier properties to polyolefin-based film structures has been to provide a thin metallized layer on a surface of the film.SUMMARY
[0003] Some metallized polyolefin films are unable to retain surface energy of the metal layer after metallization. This may lead to poor performance in laminating or printing on the metallized surface of the film. Polyolefin films having a reduced fatty acid and fatty acid salt content of less than 300 ppm may retain surface energy of the metal layer after metallization. However, relatively few polyolefin compositions have such a reduced fatty acid and fatty acid salt content. Accordingly, there is a need for polyolefin films that may retain surface energy of the metal layer after metallization while having a relatively high fatty acid and fatty acid salt content of greater than 300 ppm.
[0004] Embodiments of multilayer films described herein may retain surface energy of the metal layer after metallization, even when using polyethylene compositions having a relatively high fatty acid and fatty acid salt content. Embodiments of such multilayer films may include a core layer comprising a polyethylene composition and an outer layer comprising a polypropylene composition, and an outer layer comprising an ethylene composition. The inclusion of the polypropylene composition in the multilayer film may allow the film to retain surface energy after the multilayer film is metallized, even when a polyethylene composition having a relatively high fatty acid and fatty acid salt content is included in the core layer of the multilayer film. The metal layer may be formed on the outer layer comprising the polyethylene composition. This may improve the adhesion of the metal layer to the other layers of the multilayer film, relative to multilayer structures where the metal layer is formed on a layer comprising polypropylene.
[0005] According to one or more embodiments disclosed herein, a multilayer film comprises a core layer comprising a first polyethylene composition having a density of at least 0.918 g / cm3, a first outer layer comprising a second polyethylene composition, a second outer layer comprising a polypropylene composition, and a metal layer in direct contact with the first outer layer. The core layer is positioned between the first outer layer and the second outer layer. The first outer layer is positioned between the core layer and the metal layer. The polypropylene composition has a first fraction area in a temperature range of from 90 ℃ to 120 ℃ in an elution profile via an improved comonomer composition distribution (iCCD) analysis method, and the first fraction area comprises at least 50%of a total area of the elution profile.BRIEF DESCRIPTION OF THE DRAWINGS
[0006] The following detailed description of specific embodiments of the present disclosure can be best understood when read in conjunction with the following drawings, where like structure is indicated with like reference numerals and in which:
[0007] FIG. 1 schematically depicts a cross-section of a multilayer film comprising four layers, according to one or more embodiments of the present disclosure; and
[0008] FIG. 2 schematically depicts a cross-section of a multilayer film comprising seven layers, according to one or more embodiments of the present disclosure.DETAILED DESCRIPTION
[0009] Specific embodiments of the present application will now be described. These embodiments are provided so that this disclosure will be thorough and complete and will fully convey the scope of the claimed subject matter to those skilled in the art.
[0010] Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percent values are based on weight, all temperatures are in ℃, and all test methods are current as of the filing date of this disclosure.
[0011] The term “composition, ” as used herein, refers to a mixture of materials that comprises the composition, as well as reaction products and decomposition products formed from the materials of the composition.
[0012] The term “polymer” refers to a polymeric compound prepared by polymerizing monomers, whether of a same or a different type. The generic term polymer thus embraces the term “homopolymer, ” which usually refers to a polymer prepared from only one type of monomer as well as “copolymer, ” which refers to a polymer prepared from two or more different monomers. The term “interpolymer, ” as used herein, refers to a polymer prepared by the polymerization of at least two different types of monomers. The generic term interpolymer thus includes a copolymer or polymer prepared from more than two different types of monomers, such as terpolymers.
[0013] “Polyethylene” or “ethylene-based polymer” shall mean polymers comprising greater than 50%by mole of units derived from ethylene monomer. This includes ethylene-based homopolymers or copolymers (meaning units derived from two or more comonomers) . Common forms of ethylene-based polymers known in the art include, but are not limited to, Low Density Polyethylene (LDPE) ; Linear Low Density Polyethylene (LLDPE) ; Ultra Low Density Polyethylene (ULDPE) ; Very Low Density Polyethylene (VLDPE) ; single-site catalyzed Linear Low Density Polyethylene, including both linear and substantially linear low density resins (m-LLDPE) ; Medium Density Polyethylene (MDPE) ; and High Density Polyethylene (HDPE) .
[0014] The term “LDPE” may also be referred to as “high pressure ethylene polymer” or “highly branched polyethylene” and is defined to mean that the polymer is partly or entirely homopolymerized or copolymerized in autoclave or tubular reactors at pressures above 14, 500 psi (100 MPa) with the use of free-radical initiators, such as peroxides (see, for example, U.S. Pat. No. 4,599,392, which is hereby incorporated by reference) . LDPE resins typically have a density in the range of 0.916 g / cm3 to 0.940 g / cm3.
[0015] The term “LLDPE, ” includes resin made using Ziegler-Natta catalyst systems as well as resin made using single-site catalysts, including, but not limited to, bis-metallocene catalysts (sometimes referred to as “m-LLDPE” ) , phosphinimine, and constrained geometry catalysts, and resins made using post-metallocene, molecular catalysts, including, but not limited to, bis(biphenylphenoxy) catalysts (also referred to as polyvalent aryloxyether catalysts) . LLDPE includes linear, substantially linear, or heterogeneous ethylene-based copolymers or homopolymers. LLDPEs contain less long chain branching than LDPEs and include the substantially linear ethylene polymers, which are further defined in U.S. Pat. No. 5,272,236, U.S. Pat. No. 5,278,272, U.S. Pat. No. 5,582,923 and U.S. Pat. No. 5,733,155; the homogeneously branched linear ethylene polymer compositions such as those in U.S. Pat. No. 3,645,992; the heterogeneously branched ethylene polymers such as those prepared according to the process disclosed in U.S. Pat. No. 4,076,698; and blends thereof (such as those disclosed in U.S. Pat. No. 3,914,342 and U.S. Pat. No. 5,854,045) . The LLDPE resins can be made via gas-phase, solution-phase, or slurry polymerization or any combination thereof, using any type of reactor or reactor configuration known in the art.
[0016] The term “MDPE” refers to polyethylenes having densities from 0.924 g / cm3 to 0.942 g / cm3. “MDPE” is typically made using chromium or Ziegler-Natta catalysts or using single-site catalysts including, but not limited to, substituted mono-or bis-cyclopentadienyl catalysts (typically referred to as metallocene) , constrained geometry catalysts, phosphinimine catalysts and polyvalent aryloxyether catalysts (typically referred to as bisphenyl phenoxy) .
[0017] The term “HDPE” refers to polyethylenes having densities greater than about 0.942 g / cm3 and up to about 0.980 g / cm3, which are generally prepared with Ziegler-Natta catalysts, chrome catalysts or single-site catalysts including, but not limited to, substituted mono-or bis-cyclopentadienyl catalysts (typically referred to as metallocene) , constrained geometry catalysts, phosphinimine catalysts & polyvalent aryloxyether catalysts (typically referred to as bisphenyl phenoxy) .
[0018] The term “ULDPE” refers to polyethylenes having densities of 0.855 g / cm3 to 0.912 g / cm3, which are generally prepared with Ziegler-Natta catalysts, chrome catalysts, or single-site catalysts including, but not limited to, substituted mono-or bis-cyclopentadienyl catalysts (typically referred to as metallocene) , constrained geometry catalysts, phosphinimine catalysts & polyvalent aryloxyether catalysts (typically referred to as bisphenyl phenoxy) . ULDPEs include, but are not limited to, polyethylene (ethylene-based) plastomers and polyethylene (ethylene-based) elastomers. Polyethylene (ethylene-based) elastomers and plastomers generally have densities of 0.855 g / cm3 to 0.912 g / cm3.
[0019] “Polypropylene” or “propylene-based polymers” shall mean polymers comprising greater than 50%by weight of units which have been derived from propylene monomer. This includes polypropylene homopolymers or copolymers (meaning units derived from two or more comonomers) . Common forms of polypropylene known in the art include homopolymer polypropylene (hPP) , random copolymer polypropylene (rcPP) , terpolymer polypropylene (terPP) , impact copolymer polypropylene (hPP + at least one elastomeric impact modifier) (ICPP) or high impact polypropylene (HIPP) , high melt strength polypropylene (HMS-PP) , isotactic polypropylene (iPP) , syndiotactic polypropylene (sPP) , and combinations thereof.
[0020] As described herein, a “propylene-based elastomer” refers to an elastomer that includes greater than 50%by mole of units derived from propylene monomer. This includes propylene-based homopolymers or copolymers (meaning units derived from two or more comonomers) . The copolymers may be random copolymers such as VersifyTM from Dow and VistamaxxTM from ExxonMobil. The copolymers may be block copolymers such as IntuneTM from Dow. Elastomers may generally be understood as polymeric materials that exhibit viscoelasticity (i.e., those that exhibit both viscous and elastic characteristics when undergoing deformation) .
[0021] “Fatty acid” shall mean a carboxylic acid having an aliphatic chain comprising from 4 to 28 carbon atoms. The aliphatic chain may be either saturated or unsaturated. The aliphatic chain may be branched or unbranched. Examples of fatty acids include stearic acid and palmitic acid. As described herein, “fatty acid salts” refer to metal salts of fatty acids. Examples of fatty acid salts include, but are not limited to, calcium stearate, zinc stearate, and calcium palmitate.
[0022] As described herein, an “ethylene-based elastomer” refers to an elastomer that includes greater than 50%by mole of units derived from ethylene monomer. This includes ethylene-based homopolymers or copolymers (meaning units derived from two or more comonomers) . Elastomers may generally be understood as polymeric materials that exhibit viscoelasticity (i.e., those that exhibit both viscous and elastic characteristics when undergoing deformation) .
[0023] As described herein, an “ethylene-based plastomer” refers to a plastomer that includes greater than 50%by mole of units derived from ethylene monomer. This includes ethylene-based homopolymers or copolymers (meaning units derived from two or more comonomers) . Plastomers may generally be understood as polymeric materials which combine qualities of elastomers and plastics.
[0024] “Blend, ” “polymer blend, ” and like terms mean a composition of two or more polymers. Such a blend may or may not be miscible. Such a blend may or may not be phase separated. Such a blend may or may not contain one or more domain configurations, as determined from transmission electron spectroscopy, light scattering, x-ray scattering, and any other method known in the art. Blends are not laminates, but one or more layers of a laminate may contain a blend. Such blends can be prepared as dry blends, formed in situ (e.g., in a reactor) , melt blends, or using other techniques known to those of skill in the art.
[0025] “Multilayer structure” or “multilayer film” means any structure having more than one layer. For example, the multilayer structure (for example, a film) may have two, three, four, five, or more layers.
[0026] The terms “comprising, ” “including, ” “having, ” and their derivatives, are not intended to exclude the presence of any additional component, step or procedure, whether or not the same is specifically disclosed. In order to avoid any doubt, all compositions claimed through use of the term “comprising” may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term, “consisting essentially of” excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability. The term “consisting of” excludes any component, step or procedure not specifically delineated or listed.
[0027] Multilayer Films
[0028] Reference will now be made to embodiments of the multilayer films described herein. Embodiments of the presently-described multilayer films may include at least four layers.
[0029] Referring now to FIG. 1, a multilayer film 100 may comprise a core layer 110, a first outer layer 120, a second outer layer 130, and a metal layer 140. The core layer 110 may be positioned between the first outer layer 120, and the second outer layer 130. As described herein, an “outer layer” refers to a layer that is farther than another from the center or the middle. An “outer layer” is not necessarily the outermost layer of the multilayer film. As used herein, an “outermost layer” may be understood to mean that there may not be another layer deposited over the outermost layer, such that the outermost layer is in direct contact with the surrounding atmosphere.
[0030] The core layer 110 may have a first major surface 112 and a second major surface 114. The first major surface 112 may be opposite the second major surface 114. The first outer layer 120 may have a first major surface 122 and a second major surface 124. Likewise, the second outer layer 130 may have a first major surface 132 and a second major surface 134. The metal layer 140 may have a first major surface 142 and a second major surface 144.
[0031] Still referring to FIG. 1, the core layer 110 may be in direct contact with the first outer layer 120. As used herein, “direct contact” means that there may not be any other layers positioned between the two layers that are in direct contact with one another. In such embodiments, the first major surface 112 of the core layer 110 may be in direct contact with the first major surface 122 of the first outer layer 120.
[0032] In one or more embodiments, the core layer 110 may be in direct contact with the second outer layer 130. Still referring to FIG. 1, in such embodiments, the second major surface 114 of the core layer 110 may be in direct contact with the first major surface 132 of the second outer layer 130. In some embodiments, the core layer 110 may be in direct contact with both the first outer layer 120 and the second outer layer 130. In such embodiments, the first major surface 112 of the core layer 110 may be in direct contact with the first major surface 122 of the first outer layer 120, and the second major surface 114 of the core layer 110 may be in direct contact with the first major surface 132 of the second outer layer 130.
[0033] Still referring to FIG. 1, the first outer layer 120 may be positioned between the core layer 110 and the metal layer 140. In one or more embodiments, the first outer layer 120 may be in direct contact with the metal layer 140. In such embodiments, the second major surface 124 of the first outer layer 120 is in direct contact with the first major surface 142 of the metal layer. The metal layer 140 may be an outermost layer of the multilayer film 100. Still referring to FIG. 1, the second major surface 144 of the metal layer 140 may be an air-side surface of the multilayer film 100. In such embodiments, the second major surface 144 of the metal layer 140 is not in direct contact with another layer of the multilayer film 100, and the second major surface 144 of the metal layer 140 is in direct contact with the surrounding atmosphere.
[0034] In one or more embodiments, the multilayer film 100 may comprise one or more additional layers. For example, the multilayer film 100 may comprise one or more interlayers and one or more sealant layers. Referring now to FIG. 2, the multilayer film 100 may comprise an interlayer 210. The interlayer 210 may have a first major surface 212 and a second major surface 214. The interlayer 210 may be positioned between the core layer 110 and the second outer layer 130. In one or more embodiments, the interlayer 210 may be in direct contact with the core layer 110 such that the second major surface 114 of the core layer 110 is in direct contact with the first major surface 212 of the interlayer 210. In one or more embodiments, the interlayer 210 may be in direct contact with the second outer layer 130 such that the first major surface 132 of the second outer layer 130 is in direct contact with the second major surface 214 of the interlayer 210. In some embodiments, the interlayer 210 is in direct contact with both the second outer layer 130 and the core layer 110.
[0035] In one or more embodiments, the multilayer film may comprise a sealant layer 230. The sealant layer 230 may comprise a first major surface 232 and a second major surface 234. The second outer layer 130 may be positioned between the core layer 110 and the sealant layer 230. In one or more embodiments, the sealant layer 230 may be in direct contact with the second outer layer 130 such that the second major surface 134 of the second outer layer 130 is in direct contact with the first major surface 232 of the sealant layer 230. In some embodiments, the sealant layer 230 may be an outermost layer of the multilayer film 100. In such embodiments, the second major surface 234 of the sealant layer 230 may be an air-side surface of the multilayer film 100 that is exposed to the atmosphere.
[0036] According to some embodiments, the second outer layer 130 may have a thickness of less than 25%of a total thickness of the multilayer film 100. The thickness of the second outer layer 130 is the average distance between the first major surface 132 and the second major surface 134 of the second outer layer 130. The total thickness of the multilayer film 100 is the average distance between the outermost major surfaces of the multilayer film 100. In one or more embodiments, the second outer layer 130 may have a thickness of less than 25%, 20%, 15%, 10%, or even 5%of the total thickness of the multilayer film 100.
[0037] In one or more embodiments, the multilayer film 100 may comprise one or more fatty acids, one or more fatty acid salts, or both, in an amount greater than 300 ppm, based on the total mass of the multilayer film. For example, the multilayer film 100 may comprise one or more fatty acids, one or more fatty acid salts, or both, in an amount greater than 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, or even 800 pp, 900 ppm, or even 1000 ppm, based on the total mass of the multilayer film. In one or more embodiments, the multilayer film 100 may comprise one or more fatty acids, one or more fatty acid salts, or both in an amount from 300 ppm to 2000 ppm, based on the total mass of the multilayer film. For example, the multilayer film 100 may comprise one or more fatty acids, one or more fatty acid salts, or both in an amount from 300 ppm to 2000 ppm, from 500 ppm to 2000 ppm, from 700 ppm to 2000 ppm, from 900 ppm to 2000 ppm, from 1100 ppm to 2000 ppm, from 1300 ppm to 2000 ppm, from 1500 ppm to 2000 ppm, from 1700 ppm to 2000 ppm, from 1900 ppm to 2000 ppm, from 300 ppm to 1800 ppm, from 300 ppm to 1600 ppm, from 300 ppm to 1400 ppm, from 300 ppm to 1200 ppm, from 300 ppm to 1000 ppm, from 300 ppm to 800 ppm, from 300 ppm to 600 ppm, from 300 ppm to 400 ppm, or any range or combination of ranges formed from these endpoints.
[0038] In one or more embodiments, an optical density of the multilayer film 100 is from 1.0 to 4.0. For example, the multilayer film 100 may have an optical density from 1.0 to 4.0, from 1.5 to 4.0, from 2.0 to 4.0, from 2.5 to 4.0, from 3.0 to 4.0, from 3.5 to 4.0, from 1.0 to 3.5, from 1.0 to 3.0, from 1.0 to 2.5, from 1.0 to 2.0, from 1.0 to 1.5, or any range or combination of ranges formed from these endpoints. The optical density of the multilayer film 100 may be measured on an air-side surface of the metal layer 140. For example, referring again to FIG. 1, the optical density of the metal layer may be measured on the second surface 144 of the metal layer 140.
[0039] As described hereinabove, embodiments of the multilayer film 100 may comprise a core layer 110, first and second outer layers 120 and 130 respectively, and a metal layer 140. Some embodiments of multilayer films 100 may further comprise an interlayer 210 and a sealant layer 230. These layers are now described in greater detail.
[0040] Core Layer
[0041] As previously described, the multilayer film 100 may comprise a core layer 110. The core layer 110 may comprise a first polyethylene composition. In one or more embodiments, the core layer 110 may comprise at least 50 wt. %of the first polyethylene composition, based on the total weight of the core layer 110. For example, the core layer 110 may comprise at least 50 wt. %, 60 wt. %, 70 wt. %, 80 wt. %, 90 wt. %, or even 99 wt. %of the first polyethylene composition, based on the total weight of the core layer 110. In some embodiments, the core layer 110 may consist of or consist essentially of the first polyethylene composition.
[0042] The first polyethylene composition comprises one or more ethylene-based polymers, as described hereinabove. In embodiments, the first polyethylene composition may comprise at least 50 wt. %, 60 wt. %, 70 wt. %, 80 wt. %, 90 wt. %, or even 95 wt. %of one or more ethylene-based polymers. In some embodiments, the first polyethylene composition may consist of or consist essentially of ethylene-based polymers. In one or more embodiments, the core layer 110 may comprise one or more of linear low density polyethylene (LLDPE) , medium density polyethylene (MDPE) , high density polyethylene (HDPE) , and low density polyethylene (LDPE) . In one or more embodiments, the core layer 110 may comprise one or more of an ultra-low density polyethylene (ULDPE) , a polyethylene plastomer, a polyethylene elastomer, an ethylene vinyl acetate copolymer, an ethylene ethyl acrylate copolymer, and an ethylene vinyl alcohol.
[0043] In one or more embodiments, the first polyethylene composition may have a density of at least 0.918 g / cm3. For example, the first polyethylene composition may have a density of at least 0.918 g / cm3, at least 0.920 g / cm3, at least 0.925 g / cm3, at least 0.935 g / cm3, or even at least 0.945 g / cm3. In one or more embodiments, the first polyethylene composition may have a density from 0.918 g / cm3 to 0.965 g / cm3. For example, the first polyethylene composition may have a density from 0.918 g / cm3 to 0.965 g / cm3, from 0.920 g / cm3 to 0.965 g / cm3, from 0.925 g / cm3 to 0.965 g / cm3, from 0.930 g / cm3 to 0.965 g / cm3, from 0.935 g / cm3 to 0.965 g / cm3, from 0.940 g / cm3 to 0.965 g / cm3, from 0.945 g / cm3 to 0.965 g / cm3, from 0.950 g / cm3 to 0.965 g / cm3, from 0.955 g / cm3 to 0.965 g / cm3, from 0.960 g / cm3 to 0.965 g / cm3, from 0.918 g / cm3 to 0.960 g / cm3, from 0.918 g / cm3 to 0.955 g / cm3, from 0.918 g / cm3 to 0.950 g / cm3, from 0.918 g / cm3 to 0.945 g / cm3, from 0.918 g / cm3 to 0.940 g / cm3, from 0.918 g / cm3 to 0.935 g / cm3, from 0.918 g / cm3 to 0.930 g / cm3, from 0.918 g / cm3 to 0.925 g / cm3, or any range or combination of ranges formed from these endpoints. In some embodiments, the first polyethylene composition may have a density from 0.940 g / cm3 to 0.965 g / cm3.
[0044] In one or more embodiments, the first polyethylene composition may have a melt index (I2) from 0.2 g / 10 min. to 5.0 g / 10 min. For example, the first polyethylene composition may have a melt index (I2) from 0.2 g / 10 min. to 5.0 g / 10 min., from 0.5 g / 10 min. to 5.0 g / 10 min., from 1.0 g / 10 min. to 5.0 g / 10 min., from 1.5 g / 10 min. to 5.0 g / 10 min., from 2.0 g / 10 min. to 5.0 g / 10 min., from 2.5 g / 10 min. to 5.0 g / 10 min., from 3.0 g / 10 min. to 5.0 g / 10 min., from 3.5 g / 10 min. to 5.0 g / 10 min., from 4.0 g / 10 min. to 5.0 g / 10 min., from 4.5 g / 10 min. to 5.0 g / 10 min., from 0.2 g / 10 min. to 4.5 g / 10 min., from 0.2 g / 10 min. to 4.0 g / 10 min., from 0.2 g / 10 min. to 3.5 g / 10 min., from 0.2 g / 10 min. to 3.0 g / 10 min., from 0.2 g / 10 min. to 2.5 g / 10 min., from 0.2 g / 10 min. to 2.0 g / 10 min., from 0.2 g / 10 min. to 1.5 g / 10 min., from 0.2 g / 10 min. to 1.0 g / 10 min., from 0.2 g / 10 min. to 0.5 g / 10 min., or any range or combination of ranges formed from these endpoints.
[0045] Outer Layers
[0046] As described hereinabove, the multilayer film 100 comprises a first outer layer 120 and a second outer layer 130. The first outer layer 120 may comprise a second polyethylene composition. In one or more embodiments, the first outer layer 120 may comprise at least 50 wt. %of the second polyethylene composition, based on the total weight of the first outer layer 120. For example, the first outer layer 120 may comprise at least 50 wt. %, 60 wt. %, 70 wt. %, 80 wt. %, 90 wt. %, or even 99 wt. %of the second polyethylene composition, based on the total weight of the first outer layer 120. In some embodiments, the first outer layer 120 may consist of or consist essentially of the second polyethylene composition.
[0047] The second polyethylene composition comprises one or more ethylene-based polymers, as described hereinabove. In embodiments, the second polyethylene composition may comprise at least 50 wt. %, 60 wt. %, 70 wt. %, 80 wt. %, 90 wt. %, or even 95 wt. %of one or more ethylene-based polymers. In some embodiments, the second polyethylene composition may consist of or consist essentially of ethylene-based polymers. In one or more embodiments, the first outer layer 120 may comprise one or more of linear low density polyethylene (LLDPE) , medium density polyethylene (MDPE) , high density polyethylene (HDPE) , and low density polyethylene (LDPE) . In one or more embodiments, the first outer layer 120 may comprise one or more of an ultra-low density polyethylene (ULDPE) , a polyethylene plastomer, a polyethylene elastomer, an ethylene vinyl acetate copolymer, an ethylene ethyl acrylate copolymer, and an ethylene vinyl alcohol.
[0048] In one or more embodiments, the second polyethylene composition may have a density of at least 0.925 g / cm3. For example, the second polyethylene composition may have a density of at least 0.925 g / cm3, at least 0.935 g / cm3, or even at least 0.945 g / cm3. In one or more embodiments, the second polyethylene composition may have a density from 0.925 g / cm3 to 0.965 g / cm3. For example, the second polyethylene composition may have a density from 0.925 g / cm3 to 0.965 g / cm3, from 0.930 g / cm3 to 0.965 g / cm3, from 0.935 g / cm3 to 0.965 g / cm3, from 0.940 g / cm3 to 0.965 g / cm3, from 0.945 g / cm3 to 0.965 g / cm3, from 0.950 g / cm3 to 0.965 g / cm3, from 0.955 g / cm3 to 0.965 g / cm3, from 0.960 g / cm3 to 0.965 g / cm3, from 0.925 g / cm3 to 0.960 g / cm3, from 0.925 g / cm3 to 0.955 g / cm3, from 0.925 g / cm3 to 0.950 g / cm3, from 0.925 g / cm3 to 0.945 g / cm3, from 0.925 g / cm3 to 0.940 g / cm3, from 0.925 g / cm3 to 0.935 g / cm3, from 0.925 g / cm3 to 0.930 g / cm3, or any range or combination of ranges formed from these endpoints. In some embodiments, the second polyethylene composition may have a density from 0.940 g / cm3 to 0.965 g / cm3.
[0049] In one or more embodiments, the second polyethylene composition may have a melt index (I2) from 0.2 g / 10 min. to 5.0 g / 10 min. For example, the second polyethylene composition may have a melt index (I2) from 0.2 g / 10 min. to 5.0 g / 10 min., from 0.5 g / 10 min. to 5.0 g / 10 min., from 1.0 g / 10 min. to 5.0 g / 10 min., from 1.5 g / 10 min. to 5.0 g / 10 min., from 2.0 g / 10 min. to 5.0 g / 10 min., from 2.5 g / 10 min. to 5.0 g / 10 min., from 3.0 g / 10 min. to 5.0 g / 10 min., from 3.5 g / 10 min. to 5.0 g / 10 min., from 4.0 g / 10 min. to 5.0 g / 10 min., from 4.5 g / 10 min. to 5.0 g / 10 min., from 0.2 g / 10 min. to 4.5 g / 10 min., from 0.2 g / 10 min. to 4.0 g / 10 min., from 0.2 g / 10 min. to 3.5 g / 10 min., from 0.2 g / 10 min. to 3.0 g / 10 min., from 0.2 g / 10 min. to 2.5 g / 10 min., from 0.2 g / 10 min. to 2.0 g / 10 min., from 0.2 g / 10 min. to 1.5 g / 10 min., from 0.2 g / 10 min. to 1.0 g / 10 min., from 0.2 g / 10 min. to 0.5 g / 10 min., or any range or combination of ranges formed from these endpoints.
[0050] According to some embodiments, the second polyethylene composition may be different from the first polyethylene composition. In one or more embodiments, the first polyethylene composition may have a density at least 0.005 g / cm3 greater than a density of the second polyethylene composition. In some other embodiments, the first polyethylene composition may be the same as the second polyethylene composition.
[0051] The second outer layer 130 may comprise a polypropylene composition. In one or more embodiments, the second outer layer 130 may comprise at least 50 wt. %of the polypropylene composition, based on the total weight of the second outer layer 130. For example, the second outer layer 130 may comprise at least 50 wt. %, 60 wt. %, 70 wt. %, 80 wt. %, 90 wt. %, or even 99 wt. %of the polypropylene composition, based on the total weight of the second outer layer 130. In some embodiments, the second outer layer 130 may consist of or consist essentially of the polypropylene composition.
[0052] In one or more embodiments, the polypropylene composition may comprise one or more propylene-based polymers, as described hereinabove. In embodiments, the polypropylene composition may comprise at least 50 wt. %, 60 wt. %, 70 wt. %, 80 wt. %, 90 wt. %, or even 95 wt. %of one or more propylene-based polymers. In some embodiments, the polypropylene composition may consist of or consist essentially of propylene-based polymers. In some embodiments, the polypropylene composition may comprise one or more of a propylene homopolymer, a propylene-ethylene copolymer, and a propylene terpolymer having at least one of ethylene and 1-butene.
[0053] In one or more embodiments, the polypropylene composition may have a melting point greater than 135℃. For example, the polypropylene composition may have a melting point greater than 135℃, 140℃, 145℃, 150℃, 155℃ or even 160℃. In some embodiments, the polypropylene composition may have a melting point from 135℃ to 165℃. For example, the polypropylene composition may have a melting point from 135℃ to 165℃, from 140℃ to 165℃, from 145℃ to 165℃, from 150℃ to 165℃, from 155℃ to 165℃, from 160℃ to 165℃, from 135℃ to 160℃, from 135℃ to 155℃, from 135℃ to 150℃, from 135℃ to 145℃, from 135℃to 140℃, or any range or combination of ranges formed from these endpoints.
[0054] As described herein, a polypropylene “fraction” refers to a portion of the total composition of a polypropylene composition. The present disclosed embodiments include at least a “first fraction. ” Various fractions included in the polypropylene composition may be quantified by their temperature range in an elution profile via improved comonomers composition distribution (iCCD) analysis method. Unless specified, any elution profile referred to herein is the elution profile observed via iCCD. Examples of such fractions will be better understood in view of the examples provided herewith. In general, the first fraction may include a single peak in the temperature range of the first fraction. As used herein, a “single peak” refers to an iCCD wherein a particular fraction include only a single peak. That is, in some embodiments, the iCCD of the first fraction includes only an upward sloping region followed by a downward sloping region to form the single peak.
[0055] In one or more embodiments, the polypropylene composition may have a first fraction area in a temperature range of from 90℃ to 120℃ in an elution profile via an improved comonomer composition distribution (iCCD) analysis method. For example, the polypropylene composition may have a first fraction area, in an elution profile via an improved comonomer composition distribution (iCCD) analysis method, in a temperature range from 90℃ C to 120℃, from 95℃ C to 120℃, from 100℃ C to 120℃, from 105℃ C to 120℃, from 110℃ C to 120℃, from 115℃ C to 120℃, from 90℃ C to 115℃, from 90℃ C to 110℃, from 90℃ C to 105℃, from 90℃ C to 100℃, from 90℃ C to 95℃, or any range or combination of ranges formed from these endpoints. In one or more embodiments, the first fraction area comprises at least 50%of a total area of the elution profile. For example, the first fraction area may comprise at least 50%, 60%, 70%, 80%, or even 90%of a total area of the elution profile.
[0056] Without intending to be bound by theory, multilayer films 100 including a second outer layer 130 comprising a polypropylene composition, as described hereinabove, may allow the multilayer film 100 to retain surface energy after metallization, even when the core layer comprises a polyethylene composition having a relatively high fatty acid or fatty acid salt content (a fatty acid or fatty acid salt content greater than 300 ppm) . This may increase the number of polyethylene compositions that may be used in the core layer 110 of the metallized multilayer films without sacrificing surface energy retention of the metal layer 140 the multilayer film 100. For example, the core layer 110 may not be limited to polyethylene compositions having a low fatty acid or fatty acid salt content. In turn, retaining surface energy of the metal layer 140 of the multilayer film 100 may improve the properties of the multilayer film for subsequent laminating or printing processes. Additionally, forming the metal layer 140 on the first outer layer 120 comprising the second polyethylene composition may result in improved adhesion of the metal layer 140 relative to other multilayer films where the metal layer is formed on a layer comprising polypropylene composition.
[0057] Metal Layer
[0058] As previously described, the multilayer film 100 comprises a metal layer 140. The metal layer may comprise one or more of aluminum (Al) , zinc (Zn) , gold (Au) , silver (Ag) , copper (Cu) , nickel (Ni) , chromium (Cr) , germanium (Ge) , selenium (Se) , titanium (Ti) , and tin (Sn) . The metal layer may comprise any of these metals in an oxide form. For example, the metal layer may comprise a metal, a metal oxide, or a combination of metals and metal oxides.
[0059] In one or more embodiments, a surface energy of the metal layer 140 may be greater than 34 dyne / cm. For example, the surface energy of the metal layer 140 may be greater than 34 dyne / cm, 35 dyne / cm, 36 dyne / cm, 37 dyne / cm, 38 dyne / cm, 39 dyne / cm or even 40 dyne / cm. The surface energy of the metal layer 140 may be measured on an air-side surface of the metal layer 140. Referring to FIG. 1, the surface energy of the metal layer may be measured on the second surface 144 of the metal layer 140. In one or more embodiments, the surface energy of the metal layer 140 may be greater than 34 dyne / cm at a time of greater than or equal to 2 weeks, or greater than or equal to 1 month after metallization. In some embodiments, the surface energy of the metal layer 140 may be greater than 34 dyne / cm at a time from 2 weeks to 2 months after metallization. For example, the surface energy of the metal layer 140 may be greater than 34 dyne / cm at a time of 2 weeks, 1 month, or 2 months after metallization.
[0060] Additional Layers
[0061] As previously described, the multilayer film 100 may comprise an interlayer 210. The interlayer 210 may comprise one or more of one or more of a polypropylene composition, a polyethylene composition, an ethylene-based plastomer composition, an ethylene-based elastomer composition, and a propylene-based elastomer composition. In some embodiments, the interlayer 210 may comprise a propylene homopolymer, a propylene-ethylene copolymer or a propylene terpolymer having at least one of ethylene and 1-butene as a comonomer. In some embodiments, the interlayer 210 may comprise a linear low density polyethylene (LLDPE) , or a medium density polyethylene (MDPE) , or a high density polyethylene (HDPE) , or an ultra-low density polyethylene (ULDPE) . In some embodiments, the interlayer 210 may comprise a block copolymer of ethylene and a C3 to C8 comonomer.
[0062] As previously described, the multilayer film 100 may comprise a sealant layer 230. In one or more embodiments, the sealant layer 230 may comprise linear low density polyethylene (LLDPE) . The sealant layer 230 may further comprise on or more additional polyethylene, such as low density polyethylene (LDPE) . In one or more embodiments, the sealant layer 230 may comprise an anti-blocking agent. For example, the anti-block agent may be present in amounts of at least 1000 or at least 1500 ppm and up to 5000 ppm in certain embodiments. In addition, the sealant layer 230 may comprise an anti-slip agent. For example, the anti-slip agents may be present in amounts of from 100 ppm or 200 ppm to 1000 ppm or to 800 ppm. The combined amount of the additives in the sealant layer 230 may be less than 10 wt. %or less than 5 wt. %based on the total weight of the sealant layer 230.
[0063] It should be understood that any of the previously described layers can further comprise one or more additives as known to those of skill in the art such as, for example, plasticizers, stabilizers including viscosity stabilizers, hydrolytic stabilizers, antioxidants, ultraviolet light absorbers, anti-static agents, dyes, pigments or other coloring agents, inorganic fillers, fire-retardants, lubricants, reinforcing agents such as glass fiber and flakes, synthetic (for example, aramid) fiber or pulp, foaming or blowing agents, processing aids, slip additives, antiblock agents such as silica or talc, release agents, tackifying resins, or combinations of two or more thereof. Inorganic fillers, such as calcium carbonate, and the like can also be incorporated into one or more of the previously described layers. In some embodiments, any one of the previously described layers may include up to 5 weight percent of such additional additives based on the total weight of the respective layer. All individual values and subranges from 0 wt. %to 5 wt. %are included and disclosed herein; for example, the total amount of additives in the first layer, the second layer, or the third layer can be from 0.5 wt. %to 5 wt. %, from 0.5 wt. %to 4 wt. %, from 0.5 wt. %to 3 wt. %, from 0.5 wt. %to 2 wt. %, from 0.5 wt. %to 1 wt. %, from 1 wt. %to 5 wt. %, from 1 wt. %to 4 wt. %, from 1 wt. %to 3 wt. %, from 1 wt. %to 2 wt. %, from 2 wt. %to 5 wt. %, from 2 wt. %to 4 wt. %, from 2 wt. %to 3 wt. %, from 3 wt. %to 5 wt. %, from 3 wt. %to 4 wt. %, or from 4 wt. %to 5 wt. %based on the total weight of the respective layer. In one or more embodiments, the amount of antioxidants in the multilayer film may be less than 3000 ppm, based on the total weight of the multilayer film. For example, the multilayer film 100 may comprise antioxidants in an amount less than 3000 ppm, 2750 ppm, 2500 ppm, 2250 ppm, or even 2000 ppm. The incorporation of the additives can be carried out by any known process such as, for example, by dry blending, by extruding a mixture of the various constituents, by the conventional masterbatch technique, or the like.
[0064] Method of Forming the Multilayer Films
[0065] Embodiments of the multilayer films 100 described hereinabove may be formed by any suitable process. In one or more embodiments, layers comprising polymer compositions including the core layer 110, the first and second outer layers 120 and 130 and any additions layers such as the interlayer 210 and the sealant layer 230 may be formed using various processes that include one or more of blowing, casting, water quenching, double bubble processing, triple bubble processing, machine direction orientation, or biaxial orientation processes.
[0066] The metal layer 140 may be formed by any known method for metallizing multilayer films. For example, the metal layer 140 can be applied using vacuum metallization. This can include providing a metal source and evaporating it in a vacuum environment causing it to condense on the surface of the film.
[0067] After metallization, the multilayer film 100 may be stored in rolls. For example, the metal layer 140 may be in contact with the layer on the opposite side of the film. In some embodiments, this may be the second outer layer 130 or the sealant layer 230. Storage of the multilayer film may be at temperatures in the range of 20℃ to 25℃ and a relative humidity of 10%to 20%.
[0068] Articles formed from the Multilayer Films
[0069] Embodiments of the multilayer films 100 described hereinabove may be used to form various articles. The multilayer films 100 may be printed on and / or laminated to a substrate, such as another film. The other film may be another polymeric material, such as a polyester (e.g., polyethylene terephthalate or PET) . The high surface energy of the metal layer 140 of the multilayer film 100 may reduce problems previously encountered with lamination or printing on the metal layer 140 of the multilayer film 100.
[0070] The multilayer film 100 (with our without lamination to another film) can be used to form articles such as packages. Examples of packages that may be formed from the multilayer film 100 include, but are not limited to, flexible packages, pouches, stand-up pouches, and pre-made packages or pouches. The multilayer film 100 may be used for food packages. Examples of foods that may be included in such packages include, but are not limited to, meats, cheeses, cereal, nuts, juices, and sauces. Such packages may be formed using techniques known to those skilled in the art based on the particular use of the packages.
[0071] Test Methods
[0072] Melt Index
[0073] Melt indices I2 (I2) and / or I10 (I10) were measured in accordance with ASTM D1238 (method B) at 190 ℃ and at 2.16 kg and 10 kg load, respectively. Their values are reported in g / 10 min.
[0074] Density
[0075] Density measurements were made in accordance with ASTM D792.
[0076] Optical Density
[0077] Optical density was determined using an optical density meter (Model No. LSI77 from Shenzhen Linshang Technology) . The transmittance (T, %) was used to derive the optical density value.
[0078] Haze
[0079] Haze measurements were made in accordance with ASTM D1003.
[0080] Gloss
[0081] Gloss measurements were made in accordance with ASTM D2457.
[0082] Surface Energy
[0083] Surface energy of the outer surface of metal layer was measured according to the following method. Multiple metallized multilayer films are stacked such that the metal layer of one metallized multilayer film is in direct contact with the opposite side of an adjacent metallized multilayer film. The stacked metallized multilayer film is stored at ambient conditions (23 ℃ and 15 %relative humidity) between polished and cleansed glass plates with controlled load of 0.2 N / cm2 to ensure a solid contact between the multilayer films. At pre-determined time intervals, the surface energy of the metal layer of the multilayer film is tested according to ASTM D2578.
[0084] Improved Method for Comonomer Content Analysis (iCCD)
[0085] Improved method for comonomer content analysis (iCCD) was developed in 2015 (Cong and Parrott et al., WO 2017 / 040127 A1) . iCCD test was performed with Crystallization Elution Fractionation instrumentation (CEF) (PolymerChar, Spain) equipped with IR-5 detector (PolymerChar, Spain) and two angle light scattering detector Model 2040 (Precision Detectors, currently Agilent Technologies) . Ortho-dichlorobenzene (ODCB, 99%anhydrous grade or technical grade) was used. The CEF instrument is equipped with an autosampler with N2 purging capability.
[0086] Sample preparation was done by mixing the polymer with ODCB at 4 mg / ml (unless otherwise specified) in an autosampler under shaking at 158℃. for 1 hour. The injection volume was 200 μl. The temperature profile of iCCD was: crystallization at 3℃ / min from 110℃ to 30℃, the thermal equilibrium at 30° C. for 2 minute (including Soluble Fraction Elution Time being set as 2 minutes) , elution at 3℃ / min from 30℃ to 140° C. The flow rate during crystallization is 0.0 ml / min. The flow rate during elution is 0.50 ml / min. The data was collected at one data point / second.
[0087] The iCCD data displays as an elution profile of “dWf / dT versus elution temperature” , where dWf / dT is the weight fraction (Wf) of the polymer eluting at temperature of T. The fraction area from 90℃ to 120℃ (Area 90-120) and the total area (Area Total) of the elution profile can be calculated using the equations below:
[0088] The percentage of the fraction area comprising of the total area of the elution profile equals to the weight percentage of the elution fraction in temperature range of 90℃ to 120℃, as below equation:
[0089] The iCCD column was packed with gold coated nickel particles (Bright 7GNM8-NiS, Nippon Chemical Industrial Co. ) in a 15 cm (length) x 1 / 4 in. (ID) stainless tubing. The column packing and conditioning were with a slurry method according to the reference (Cong, R.; Parrott, A.; Hollis, C.; Cheatham, M. WO 2017 / 040127 A1) . The final pressure with TCB slurry packing was 150 Bars.
[0090] Column temperature calibration was performed by using a mixture of the Reference Material Linear homopolymer polyethylene (having zero comonomer content, Melt index (I2) of 1.0, polydispersity Mw / Mn approximately 2.6 by conventional gel permeation chromatography, 1.0 mg / ml) and Eicosane (2 mg / ml) in ODCB. iCCD temperature calibration consisted of four steps: (1) Calculating the delay volume defined as the temperature offset between the measured peak elution temperature of Eicosane minus 30.00℃; (2) Subtracting the temperature offset of the elution temperature from iCCD raw temperature data. It is noted that this temperature offset is a function of experimental conditions, such as elution temperature, elution flow rate, etc.; (3) Creating a linear calibration line transforming the elution temperature across a range of 30.00℃ and 140.00℃ so that the linear homopolymer polyethylene reference had a peak temperature at 101.0℃, and Eicosane had a peak temperature of 30.0℃; (4) For the soluble fraction measured isothermally at 30℃, the elution temperature below 30.0℃ is extrapolated linearly by using the elution heating rate of 3℃ / min according to the reference (Cerk and Cong et al., U.S. Pat. No. 9,688,795) .
[0091] Molecular weight of polymer and the molecular weight of the polymer fractions were determined directly from LS detector (90 degree angle) and concentration detector (IR-5) according Rayleigh-Gans-Debys approximation (Striegel and Yau, Modern Size Exclusion Liquid Chromatogram, Page 242 and Page 263) by assuming the form factor of 1 and all the virial coefficients equal to zero. Integration windows are set to integrate all the chromatograms in the elution temperature (temperature calibration is specified above) range from 23.0℃ to 120℃.
[0092] The calculation of Molecular Weight (Mw) from iCCD includes the following four steps:
[0093] (1) Measuring the interdetector offset. The offset is defined as the geometric volume offset between LS with respect to concentration detector. It is calculated as the difference in the elution volume (mL) of polymer peak between concentration detector and LS chromatograms. It is converted to the temperature offset by using elution thermal rate and elution flow rate. A linear high density polyethylene (having zero comonomer content, Melt index (I2) of 1.0, polydispersity Mw / Mn approximately 2.6 by conventional gel permeation chromatography) is used. Same experimental conditions as the normal iCCD method above are used except the following parameters: crystallization at 10℃ / min from 140℃ to 137℃, the thermal equilibrium at 137℃for 1 minute as Soluble Fraction Elution Time, soluble fraction (SF) time of 7 minutes, elution at 3℃ / min from 137℃ to 142℃. The flow rate during crystallization is 0.0 ml / min. The flow rate during elution is 0.80 ml / min. Sample concentration is 1.0 mg / ml.
[0094] (2) Each LS datapoint in LS chromatogram is shifted to correct for the interdetector offset before integration.
[0095] (3) Baseline subtracted LS and concentration chromatograms are integrated for the whole eluting temperature range of the Step (1) . The MW detector constant is calculated by using a known MW HDPE sample in the range of 100,000 to 140,000Mw and the area ratio of the LS and concentration integrated signals.
[0096] (4) Mw of the polymer was calculated by using the ratio of integrated light scattering detector (90 degree angle) to the concentration detector and using the MW detector constant.
[0097] The molecular weight calculations and calibrations were performed in GPCOneTMsoftware.
[0098] EXAMPLES
[0099] The following Examples illustrate features of the present disclosure but are not intended to limit the scope of the disclosure. The following experiments analyzed the performance of embodiments of the multilayer films described herein.
[0100] Materials
[0101] Materials used to form the multilayer films of the examples and comparative examples are described below.
[0102] RD265CF is a random copolymer polypropylene commercially available from Borouge Pte Ltd having a melt flow rate of 8.0 g / 10 min 230℃ and a density of 0.900 to 0.910 g / cm3. RD265CF is used in outer layers of example multilayer films.
[0103] DS6D82 is a random copolymer polypropylene from Braskem having a MFR of 7.0 g / 10 min 230℃ and a density of 0.900 to 0.910 g / cm3. DS6D82 is used in the outer layers of comparative example multilayer films.
[0104] XUS 59910.18 is a high density polyethylene from Dow having a melt index of 1.5 g / 10 min at 190℃ and a density of 0.955 g / cm3. XUS 59910.18 is used in the core layer and outer layers of example multilayer films and comparative example multilayer films.
[0105] DowlexTM 2750ST is a high density polyethylene commercially available from Dow having a melt index of 1.5 g / 10 min at 190℃ and a density of 0.950 g / cm3. Dowlex 2750ST is used in the core layer and outer layers of example multilayer films and comparative example multilayer films.
[0106] Forming the Example and Comparative Example Multilayer Films
[0107] Example multilayer films and comparative example multilayer films were formed as described herein. Six different three-layer co-extruded sheets were made on a lab-scale multilayer cast sheet line supplied by POTP following a regular casting sheet process with a melt temperature of about 200℃. The multilayer sheets each had a thickness of about 700 μm.
[0108] Biaxial orientation of each multilayer sheet was conducted on a Karo IV dual chamber lab stretcher supplied by Bureckner to make the Example multilayer film and the Comparative Example multilayer film. Samples of each multilayer sheet were cut into 10 cm by 10 cm squares along a machine direction and a transverse direction respectively and loaded onto the stretching frame. A sample was secured with five clips positioned on each of the four sides of the sample. Then, the stretching frame was moved into the first chamber.
[0109] For each of Example and Comparative Examples, the sheet sample was heated by hot air with forced convection at a temperature of 129℃ for 180 seconds. Then, the sample was stretched to five times the original length in the machine direction with a 500% / sstretch rate. Immediately after the machine direction stretch, the sample was moved to the second chamber and heated by circulating air at a temperature of 128℃ for 30 seconds. Then, the sample was stretched to eight times its original length in the transverse direction at a 250% / sstretch rate. The stretched multilayer film sample was then unloaded from the stretching frame and aged for at least one week.
[0110] The composition of each layer of the multilayer film and the layer ratio of each multilayer film is given in Table 1.
[0111] Table 1.
[0112] Metallization of each Example multilayer film and Comparative Example multilayer film was conducted on a lab scale vacuum deposition chamber supplied by Shenyang Vacuum Technology Institute. For each Example and Comparative Example, Layer A given in Table 2 was metallized. Before metallization, surface of the multilayer film to be metallized was corona treated to bring the surface energy of the treated surface to greater than 46 dyne / cm. A substrate holder fixed the multilayer film in the deposition chamber with the treated surface facing the outside. An aluminum wire (99.9999%purity) was inserted into the resistance heater. The pressure within the deposition chamber was reduced to 3x10-3 Pa. The resistance heater was turned on to melt and evaporate the aluminum wire. The current of the resistance heater was adjusted to induce a deposition rate of 40 Angstrom / s. The multilayer film was spun at a constant speed to facilitate uniform deposition of aluminum onto the multilayer film. The deposition chamber was ventilated and then the metallized multilayer film was removed from the deposition chamber.
[0113] Characterization of the Example and Comparative Example Multilayer Films
[0114] The surface energy of the aluminum surface of each Example and Comparative Example metallized film was measured one month after metallization and then again two months after metallization. The results are given in Table 2. Each measurement was made three times, and the standard deviation is included in parentheses in Table 2.
[0115] Additionally, the bonding strength between the aluminum layer and the polymer film was measured for each Example and Comparative Example metallized film one day after metallization and one month after metallization. For each sample, the aluminum coated surface of the film is heat sealed onto an EAA film, using Lab-scale sealing Tester Model 4000, J&B. The seal bar was 5 mm wide. The seal bar on the EAA film side was set at 110℃, and the seal bar on the metallized film side was set at 70℃. The dwell time of the heat sealing was 20 seconds and the sealing pressure was 5 bar. After heat sealing, the sealed sample was aged at 23℃ for 24 hours before testing for bonding strength. The test was performed using INSTRON 5965 at a test speed of 12 in / min and a temperature of 23℃ (peel mode: T-peel, sample width: 15 mm) . The results are given in Table 2. Each measurement was made five times, and the standard deviation is included in parentheses in Table 2.
[0116] Table 2.
[0117] Each of the polypropylene compositions used in the Examples and Comparative Examples were analyzed by the iCCD method described hereinabove. The weight percent of elution fraction of the polypropylene composition in a temperature range from 90℃ to 120℃ for each sample is included in Table 5.
[0118] Table 5.
[0119] The multilayer films of Examples 1 and 2 were both metallized on a skin layer comprising polyethylene, and both had another skin layer of RD25CF random copolymer polypropylene with a relatively high weight percent (72.3 wt. %) eluting in the temperature range from 90℃ to 120℃ in the iCCD analysis. The multilayer films of Examples 1 and 2 both had good surface energy retention of greater than 42 dyne / cm one month after metallization and greater than 38 dyne / cm two months after metallization. The multilayer films of Examples 1 and 2 also both had good aluminum bonding strength with the polyethylene skin layer of about 2 N / 15 mm just after metallization and of 1.5 N / 15 mm one month after metallization.
[0120] The multilayer film of Comparative Example 1 was also metallized on a skin layer comprising polyethylene, and had another skin layer of DS6D82 random copolymer polypropylene with a relatively low weight percent (41.5%) eluting in the temperature range from 90℃ to 120℃ in the iCCD analysis. The multilayer film of Comparative Example 1 had an inferior surface energy retention of 37 dyne / cm one month after metallization and 34 dyne / cm two months after metallization.
[0121] The multilayer films of Comparative Examples 2 and 3 were metallized on a skin layer comprising RD25CF random copolymer polypropylene with a relatively high weight percent (72.3 wt. %) eluting in the temperature range from 90℃ to 120℃ in the iCCD analysis. However, the multilayer films of both Comparative Examples 2 and 3 had inferior surface energy retention of less than 34 dyne / cm one month after metallization. Additionally, the multilayer films of both Comparative Examples 2 and 3 had inferior aluminum bonding strength of less than 0.7 N / 15 mm just after metallization.
[0122] The multilayer film of Comparative Example 4 was metallized on a skin layer of polyethylene, but did not have another skin layer of polypropylene. The multilayer film of Comparative Example 4 had inferior surface energy retention of less than 34 dyne / cm one month after metallization.
[0123] It will be apparent that modifications and variations are possible without departing from the scope of the disclosure defined in the appended claims. More specifically, although some aspects of the present disclosure are identified herein as preferred or particularly advantageous, it is contemplated that the present disclosure is not necessarily limited to these aspects.
Claims
1.A multilayer film comprising:a core layer comprising a first polyethylene composition having a density of at least 0.918 g / cm3;a first outer layer comprising a second polyethylene composition;a second outer layer comprising a polypropylene composition, wherein the core layer is positioned between the first outer layer and the second outer layer, wherein the polypropylene composition has a first fraction area in a temperature range of from 90℃ to 120℃ in an elution profile via an improved comonomer composition distribution (iCCD) analysis method, and wherein the first fraction area comprises at least 50%of a total area of the elution profile; anda metal layer in direct contact with the first outer layer, wherein the first outer layer is positioned between the core layer and the metal layer.2.The multilayer film of claim 1, wherein the multilayer film comprises one or more fatty acids, one or more fatty acid salts, or both, in an amount greater than 300 ppm based on the total weight of the multilayer film.3.The multilayer film of claim 1 or claim 2, wherein the first polyethylene composition and the second polyethylene composition have a density from 0.940 g / cm3 to 0.965 g / cm3.4.The multilayer film of any one of claims 1 to 3, wherein the first polyethylene composition and the second polyethylene composition have a melt index (I2) from 0.2 g / 10 min. to 5.0 g / 10 min.5.The multilayer film of any one of claims 1 to 4, wherein the first polyethylene composition has a density at least 0.005 g / cm3 greater than a density of the second polyethylene composition.6.The multilayer film of any one of claims 1 to 5, wherein the second outer layer has a thickness of less than 25%of a total thickness of the multilayer film.7.The multilayer film of any one of claims 1 to 6, wherein the metal layer comprises one or more of Al, Zn, Au, Ag, Cu, Ni, Cr, Ge, Se, Ti, and Sn.8.The multilayer film of any one of claims 1 to 7, wherein the metal layer is an outermost layer of the multilayer film.9.The multilayer film of any one of claims 1 to 8, wherein a surface energy of the metal layer is greater than 34 dyne / cm at a time greater than or equal to two weeks after metallization.10.The multilayer film of any one of claims 1 to 9, wherein the core layer is in direct contact with the first outer layer and the second outer layer.11.The multilayer film of any one of claims 1 to 10, further comprising an interlayer positioned between the second outer layer and the core layer, wherein the interlayer comprises one or more of a polypropylene composition, a polyethylene composition, an ethylene-based plastomer composition, an ethylene-based elastomer composition, and a propylene-based elastomer composition.12.The multilayer film of any one of claims 1 to 11, further comprising a sealant layer, wherein the sealant layer is in direct contact with the second outer layer.13.The multilayer film of any one of claims 1 to 12, wherein the multilayer film has an optical density from 1.0 to 4.0.14.The multilayer film of any one of claims 1 to 13, wherein the multilayer film is stored in a roll such that the metal layer is in direct contact with a layer on an opposite side of the multilayer film.15.An article comprising the multilayer film of any one of claims 1 to 14, wherein the article is a package.
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