Multilayer articles

Abstract

Embodiments of the present disclosure are directed towards multilayer articles including a sealant portion comprising an ethylene copolymer having a crystallinity less than or equal to 45%, an ethylene acrylate copolymer layer, a LLDPE layer, a first tie layer, an ethylene vinyl alcohol copolymer layer, a second tie layer, and an outer layer.

Description

MULTILAYER ARTICLESField of Disclosure

[0001] Embodiments of the present disclosure are directed towards multilayer articles including a sealant portion comprising an ethylene copolymer having a crystallinity less than or equal to 45%, an ethylene acrylate copolymer layer, a LLDPE layer, a first tie layer, an ethylene vinyl alcohol copolymer layer, a second tie layer, and an outer layer.Background

[0002] Films can be composed of multiple layers that provide the desirable mechanical strength, chemical resistance, and / or biocompatibility useful for a number of applications, including medical applications. Various materials have been used in the formation of films. However, there remains a need for multilayer articles that can provide one or more advantageous properties.Summary

[0003] The present disclosure provides various embodiments, including, without limitation, the following.

[0004] A multilayer article including: a sealant portion comprising an ethylene copolymer having a crystallinity less than or equal to 45%; an ethylene acrylate copolymer layer; a linear low-density polyethylene (LLDPE) layer; a first tie layer; an ethylene vinyl alcohol copolymer layer; a second tie layer; and an outer layer.Detailed Description

[0005] The present disclosure is directed toward multilayer articles including a sealant portion comprising an ethylene copolymer having a crystallinity less than or equal to 45%, an ethylene acrylate copolymer layer, a LLDPE layer, a first tie layer, an ethylene vinyl alcohol copolymer layer, a second tie layer, and an outer layer. Advantageously, these multilayer articles have one or more desirable properties, as compared to a number of other films. Further advantageously, these multilayer articles can be downgauged, as compared to a number of other films, while providing barrier to oxygen, barrier to humidity, one or more tensile properties, one or more mechanical properties, and / or purity maintenance.

[0006] As mentioned, the present disclosure is directed toward multilayer articles, e.g., multilayer films. Embodiments provide that the multilayer articles can include different numbers of layers for various applications. For instance, embodimentsprovide that the multilayer articles disclosed herein can include from 6 to 12 layers. One or more embodiments provide that the multilayer article includes only 6 layers. One or more embodiments provide that the multilayer article includes only 7 layers. One or more embodiments provide that the multilayer article includes only 8 layers. One or more embodiments provide that the multilayer article includes only 9 layers. One or more embodiments provide that the multilayer article includes only 10 layers. One or more embodiments provide that the multilayer article includes only 1 1 layers. One or more embodiments provide that the multilayer article includes only 12 layers.

[0007] As used herein, “layer” refers to a continuous or substantially continuous sheet or stratum of material that forms part of a multilayer article. A layer may be comprised of a single material or a blend of materials and may possess distinct physical or chemical properties relative to adjacent layers. The layers can be laminated, coextruded, or otherwise combined to form the multilayer articles disclosed herein. Multilayer films are known and known components, e.g., known processes and conditions, may be utilized to make the multilayer articles disclosed herein. One or more embodiments provide that the multilayer articles disclosed herein can be made by a blown film forming process.

[0008] 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.

[0009] “Polyethylene” or “ethylene copolymer”, e.g., ethylene-based polymers, refer to polymers comprising greater than 50% by mole of units derived from ethylene monomer. This includes ethylene-based homopolymers or copolymers, indicating that units derived from two or more comonomers. Ethylene-based polymers comprising greater than 50% by mole of units derived from ethylene monomer are known in the art and include, but are not limited to, Low Density Polyethylene (LDPE); Linear Low Density Polyethylene (LLDPE); Ultra Low Density Polyethylene (ULDPE) High Density Polyethylene (HDPE); and ethylene vinyl acetate (EVA) copolymers.

[0010] The multilayer articles disclosed herein include a sealant portion comprising an ethylene copolymer having a crystallinity less than or equal to 45%, which may be referred to more simply as an “ethylene copolymer” herein. Embodiments provide that the sealant portion comprising an ethylene copolymer can include differentnumbers of layers for various applications. For instance, embodiments provide that the sealant portion comprising an ethylene copolymer can include from 1 to 5 layers. One or more embodiments provide that the sealant portion comprising an ethylene copolymer includes only 1 layer. One or more embodiments provide that the sealant portion comprising an ethylene copolymer includes only 2 layers. One or more embodiments provide that the sealant portion comprising an ethylene copolymer includes only 3 layers. One or more embodiments provide that the sealant portion comprising an ethylene copolymer includes only 4 layers. One or more embodiments provide that the sealant portion comprising an ethylene copolymer includes only 5 layers.

[0011] One or more embodiments provide that the sealant portion comprises an ethylene copolymer, where the ethylene copolymer is ultra-low density polyethylene (ULDPE). One or more embodiments provide that the ULDPE is an ethylene alpha olefin copolymer. One or more embodiments provide that the sealant portion comprises an ethylene copolymer, where the ethylene copolymer is an ethylene-octene copolymer. One or embodiments provide that the sealant portion comprises an ethylene copolymer, where the ethylene copolymer is an ethylene-hexene copolymer. One or embodiments provide that the sealant portion comprises an ethylene copolymer, where the ethylene copolymer is an ethylene-butene copolymer.

[0012] “ULDPE” refers to polyethylenes having densities of 0.855 g / cm3to 0.912 g / cm3, which can be prepared with Ziegler-Natta catalysts, chrome catalysts, or single-site catalysts including, but not limited to, substituted mono- or bis- cyclopentadienyl catalysts (which can be referred to as metallocenes), constrained geometry catalysts, phosphinimine catalysts & polyvalent aryloxyether catalysts (typically referred to as bisphenyl phenoxy). ULDPEs include, but are not limited to, a number of ethylene copolymers, polyethylene (ethylene-based) plastomers, and polyethylene (ethylene-based) elastomers.

[0013] One or more embodiments provide that the sealant portion comprises an ethylene copolymer, where the ethylene copolymer is made with ethylene and a polar comonomer. One or more embodiments provide that the sealant portion comprises an ethylene copolymer, where the ethylene copolymer is an ethylene-vinyl acetate (EVA) copolymer.

[0014] One or more embodiments provide that from 55 to 95 wt% of the ethylene copolymer is derived from ethylene monomers, based on a total weight of the ethylene copolymer. All individual values and subranges from 55 to 95 wt% are included; forexample, the ethylene copolymer can have from a lower limit of 55, 60, 70, or 75 wt% of units derived ethylene monomers to an upper limit of 90, 85, or 80 wt% of units derived ethylene monomers based upon the total weight of the ethylene copolymer.

[0015] One or more embodiments provide that from 5 to 45 wt% of ethylene copolymer is derived from alpha olefin comonomers, based on a total weight of the ethylene copolymer. All individual values and subranges from 5 to 45 wt% are included; for example, the ethylene copolymer can have from a lower limit of 5, 10, 15, or 20 wt% of units derived alpha olefin comonomers to an upper limit of 45, 40, 30, or 25 wt% of units derived alpha olefin based upon the total weight of the ethylene copolymer.

[0016] One or more embodiments provide that from 5 to 45 wt% of ethylene copolymer is derived from polar comonomers, e.g., vinyl acetate monomers, based on a total weight of the ethylene copolymer. All individual values and subranges from 5 to 45 wt% are included; for example, the ethylene copolymer can have from a lower limit of 5, 10, 15, or 20 wt% of units derived polar comonomers to an upper limit of 45, 40, 30, or 25 wt% of units derived from polar comonomers based upon the total weight of the ethylene copolymer.

[0017] One or more embodiments provide that the ethylene copolymer, e.g., ULDPE, can have a density from 0.880 g / cm3to 0.910 g / cm3. All individual values and subranges from 0.880 g / cm3to 0.910 g / cm3are included; for example, the ethylene copolymer can have a density from a lower limit of 0.899, or 0.900 g / cm3to an upper limit of 0.910 or 0.905 g / cm3. Density can be determined according to ASTM D 792.

[0018] The ethylene copolymer can have a crystallinity less than or equal to 45%. For instance, the ethylene copolymer can have a crystallinity from 12% to 45%. All individual values and subranges from 12% to 45% are included; for example, the ethylene copolymer can have a crystallinity from a lower limit of 12, 15, or 20% to an upper limit of 45, 42, 40, 38, or 35 %. Crystallinity can be determined according to Differential Scanning Calorimetry (DSC), as discussed further herein.

[0019] The ethylene copolymer can have a melt index (l2) from 0.5 to 10 dg / min. All individual values and subranges from 0.5 to 10 dg / min are included; for example, the ethylene copolymer can have an l2from a lower limit of 0.50 or 0.75 dg / min to an upper limit of 10, 8, 6, 5, 4, 3, or 2.5 dg / min. I2can be determined according to ASTM D1238, measured at 190 °C and with a 2.16 kg weight.

[0020] The ethylene copolymer can have a melting temperature from 70 to 120 °C. All individual values and subranges from 70 to 120 °C are included; for example, theethylene copolymer can have a melting temperature from a lower limit of 70, 75, 80, 85, 90, or 95 °C to an upper limit of 120, 115, 110, or 100 °C. Melting temperature can be determined according to ASTM D 3418.

[0021] Embodiments of the present disclosure provide that the ethylene copolymer can be made by a number of processes, e.g. with conventional reaction components, reaction conditions, reaction times, and isolation procedures, utilized for making known ethylene copolymers. Embodiments of the present disclosure provide that the ethylene copolymer can be obtained commercially. Examples of commercially available ethylene copolymers are ENGAGE 8480K HEALTH+, and ethylene copolymers available under the trade name ELVAX, from The Dow Chemical Company, among other commercially available ethylene copolymers.

[0022] One or more embodiments provide that one or more layers of the sealant portion comprising the ethylene copolymer are a blend of materials, e.g., a blend of the ethylene copolymer and one or more other materials. Various other materials can be used for different applications.

[0023] “Blend” and “blend of materials,” refer to 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 / or any other method known in the art. “Blend” and “blend of materials,” do not refer to laminates, but one or more layers a, as discussed herein, 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.

[0024] Embodiments provide that the blend of ethylene copolymer and one or more other materials can be from 60 to 99 weight percent ethylene copolymer based upon a total weight of the blend. All individual values and subranges from 60 to 99 wt% are included; for example, the blend of ethylene copolymer and one or more other materials can be from a lower limit of 60, 65, 70, 75, or 80 wt% ethylene copolymer to an upper limit of 99, 95, or 93 wt% ethylene copolymer based on the total weight of the blend.

[0025] Embodiments provide that the blend of ethylene copolymer and one or more other materials can be from 1 to 40 weight percent of the one or more other materials based upon a total weight of the blend. All individual values and subranges from 1 to 40 wt% are included; for example, the blend of ethylene copolymer and one ormore other materials can be from a lower limit of 1 , 5, or 7 wt% of the one or more other materials to an upper limit of 40, 35, 30, 25, or 20 wt% of the one or more other materials based on the total weight of the blend.

[0026] One or more embodiments provide that one or more layers of the sealant portion comprise a blend of ethylene copolymer and low-density polyethylene (LDPE). One or more embodiments provide that the LDPE is a homopolymer.

[0027] The term “LDPE” may also be referred to as “high pressure ethylene polymer” or “highly branched polyethylene” and is defined to refer 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. LDPE is well known, e.g., as discussed in U.S. Patent No. 4,599,392, for instance.

[0028] The LDPE can have a density from 0.910 and 0.935 g / cm3. All individual values and subranges from 0.910 and 0.935 g / cm3are included; for example, the LDPE can have a density from a lower limit of 0.910, 0.914, 0.916, or 0.918 g / cm3to an upper limit of 0.935, 0.930, or 0.925 g / cm3. Density can be determined according to ASTM D 792.

[0029] The LDPE can have a melt index (l2) from 0.1 to 10 dg / min. All individual values and subranges from 0.1 to 10 dg / min are included; for example, the LDPE can have an l2from a lower limit of 0.1 , 0.2, 0.75, or 0.10 dg / min to an upper limit of 10, 7, 5, or 2 dg / min. I2can be determined according to ASTM D1238.

[0030] The LDPE can have a melting temperature from 100 to 120 °C. All individual values and subranges from 100 to 120 °C are included; for example, the LDPE can have a melting temperature from a lower limit of 100°C to an upper limit of 1 15, or 110 °C. Melting temperature can be determined according to ASTM D 3418.

[0031] Embodiments of the present disclosure provide that the LDPE can be made by a number of processes, e.g. with conventional reaction components, reaction conditions, reaction times, and isolation procedures, utilized for making known LDPEs. Embodiments of the present disclosure provide that the LDPE can be obtained commercially. An example of a commercially available LDPE is AGILITY AT 1604 from The Dow Chemical Company.

[0032] The multilayer articles disclosed herein include an ethylene acrylate copolymer layer. The ethylene acrylate copolymer layer comprises an ethylene acrylate copolymer.

[0033] The ethylene acrylate copolymer includes compositional units derived from monomers, i.e., ethylene and acrylate, such as methyl acrylate, ethyl acrylate, and / or butyl acrylate.

[0034] Embodiments provide that the ethylene acrylate copolymer can have from 5 to 40 weight percent of constitutional units derived from acrylate, e.g., methyl acrylate, ethyl acrylate, and / or butyl acrylate, based upon a total weight of constitutional units derived from acrylate and ethylene. All individual values and subranges from 5 to 40 weight percent are included; for example, the ethylene acrylate copolymer can have from a lower limit of 5, 10, 15, or 20 weight percent of constitutional units derived from acrylate to an upper limit of 40, 35, or 30 weight percent of constitutional units derived from acrylate based upon the total weight of constitutional units derived from acrylate and ethylene.

[0035] Embodiments provide that the ethylene acrylate copolymer can have from 60 to 95 weight percent of constitutional units derived from ethylene based upon a total weight of constitutional units derived from acrylate and ethylene. All individual values and subranges from 60 to 95 weight percent are included; for example, the ethylene acrylate copolymer can have from a lower limit of 60, 65, or 70 weight percent of constitutional units derived from ethylene to an upper limit of 95, 90, 85, or 80 weight percent of constitutional units derived from ethylene based upon the total weight of constitutional units derived from acrylate and ethylene.

[0036] The ethylene acrylate copolymer can be prepared using known equipment, reaction conditions, and reaction components. The ethylene acrylate copolymer can be obtained commercially. A commercial example of the ethylene acrylate copolymer (ethylene methyl acrylate copolymer) is ELVALOY AC 1224 from The Dow Chemical Company, among other ethylene acrylate copolymers.

[0037] Embodiments provide that the ethylene acrylate copolymer can have a melt index (I2) from 0.1 dg / min to 50 dg / min. All individual values and subranges from 0.1 to 50 dg / min are included; for example, the ethylene acrylate copolymer can have an I2 from a lower limit of 0.1 , 0.2, 0.5, or 1 dg / min to an upper limit of 50, 40, 30, 20, 15, 10, or 5 dg / min. Melt index (I2) can be determined according to ASTM D1238.

[0038] Embodiments provide that the ethylene acrylate copolymer can have a density from 0.920 g / cm3to 0.960 g / cm3. All individual values and subranges from 0.920 g / cm3to 0.960 g / cm3are included; for example, the ethylene acrylate copolymer can have adensity from a lower limit of 0.920, 0.930, or 0.940 g / cm3to an upper limit of 0.960, 0.950, 0.94 g / cm3. Density can be determined according to ASTM D 792.

[0039] Embodiments provide that the ethylene acrylate copolymer can have a peak melting point from 70 to 105 °C. All individual values and subranges from 70 to 105 °C are included; for example, the ethylene acrylate copolymer can have a peak melting point from a lower limit of 70, 75, 80, or 85 °C to an upper limit of 99, 95, or 93 °C. Peak melting point can be determined according to ASTM D3418.

[0040] The multilayer articles disclosed herein include a linear low-density polyethylene (LLDPE) layer. The LLDPE layer comprises LLDPE.

[0041] 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. LLDPEs are well known. LLDPEs contain less long chain branching than LDPEs and include the substantially linear ethylene polymers, which are discussed in U.S. Patent No. 5,272,236, U.S. Patent No. 5,278,272, U.S. Patent No. 5,582,923 and U.S. Patent No. 5,733,155, among others. 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.

[0042] One or more embodiments provide that the LLDPE is a copolymer. One or more embodiments provide that the LLDPE is an ethylene-octene copolymer. One or embodiments provide that the LLDPE is an ethylene-hexene copolymer. One or embodiments provide that the LLDPE is an ethylene-butene copolymer.

[0043] One or more embodiments provide that from 70 to 96 wt% of the LLDPE is derived from ethylene monomers, based on a total weight of the LLDPE. All individual values and subranges from 60 to 96 wt% are included; for example, the LLDPE can have from a lower limit of 70 or 80 wt% of units derived ethylene monomers to an upper limit of 99, 98, or 96 wt% of units derived ethylene monomers based upon the total weight of the LLDPE.

[0044] One or more embodiments provide that from 4 to 30 wt% of the LLDPE are derived from alpha olefin monomers, based on a total weight of the LLDPE. All individual values and subranges from 4 to 30 wt% are included; for example, the LLDPEcan have from a lower limit of 4, 2, or 1 wt% of units derived alpha olefin monomers to an upper limit of 30 or 20 wt% of units derived alpha olefin monomers based upon the total weight of the LLDPE.

[0045] The LLDPE can have a density from 0.910 g / cm3to 0.935 g / cm3. All individual values and subranges from 0.910 g / cm3to 0.935 g / cm3are included; for example, the LLDPE can have a density from a lower limit of 0.910, 0.915, 0.917, or 0.920 g / cm3to an upper limit of 0.935, 0.930, 0.929, or 0.928 g / cm3. Density can be determined according to ASTM D 792.

[0046] The LLDPE can have a melt index (l2) from 0.2 to 10 dg / min. All individual values and subranges from 0.2 to 10 dg / min are included; for example, the LLDPE can have an l2from a lower limit of 0.2, 0.5, or 0.75 dg / min to an upper limit of 10, 5, 4, 3, or 2.5 dg / min. I2can be determined according to ASTM D1238.

[0047] Embodiments of the present disclosure provide that the LLDPE can be made by a number of processes as previously mentioned, e.g. with conventional reaction components, reaction conditions, reaction times, and isolation procedures, utilized for making known LLDPEs. Embodiments of the present disclosure provide that the LLDPE can be obtained commercially. Examples of commercially available LLDPE are INNATE ST 100 from The Dow Chemical Company.

[0048] The multilayer articles disclosed herein include a first tie layer and a second tie layer. Tie layers are known. The tie layers may be utilized to promote adhesion and / or bonding of a number of components of the multilayer articles disclosed herein. Different tie layers, e.g., different materials, may be utilized for various applications.

[0049] One or more embodiments provide that the first tie layer and the second tie layer comprise a polymer having a number of polar groups grated thereto. Suitable polymers for the tie layers include thermoplastic polymers, such as ethylene-unsaturated acid copolymers, ethylene-unsaturated ester copolymers, polyurethane, ethylene-vinyl acetate copolymers, ethylene- (meth)acrylic acid copolymers, ethylene / methyl acrylate copolymers, ethylene homo-polymers or co-polymers modified with anhydride or carboxylic acid functionalities, mixtures of these resins or mixtures of any of the above resins with an ethylene homo- or co-polymer, and the like known resins, such as, for example, anhydride modified grafted linear low density polyethylene, anhydride grafted low density polyethylene, homogeneous ethylene / alpha-olefin copolymer, anhydride grafted ethylene / vinyl acetate copolymer, anhydride grafted ethylene / methyl acrylatecopolymers, anhydride grafted styrene / ethylene / butadiene / styrene copolymers. Some suitable commercial tie resins are, for example BYNEL 4164, BYNEL 21 E810, BYNEL 21 E780, BYNEL 46E1060, and BYNEL 21 E787 from The Dow Chemical Company. One or more embodiments provide that the first tie layer and the second tie layer comprise anhydride modified ethylene acrylate resin.

[0050] The multilayer articles disclosed herein include an ethylene vinyl alcohol (EVOH) copolymer layer. The EVOH copolymer layer comprises an EVOH copolymer.

[0051] The EVOH copolymer can have from 25 to 45 mole% of units derived from ethylene, based a total mole% of units derived from ethylene and vinyl alcohol. All individual values and subranges from 25 to 45 mole% are included; for example the EVOH copolymer can have from a lower limit of 25, 30, or 33 mole% to an upper limit of 45, 43, or 40 mole% of units derived from ethylene, based the total mole% of units derived from ethylene and vinyl alcohol.

[0052] The EVOH copolymer can have from 55 to 75 mole% of units derived from vinyl alcohol, based a total mole% of units derived from ethylene and vinyl alcohol. All individual values and subranges from 55 to 75 mole% are included; for example the EVOH copolymer can have from a lower limit of 55, 57, or 60 mole% to an upper limit of 75, 70, or 67 mole% of units derived from vinyl alcohol, based the total mole% of units derived from ethylene and vinyl alcohol.

[0053] The EVOH copolymer can have a density from 0.9 to 2.0 g / cm3. All individual values and subranges from 0.9 to 2.0 g / cm3are included; for example, the EVOH copolymer can have a density from a lower limit of 0.3, 0.5, 0.7, or 0.9 g / cm3to an upper limit 2.0 or 1 .5 g / cm3. Density can be determined according to ASTM D 792.

[0054] The EVOH copolymer can have a melt index (l2) from 0.2 to 10 dg / min. All individual values and subranges from 0.2 to 10 dg / min are included; for example, the EVOH copolymer can have an l2from a lower limit of 0.2, 0.50, 0.75, or 1 .00 dg / min to an upper limit of 10, 7, 5, 4, 3, or 2.5 dg / min. I2can be determined according to ASTM D1238.

[0055] The EVOH copolymer can have an oxygen transmission rate from 0.1 to 3 cm3-20 pm / m3-day-atm. All individual values and subranges from 0.1 to 3 cm3-20 pm / m3-day-atm are included; for example, the EVOH copolymer can have an oxygen transmission rate from a lower limit of 0.1 , 0.2, 0.3 0.4, or 0.5 cm3-20 pm / m3-day-atm to an upper limit of 3, 2.7, 2.5, 2.2, or 2 cm3-20 pm / m3-day-atm. Oxygen transmission rate can be determined according to ASTM D3985.

[0056] The EVOH copolymer can be prepared using known equipment, reaction conditions, and reaction components. The EVOH copolymer can be obtained commercially. A commercial example of the EVOH copolymer is EVAL H171 B from Kuraray, among other EVOH copolymers.

[0057] The multilayer articles disclosed herein include an outer layer. Different outer layers can be utilized for various applications. As used herein, “outer layer” refers to a layer that is located on the outside of the multilayer article, e.g., a layer that is positioned to be in contact with the environment.

[0058] One or more embodiments provide that the outside layer comprises LLDPE, as discussed herein. Examples of LLDPE is INNATE ST 50, ELITE 5400, DOWLEX GM 8090, and DOWLEX 2045G, from The Dow Chemical Company.

[0059] One or more embodiments provide that the outside layer comprises high density polyethylene (HDPE). One or more embodiments provide that the HDPE is a homopolymer. One or embodiments provide that the HDPE is a copolymer.

[0060] The term “HDPE” refers to polyethylenes having densities greater than 0.935 g / cm3and up to 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).

[0061] The HDPE can have a density from 0.940 g / cm3to 0.980 g / cm3. All individual values and subranges from 0.940 g / cm3to 0.980 g / cm3are included; for example, the HDPE can have a density from a lower limit of 0.940, 0.945, 0.950, or 0.955 g / cm3to an upper limit of 0.980, 0.975, or 0.970 g / cm3. Density can be determined according to ASTM D 792.

[0062] The HDPE can have a melt index (l2) from 0.2 to 10 dg / min. All individual values and subranges from 0.2 to 10 dg / min are included; for example, the HDPE can have an l2from a lower limit of 0.2, 0.5, or 0.75 dg / min to an upper limit of 10, 5, 4, 3, or 2.5 dg / min. I2can be determined according to ASTM D1238.

[0063] Embodiments of the present disclosure provide that the HDPE can be made by a number of processes, e.g. with conventional reaction components, reaction conditions, reaction times, and isolation procedures, utilized for making known HDPEs. Embodiments of the present disclosure provide that the HDPE can be obtainedcommercially. Examples of commercially available HDPE are ELITE AT 6900, DOWLEX 2750ST, ELITE 5960G1 , CONTINUUM DMDA 6400, from The Dow Chemical Company.

[0064] As mentioned, the multilayer articles disclosed herein include a sealant portion comprising an ethylene copolymer having a crystallinity less than or equal to 45%, an ethylene acrylate copolymer layer, a LLDPE layer, a first tie layer, an ethylene vinyl alcohol copolymer layer, a second tie layer, and an outer layer.

[0065] Embodiments provide that the sealant portion comprising an ethylene copolymer having a crystallinity less than or equal to 45%, contacts and is adjacent to the ethylene acrylate copolymer layer. As discussed herein, embodiments provide that the sealant portion can include different numbers of layers for various applications. In other words, one layer of the sealant portion contacts and is adjacent to the ethylene acrylate copolymer layer. One or more embodiments provide that a number of layers of the sealant portion do not contact and are not adjacent to the ethylene acrylate copolymer layer, e.g., the number of layers of the sealant portion are separated from the ethylene acrylate copolymer layer by the one layer of the sealant portion that contacts and is adjacent to the ethylene acrylate copolymer layer.

[0066] Embodiments provide that the ethylene acrylate copolymer layer contacts and is adjacent to the sealant portion comprising an ethylene copolymer having a crystallinity less than or equal to 45% and that the ethylene acrylate copolymer layer contacts and is adjacent to the LLDPE layer.

[0067] Embodiments provide that the LLDPE layer contacts and is adjacent to the ethylene acrylate copolymer layer and that the LLDPE layer contacts and is adjacent to the first tie layer.

[0068] Embodiments provide that the first tie layer contacts and is adjacent to the LLDPE layer and that the first tie layer contacts and is adjacent to the ethylene vinyl alcohol copolymer layer.

[0069] Embodiments provide that the ethylene vinyl alcohol copolymer layer contacts and is adjacent to the first tie layer and that the ethylene vinyl alcohol copolymer layer contacts and is adjacent to the second tie layer.

[0070] Embodiments provide that the second tie layer contacts and is adjacent to the ethylene vinyl alcohol copolymer layer and that the second tie layer contacts and is adjacent to the outer layer.

[0071] Embodiments provide that the outer layer contacts and is adjacent to the second tie layer.

[0072] Embodiments provide that the multilayer articles disclosed herein, and components thereof can have different thicknesses and / or total thicknesses for various applications. As used herein, “thickness”, refers to a distance that is inclusive of and normal to a planar portion of a respective layer or portion of the multilayer article, e.g., e.g. a height of a cross section of the respective layer or portion of the multilayer article.

[0073] A “total thickness”, refers to a distance that is inclusive of and normal to a combination of non-intersecting planar portions of the sealant portion, the ethylene acrylate copolymer layer, the LLDPE layer, the first tie layer, the ethylene vinyl alcohol copolymer layer, the second tie layer, and the outer layer, e.g. a height of a cross section of the multilayer article.

[0074] Embodiments provide that the multilayer articles disclosed herein can have a total thickness from 100 micrometers (pm) to 400 pm. All individual values and subranges from 100 pm to 400 pm are included; for example, the multilayer article can have total thickness from a lower limit of 100, 110, 1 15, 125, 135, or 140 pm to an upper limit of 400, 350, 300, 275, 250, or 225 pm. One or more embodiments provide that the multilayer articles disclosed herein can have a total thickness from 150 pm to 200 pm. One or more embodiments provide that the multilayer articles disclosed herein can have a total thickness from 100 to 150 pm.

[0075] The multilayer articles disclosed herein can be made using known equipment, conditions, and components, and such. One or more embodiments provide that the multilayer articles disclosed herein can be made a blown film process.

[0076] As mentioned, advantageously, these multilayer articles can be downgauged, i.e., have a reduced total thickness, as compared to a number of other films, while providing barrier to oxygen, barrier to humidity, one or more tensile properties, one or more mechanical properties, and / or purity maintenance.

[0077] Embodiments provide that the sealant portion comprising an ethylene copolymer having a crystallinity less than or equal to 45% can be from 20% to 70% of the total thickness (100%) of the multilayer articles disclosed herein. For instance, in an embodiment where the multilayer article has a total thickness of 100 pm and the sealant portion is 50% of the total thickness of the multilayer article, then the sealant portion will have thickness of 50 pm. All individual values and subranges from 20% to 70% are included; for example, the sealant portion comprising the ethylene copolymer having a crystallinity less than or equal to 45% can be from a lower limit of 20, 30, or 40% to anupper limit of 70, 65, 60, or 55% of the total thickness the multilayer articles disclosed herein.

[0078] As mentioned, embodiments provide that the sealant portion comprising an ethylene copolymer having a crystallinity less than or equal to 45% can include different numbers of layers for various applications.

[0079] One or more embodiments provide that the sealant portion includes only 3 layers. As such, a first layer of the sealant portion comprising ethylene copolymer having a crystallinity less than or equal to 45% can be from 30% to 50% of a thickness (100%) of the sealant portion comprising an ethylene copolymer having a crystallinity less than or equal to 45%. All individual values and subranges from 30% to 50% are included; for example, the first layer of the sealant portion comprising an ethylene copolymer having a crystallinity less than or equal to 45% can be from a lower limit of 30, 32, or 35% to an upper limit of 50, 48, or 45% of the thickness of the sealant portion comprising an ethylene copolymer having a crystallinity less than or equal to 45%.

[0080] A second layer of the sealant portion can be from 30% to 50% of a thickness (100%) of the sealant portion comprising ethylene copolymer having a crystallinity less than or equal to 45%. All individual values and subranges from 30% to 50% are included; for example, the second layer of the sealant portion can be from a lower limit of 30, 32, or 35% to an upper limit of 50, 48, or 45% of the thickness of the sealant portion comprising an ethylene copolymer having a crystallinity less than or equal to 45%.

[0081] A third layer of the sealant portion comprising can be from 30% to 50% of a thickness (100%) of the sealant portion comprising an ethylene copolymer having a crystallinity less than or equal to 45%. All individual values and subranges from 30% to 50% are included; for example, the third layer of the sealant portion can be from a lower upper limit of 30, 32, or 35% to an upper limit of 50, 48, or 45% of the thickness of the sealant portion comprising an ethylene copolymer having a crystallinity loess than or equal to 45%.

[0082] Embodiments provide that the ethylene acrylate copolymer layer can be from 1% to 20% of the total thickness (100%) of the multilayer articles disclosed herein. All individual values and subranges from 1 % to 20% are included; for example, the ethylene acrylate copolymer layer can be from a lower limit of 1 , 2, 3 or 4% to an upper limit of 20, 15, 10, 9, 8, 7, or 6% of the total thickness the multilayer articles disclosed herein.

[0083] Embodiments provide that the LLDPE layer can be from 1% to 20% of the total thickness (100%) of the multilayer articles disclosed herein. All individual values and subranges from 1% to 20% are included; for example, the LLDPE layer can be from a lower limit of 1 , 2, 3 or 4% to an upper limit of 20, 15, 10, 9, 8, 7, or 6% of the total thickness the multilayer articles disclosed herein.

[0084] Embodiments provide that the first tie layer can be from 1 % to 10% of the total thickness (100%) of the multilayer articles disclosed herein. All individual values and subranges from 1% to 10% are included; for example, the first tie layer can be from a lower limit of 1 , 2, 3 or 4% to an upper limit of 10, 9, 8, 7, or 6% of the total thickness the multilayer articles disclosed herein.

[0085] Embodiments provide that the ethylene vinyl alcohol copolymer layer can be from 1% to 10% of the total thickness (100%) of the multilayer articles disclosed herein. All individual values and subranges from 1% to 10% are included; for example, the ethylene vinyl alcohol copolymer layer can be from a lower limit of 1 , 2, 3 or 4% to an upper limit of 10, 9, 8, 7, or 6% of the total thickness the multilayer articles disclosed herein.

[0086] Embodiments provide that the second tie layer can be from 1 % to 10% of the total thickness (100%) of the multilayer articles disclosed herein. All individual values and subranges from 1% to 10% are included; for example, the second tie layer can be from a lower limit of 1 , 2, 3, or 4% to an upper limit of 10, 9, 8, 7, or 6% of the total thickness the multilayer articles disclosed herein.

[0087] Embodiments provide that the outer layer can be from 10% to 30% of the total thickness (100%) of the multilayer articles disclosed herein. All individual values and subranges from 10% to 30% are included; for example, the outer layer can be from a lower limit of 10, 12, 14, or 16 % to an upper limit of 30, 26, 24, 22, or 20% of the total thickness the multilayer articles disclosed herein.

[0088] As mentioned, advantageously, the multilayer articles disclosed herein provide one or more desirable properties, as compared to a number of other films, e.g., films having a similar sealant portion, a first tie layer, an ethylene vinyl alcohol copolymer layer, a second tie layer, and an outer layer.

[0089] One or more embodiments provide that the multilayer articles disclosed herein provide an improved, i.e., greater, Elmendorf tear resistance machine direction, as compared to films having a similar sealant portion, a first tie layer, an ethylene vinylalcohol copolymer layer, a second tie layer, and an outer layer. Elmendorf tear can be determined according to ASTM D-1922-09.

[0090] One or more embodiments provide that the multilayer articles disclosed herein, e.g., having total thicknesses of 150 pm and 200 pm, provide a maintained, e.g., essentially equivalent, or an improved optical performance measured by haze %, as compared to films having a similar sealant portion, a first tie layer, an ethylene vinyl alcohol copolymer layer, a second tie layer, and an outer layer. A relatively lower haze % can indicate an improved optical performance. Haze can be determined according to ASTM D-1003.

[0091] One or more embodiments provide that the multilayer articles disclosed herein, e.g., having total thicknesses of 150 pm and 200 pm, provide a maintained, e.g., essentially equivalent, or an improved, i.e. greater, secant modulus machine direction at 2% strain, as compared to films having a similar sealant portion, a first tie layer, an ethylene vinyl alcohol copolymer layer, a second tie layer, and an outer layer. Secant modulus machine direction at 2% strain can be determined according to ASTM D-882.

[0092] One or more embodiments provide that the multilayer articles disclosed herein, e.g., having total thicknesses of 150 pm and 200 pm, provide a maintained, e.g., essentially equivalent, or an improved, i.e. greater, secant modulus cross direction at 2% strain, as compared to films having a similar sealant portion, a first tie layer, an ethylene vinyl alcohol copolymer layer, a second tie layer, and an outer layer. Secant modulus cross direction at 2% strain can be determined according to ASTM D-882.

[0093] One or more embodiments provide that the multilayer articles disclosed herein, e.g., having total thicknesses of 150 pm and 200 pm, provide an improved, i.e. reduced, Water Vapor Transmission Rate, as compared to films having a similar sealant portion, a first tie layer, an ethylene vinyl alcohol copolymer layer, a second tie layer, and an outer layer. Water Vapor Transmission Rate can be determined according to ASTM E96 / E96M.

[0094] The multilayer articles disclosed herein can advantageously be utilized for a number of applications. For instance, the multilayer articles disclosed herein can utilized for a number of single-use applications, such as films that are designed for onetime use in bioprocessing applications. The multilayer articles disclosed herein can be used to make single-use bioreactor bags, which can be utilized in the production of pharmaceuticals, vaccines, and other biotechnological products, among other applications.EXAMPLES

[0095] In the Examples, various terms and designations for materials are used including, for instance, the following:

[0096] Ethylene copolymer (UDLPE; ethylene-octene copolymer; crystallinity 39%; density 0.902 g / cm3; melt index I2 1 .0 dg / min; ENGAGE 8480K obtained from the Dow Chemical Company).

[0097] LDPE (density 0.92 g / cm3; melt index l20.15 dg / min; AGILITY AT 1604 obtained from the Dow Chemical Company).

[0098] Ethylene acrylate copolymer (ethylene methyl acrylate copolymer; 24 wt% methyl acrylate; density 0.944 g / cm3; melt index l22.0 dg / min; ELVALOY AC 1224 obtained from the Dow Chemical Company).

[0099] LLDPE (ethylene-octene copolymer; density 0.928 g / cm3; melt index I2 0.85 dg / min; INNATE ST 100 obtained from the Dow Chemical Company).

[0100] Tie layer (anhydride modified ethylene acrylate resin; density 0.94 g / cm3; BYNEL 21 E810 obtained from the Dow Chemical Company).

[0101] Ethylene vinyl alcohol copolymer (38 mol% ethylene; density 1.17 g / cm3; melt index I2 1.7 dg / min; EVAL H171 B obtained from Kuraray).

[0102] Outer layer 1 (LLDPE; ethylene-octene copolymer; density 0.918 g / cm3; melt index l20.85 dg / min; INNATE ST 50 obtained from the Dow Chemical Company).

[0103] Outer layer 2 (HDPE; density 0.969 g / cm3; melt index l21 .2 dg / min;ELITE AT 6900 obtained from the Dow Chemical Company).

[0104] Example 1 , a multilayer article, was made using a blown film line as follows.

[0105] A sealant portion was made with a first layer of ethylene copolymer, second layer of a blend of ethylene copolymer (90 wt%) and LDPE (10 wt%), and third layer of ethylene copolymer. A fourth layer was made of ethylene acrylate copolymer. A fifth layer was made of LLDPE. A sixth layer was made of a first tie layer. A seventh layer was made of ethylene vinyl alcohol copolymer. An eighth layer was made of a second tie layer. A ninth layer was made with outer layer 1 . Example 1 had a total thickness of 200 pm.

[0106] Comparative Example A was made as Example 1 , with the following changes. Comparative Example A was made with a first layer of ethylene copolymer, second layer of a blend of ethylene copolymer (90 wt%) and LDPE (10 wt%), third layer of ethylene copolymer, a fourth layer of a first tie layer, a fifth layer of ethylene vinyl alcohol copolymer, a sixth layer of a second tie layer, and a seventh layer of outer layer 1 . Comparative Example A had a total thickness of 200 pm.Table 1

[0107] A number of properties were determined for Example 1 and Comparative Example A. The results are reported below.Table 2

[0108] The data of Table 2 illustrate that Example 1 had an improved, i.e., greater, Elmendorf tear resistance machine direction, as compared to Comparative Example A.

[0109] The data of Table 2 illustrate that Example 1 had an improved, i.e., greater, Elmendorf tear resistance cross direction, as compared to Comparative Example A.

[0110] The data of Table 2 illustrate that Example 1 had a maintained, or an improved i.e., lower, optical performance measured by haze%, as compared to Comparative Example A.

[0111] The data of Table 2 illustrate that Example 1 had a maintained, or an improved, i.e., greater, secant modulus machine direction at 2% strain, as compared to Comparative Example A.

[0112] The data of Table 2 illustrate that Example 1 had a maintained, or an improved, i.e., greater, secant modulus cross direction at 2% strain, as compared to Comparative Example A.

[0113] The data of Table 2 illustrate that Example 1 had an improved, i.e., lower, Water Vapor Transmission Rate, as compared to Comparative Example A.

[0114] Example 2, a multilayer article, was made as Example 1 , with the change that Example 2 had a total thickness of 150 pm.

[0115] Comparative Example B was made as Comparative Example A, with the change that Comparative Example B had a total thickness of 150 pm.Table 3

[0116] A number of properties were determined for Example 2 and Comparative Example B. The results are reported below.Table 4

[0117] The data of Table 4 illustrate that Example 2 had an improved, i.e., greater, Elmendorf tear resistance machine direction, as compared to Comparative Example B.

[0118] The data of Table 4 illustrate that Example 2 had an improved, i.e., greater, Elmendorf tear resistance cross direction, as compared to Comparative Example B.

[0119] The data of Table 4 illustrate that Example 2 had a maintained, or an improved i.e., lower, optical performance measured by haze%, as compared to Comparative Example B.

[0120] The data of Table 4 illustrate that Example 2 had a maintained, or an improved, i.e., greater, secant modulus machine direction at 2% strain, as compared to Comparative Example B.

[0121] The data of Table 4 illustrate that Example 2 had a maintained, or an improved, i.e., greater, secant modulus cross direction at 2% strain, as compared to Comparative Example B.

[0122] The data of Table 4 illustrate that Example 2 had an improved, i.e., lower, Water Vapor Transmission Rate, as compared to Comparative Example B.

[0123] Example 3, a multilayer article, was made as Example 1 , with the change that outer layer 2 was utilized rather than outer layer 1 . Example 4, a multilayer article, was made as Example 2, with the change that outer layer 2 was utilized rather than outer layer 1 .Table 5

[0124] A number of properties were determined for Example 3 and Example 4.The results are reported below.Table 6

[0125] Density was determined in accordance with ASTM D 792.

[0126] Melt Index (l2) was determined in accordance with ASTM D 1238 at 190 °C and 2.16 kg.

[0127] Differential Scanning Calorimetry (DSC) / Crystallization and Melting Point.

[0128] Differential Scanning Calorimetry (DSC) was used to measure the melting and crystallization behavior of a respective polymer over a range of temperatures. A TAInstruments Q1000 DSC, equipped with an RCS (refrigerated cooling system) and an autosampler was used to perform this analysis. The instrument was first calibrated using the software calibration wizard. A baseline was obtained by heating a cell from -80 °C to 280 °C without any sample in an aluminum DSC pan. Sapphire standards were then used as instructed by the calibration wizard. Next, 1 to 2 milligrams (mg) of a fresh indium sample were analyzed by heating the standards sample to 180 °C, cooling to 120 °C at a cooling rate of 10 °C / minute, and then maintaining the standards sample isothermally at 120 °C for 1 minute. The standards sample was then heated from 120 °C to 180 °C at a heating rate of 10 °C / minute. Then, it was determined that indium standards sample had heat of fusion (Hf ) = 28.71 ± 0.50 Joules per gram (J / g) and onset of melting = 156.6 °C ± 0.5 °C. Test samples were then analyzed on the DSC instrument.

[0129] During testing, a nitrogen purge gas flow of 50 ml / min was used. Each sample was melt pressed into a thin film at approximately 175 °C; the melted sample was then air-cooled to room temperature (approximately 25eC). The film sample was formed by pressing a sample (0.1 to 0.2 gram) at 175 °C, 1 ,500 psi, and 30 seconds, to form a film (0.1 to 0.2 mil thick). A 3-10 mg, 6 mm diameter specimen was extracted from the cooled polymer, weighed, placed in a light aluminum pan (ca 50 mg), and crimped shut. Analysis was then performed to determine thermal properties.

[0130] The thermal behavior of the sample was determined by ramping the sample temperature up and down to create a heat flow versus temperature profile. First, the sample is rapidly heated to 180 °C, and held isothermal for five minutes to remove its thermal history. Next, the sample was cooled to -40 °C, at a 10 °C / minute cooling rate, and held isothermal at -40 °C for five minutes. The sample was then heated to 150 °C, for a second heat ramp, at a 10 °C / minute heating rate. The cooling and second heating curves were recorded. The cool curve was analyzed by setting baseline endpoints from the beginning of crystallization to -20 °C. The heat curve was analyzed by setting baseline endpoints from -20 °C to the end of melt. The values determined included highest peak melting temperature (Tm), highest peak crystallization temperature (Tc), onset crystallization temperature (Tc onset), heat of fusion (Hf) (in Joules per gram), and the calculated % crystallinity for polyethylene samples using: % Crystallinity for PE = ((Hf) / (292 J / g)) x 100. The heat of fusion (Hf) and the highest peak melting temperature were determined from the second heat curve. Highest peak crystallization temperature and onset crystallization temperature were determined from the cooling curve. Thehighest peak melting temperature (Tm) is the “melting point” (as used herein) of the sample.

[0131] Haze is reported as a percentage (%), was determined according to ASTM D-1003-11.

[0132] 2% Secant modulus was determined according to ISO 527-3.

[0133] Elmendorf tear was determined according to ASTM D-1922-09.

[0134] Water Vapor Transmission Rate was determined using testing conditions : a temperature of 23 °C and a relative humidity of 90 % with a standard compliance of ASTM E398-03.

Claims

1. What is claimed is:1 . A multilayer article comprising: a sealant portion comprising an ethylene copolymer having a crystallinity less than or equal to 45%; an ethylene acrylate copolymer layer; a linear low-density polyethylene (LLDPE) layer; a first tie layer; an ethylene vinyl alcohol copolymer layer; a second tie layer; and an outer layer.

2. The multilayer article of claim 1 , wherein the ethylene copolymer is ultra-low density polyethylene (ULDPE).

3. The multilayer article of claim 2, wherein the ethylene copolymer has a density from 0.880 g / cm3to 0.910 g / cm3.

4. The multilayer article of claim 3, wherein the ethylene acrylate copolymer layer contacts the sealant portion and the LLDPE layer.

5. The multilayer article of claim 4, wherein the first tie layer contacts the LLDPE layer and the ethylene vinyl alcohol copolymer layer.

6. The multilayer article of claim 5, wherein the second tie layer contacts the ethylene vinyl alcohol copolymer layer and the outer layer.

7. The multilayer article of claim 1 , wherein the multilayer article has a total thickness from 100 pm to 400 pm.

8. The multilayer article of claim 7, wherein the sealant portion is from 20% to 70% of the total thickness of the multilayer article.

9. The multilayer article of claim 1 , wherein the ethylene acrylate copolymer layer comprises an ethylene acrylate copolymer having from 5 to 40 weight percent of constitutional units derived from acrylate, based upon a total weight of constitutional units derived from acrylate and ethylene.

10. The multilayer article of claim 1 , wherein the multilayer article has from 6 to 12 layers.

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