Patent ID: 12233629

DETAILED DESCRIPTION

The present disclosure provides a flexible multilayer film. The flexible multilayer film has at least three layers. The flexible multilayer film includes a seal layer and a backing layer. The seal layer includes an ionomer. The backing layer is in direct contact with the seal layer. The backing layer includes an ethylene/α-olefin multi-block copolymer.

1. Flexible Multilayer Film

The flexible multilayer film is resilient, flexible, deformable, and pliable. The flexible multilayer film may be (i) a coextruded multilayer structure, (ii) a laminate, or (iii) a combination of (i) and (ii). The flexible multilayer film includes at least three layers. The flexible multilayer has at least three, or four, or five, or six, or seven, or eight, or nine, or ten, or eleven or more layers. The flexible multilayer film has a seal layer, and a backing layer.

The flexible multilayer film includes a seal layer. The seal layer includes an ionomer. An “ionomer,” as used herein, is an ion-containing polymer. An “ion” is an atom that has an electrical charge, either positive or negative. The ionomer has a majority weight percent (generally 85% to 90%) of repeating monomer units that are non-ionic (non-polar), and a minority weight percent (generally 10% to 15%) of repeating comonomer units that are ionic, or polar (i.e., positively-charged or negatively-charged). The positive charges of the ionic groups attract the negative charges of the ionic groups, creating ionic bonds. Ionomer resins exhibit what is known as “reversible crosslinking” behavior, i.e. when an ionomer is heated, the polymer chains have increased mobility, and the ionic bonds cannot stay intact because the positive charges and negative charges are pulled away from each other.

Non-limiting examples of the monomers and comonomers from which an ionomer is derived include a copolymer of at least one alphα-olefin and at least one ethylenically unsaturated carboxylic acid and/or anhydride. Non-limiting examples of suitable alpha-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 3-methylbutene. Non-limiting examples of suitable carboxylic acids and anhydrides include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, and maleic anhydride.

In an embodiment, the ionomer is a copolymer of ethylene and methacrylic acid.

In an embodiment, the ionomer is a copolymer of ethylene and acrylic acid.

In an embodiment, the ionomer is a metal ionomer. A “metal ionomer,” as used herein, refers to a copolymer based on a metal salt of a copolymer of an alphα-olefin and an ethylenically unsaturated carboxylic acid and/or anhydride. The metal ionomer may be fully or partially neutralized by a metal ion. Non-limiting examples of metals suitable for neutralizing an ionomer include the alkali metals, i.e., cations such as sodium, lithium, and potassium; alkaline earth metals, i.e., cations such as calcium, magnesium; and transition metals such as zinc.

In an embodiment, the metal ionomer has a density from 0.93 to 0.96 g/cc, a Tmfrom 85° C. to 105° C., and a MI from 0.5 to 6.0 g/10 min.

In an embodiment, the ionomer is a sodium ionomer. The term “sodium ionomer,” (or “NaI/O”) as used herein, refers to a copolymer based on a sodium salt of a copolymer of ethylene and a vinyl comonomer with carboxylic acid/or anhydride. Non-limiting examples of suitable comonomer having vinyl comonomer with an acid group include methyl/methacrylic acid, vinyl acrylic acid, methacrylate, n-butyl acrylic acid, and acrylic acid.

In an embodiment, the metal ionomer is a zinc ionomer. The term “zinc ionomer,” (or “ZnI/O”) as used herein, refers to a copolymer based on a zinc salt of a copolymer of ethylene and a vinyl comonomer with carboxylic acid/or anhydride. Non-limiting examples of suitable comonomer having vinyl comonomer with an acid group include methyl/methacrylic acid, vinyl acrylic acid, methacrylate, n-butyl acrylic acid, and acrylic acid.

Non-limiting examples of suitable zinc ionomer include zinc salt of ethylene/acrylic acid comonomer, zinc salt of ethylene/methyl-methacrylic acid copolymer, zinc salt of ethylene/vinyl acrylic acid copolymer, zinc salt of ethylene/methacrylate copolymer, zinc salt of ethylene/n-butyl acrylic acid copolymer, and any combination thereof.

In an embodiment, the ionomer is a zinc salt of an ethylene and methacrylic acid (“MAA”) copolymer having one, some, or all of the following properties:(i) a density from 0.93 g/cc to 0.96 g/cc; and/or(ii) a Tm from 95° C. to 99° C.; and/or(iii) a MI from 01.0 g/10 min to 2.0 g/10 min; and/or(iv) a % MAA from 5% to 20%, based on the total weight of the zinc ionomer.

Non-limiting examples of a suitable zinc ionomer include Surlyn® 1650, which is a zinc salt of an ethylene and methacrylic acid copolymer, available from Dow-DuPont.

The seal layer may have a thickness from 1 μm to 40 μm, or from 2 μm to 38 μm, or from 3 μm to 26 μm, or from 3 μm to 24 μm, or from 5 μm to 22 μm, or from 6 μm to 20 μm, or from 7 μm to 12 μm, or from 8 μm to 14 μm, or from 8 μm to 15 μm, or from 9 μm to 16 μm, or from 8 μm to 18 μm, or from 10 μm to 15 μm, or from 10 μm to 20 μm, or from 10 μm to 30 μm.

In an embodiment, the seal layer has a thickness from 1 μm to 20 μm.

In an embodiment, the seal layer has a thickness from 8 μm to 18 μm, or from 10 μm to 15 μm.

The flexible multilayer film includes a backing layer that is in direct contact with the seal layer. The backing layer is composed of an ethylene-α-olefin multi-block copolymer. In an embodiment, the backing layer is composed of a single polymeric material, namely, an ethylene-α-olefin multi-block copolymer.

The ethylene/α-olefin multi-block copolymer is an ethylene/α-olefin multi-block copolymer. The term “ethylene/α-olefin multi-block copolymer” refers to an ethylene/C4-C8α-olefin multi-block copolymer consisting of ethylene and one copolymerizable C4-C8α-olefin comonomer in polymerized form (and optional additives), the polymer characterized by multiple blocks or segments of two polymerized monomer units differing in chemical or physical properties, the blocks joined (or covalently bonded) in a linear manner, that is, a polymer comprising chemically differentiated units which are joined end-to-end with respect to polymerized ethylenic functionality. Ethylene/α-olefin multi-block copolymer includes block copolymer with two blocks (di-block) and more than two blocks (multi-block). The C4-C8α-olefin is selected from butene, hexene, and octene. The ethylene/α-olefin multi-block copolymer is void of, or otherwise excludes, styrene (i.e., is styrene-free), and/or vinyl aromatic monomer, and/or conjugated diene. When referring to amounts of “ethylene” or “comonomer” in the copolymer, it is understood that this refers to polymerized units thereof. In some embodiments, the ethylene/α-olefin multi-block copolymer can be represented by the following formula: (AB)n; where n is at least 1, preferably an integer greater than 1, such as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or higher, “A” represents a hard block or segment, and “B” represents a soft block or segment. The As and Bs are linked, or covalently bonded, in a substantially linear fashion, or in a linear manner, as opposed to a substantially branched or substantially star-shaped fashion. In other embodiments, A blocks and B blocks are randomly distributed along the polymer chain. In other words, the block copolymers usually do not have a structure as follows: AAA-AA-BBB-BB. In an embodiment, the ethylene/α-olefin multi-block copolymer does not have a third type of block, which comprises different comonomer(s). In another embodiment, each of block A and block B has monomers or comonomers substantially randomly distributed within the block. In other words, neither block A nor block B comprises two or more sub-segments (or sub-blocks) of distinct composition, such as a tip segment, which has a substantially different composition than the rest of the block.

Ethylene comprises the majority mole fraction of the whole ethylene/α-olefin multi-block copolymer, i.e., ethylene comprises at least 50 wt % of the whole ethylene/α-olefin multi-block copolymer. More preferably, ethylene comprises at least 60 wt %, at least 70 wt %, or at least 80 wt %, with the substantial remainder of the whole ethylene/α-olefin multi-block copolymer comprising the C4-C8α-olefin comonomer. In an embodiment, the ethylene/α-olefin multi-block copolymer contains from 50 wt % to 90 wt % ethylene, or from 60 wt % to 85 wt % ethylene, or from 65 wt % to 80 wt % ethylene. For many ethylene/octene multi-block copolymers, the composition comprises an ethylene content greater than 80 wt % of the whole ethylene/octene multi-block copolymer and an octene content of from 10 wt % to 15 wt %, or from 15 wt % to 20 wt % of the whole multi-block copolymer.

The ethylene/α-olefin multi-block copolymer includes various amounts of “hard” segments and “soft” segments. “Hard” segments are blocks of polymerized units in which ethylene is present in an amount greater than 90 wt %, or 95 wt %, or greater than 95 wt %, or greater than 98 wt %, based on the weight of the polymer, up to 100 wt %. In other words, the comonomer content (content of monomers other than ethylene) in the hard segments is less than 10 wt %, or 5 wt %, or less than 5 wt %, or less than 2 wt %, based on the weight of the polymer, and can be as low as zero. In some embodiments, the hard segments include all, or substantially all, units derived from ethylene. “Soft” segments are blocks of polymerized units in which the comonomer content (content of monomers other than ethylene) is greater than 5 wt %, or greater than 8 wt %, greater than 10 wt %, or greater than 15 wt %, based on the weight of the polymer. In an embodiment, the comonomer content in the soft segments is greater than 20 wt %, greater than 25 wt %, greater than 30 wt %, greater than 35 wt %, greater than 40 wt %, greater than 45 wt %, greater than 50 wt %, or greater than 60 wt % and can be up to 100 wt %.

The soft segments can be present in an ethylene/α-olefin multi-block copolymer from 1 wt % to 99 wt % of the total weight of the ethylene/α-olefin multi-block copolymer, or from 5 wt % to 95 wt %, from 10 wt % to 90 wt %, from 15 wt % to 85 wt %, from 20 wt % to 80 wt %, from 25 wt % to 75 wt %, from 30 wt % to 70 wt %, from 35 wt % to 65 wt %, from 40 wt % to 60 wt %, or from 45 wt % to 55 wt % of the total weight of the ethylene/α-olefin multi-block copolymer. Conversely, the hard segments can be present in similar ranges. The soft segment weight percentage and the hard segment weight percentage can be calculated based on data obtained from DSC or NMR. Such methods and calculations are disclosed in, for example, U.S. Pat. No. 7,608,668, entitled “Ethylene/α-Olefin Block Inter-Polymers,” filed on Mar. 15, 2006, in the name of Colin L. P. Shan, Lonnie Hazlitt, et. al. and assigned to Dow Global Technologies Inc., the disclosure of which is incorporated by reference herein in its entirety. In particular, hard and soft segment weight percentages and comonomer content may be determined as described in column 57 to column 63 of U.S. Pat. No. 7,608,668.

The ethylene/α-olefin multi-block copolymer comprises two or more chemically distinct regions or segments (referred to as “blocks”) joined (or covalently bonded) in a linear manner, that is, it contains chemically differentiated units which are joined end-to-end with respect to polymerized ethylenic functionality, rather than in pendent or grafted fashion. In an embodiment, the blocks differ in the amount or type of incorporated comonomer, density, amount of crystallinity, crystallite size attributable to a polymer of such composition, type or degree of tacticity (isotactic or syndiotactic), regio-regularity or regio-irregularity, amount of branching (including long chain branching or hyper-branching), homogeneity or any other chemical or physical property. Compared to block interpolymers of the prior art, including interpolymers produced by sequential monomer addition, fluxional catalysts, or anionic polymerization techniques, the present ethylene/α-olefin multi-block copolymer is characterized by unique distributions of both polymer polydispersity (PDI or Mw/Mn or MWD), polydisperse block length distribution, and/or polydisperse block number distribution, due, in an embodiment, to the effect of the shuttling agent(s) in combination with multiple catalysts used in their preparation.

In an embodiment, the ethylene/α-olefin multi-block copolymer is produced in a continuous process and possesses a polydispersity index (Mw/Mn) from 1.7 to 3.5, or from 1.8 to 3, or from 1.8 to 2.5, or from 1.8 to 2.2. When produced in a batch or semi-batch process, the ethylene/α-olefin multi-block copolymer possesses Mw/Mn from 1.0 to 3.5, or from 1.3 to 3, or from 1.4 to 2.5, or from 1.4 to 2.

In addition, the ethylene/α-olefin multi-block copolymer possesses a PDI (or Mw/Mn) fitting a Schultz-Flory distribution rather than a Poisson distribution. The present ethylene/α-olefin multi-block copolymer has both a polydisperse block distribution as well as a polydisperse distribution of block sizes. This results in the formation of polymer products having improved and distinguishable physical properties. The theoretical benefits of a polydisperse block distribution have been previously modeled and discussed in Potemkin,Physical Review E(1998) 57 (6), pp. 6902-6912, and Dobrynin,J. Chem. Phvs. (1997) 107 (21), pp 9234-9238.

In an embodiment, the present ethylene/α-olefin multi-block copolymer possesses a most probable distribution of block lengths.

In a further embodiment, the ethylene/α-olefin multi-block copolymer of the present disclosure, especially those made in a continuous, solution polymerization reactor, possess a most probable distribution of block lengths. In one embodiment of this disclosure, ethylene/α-olefin multi-block copolymers are defined as having:(A) Mw/Mn from about 1.7 to about 3.5, at least one melting point, Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter, where in the numerical values of Tm and d correspond to the relationship:
Tm>−2002.9+4538.5(d)−2422.2(d)2, and/or(B) Mw/Mn from about 1.7 to about 3.5, and is characterized by a heat of fusion, ΔH in J/g, and a delta quantity, ΔT, in degrees Celsius defined as the temperature difference between the tallest DSC peak and the tallest Crystallization Analysis Fractionation (“CRYSTAF”) peak, wherein the numerical values of ΔT and ΔH have the following relationships:ΔT>−0.1299 ΔH+62.81 for ΔH greater than zero and up to 130 J/gΔT≥48° C. for ΔH greater than 130 J/g
wherein the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30° C.; and/or(C) elastic recovery, Re, in percent at 300 percent strain and 1 cycle measured with a compression-molded film of the ethylene/α-olefin interpolymer, and has a density, d, in grams/cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when ethylene/α-olefin interpolymer is substantially free of cross-linked phase:
Re>1481−1629(d); and/or(D) has a molecular fraction which elutes between 40° C. and 130° C. when fractionated using TREF, characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene/α-olefin interpolymer; and/or(E) has a storage modulus at 25° C., G′(25° C.), and a storage modulus at 100° C., G′(100° C.), wherein the ratio of G′(25° C.) to G′(100° C.) is in the range from 1:1 to 9:1.

The ethylene/α-olefin multi-block copolymer may also have:(F) a molecular fraction which elutes between 40° C. and 130° C. when fractionated using TREF, characterized in that the fraction has a block index of at least 0.5 and up to 1 and a molecular weight distribution, Mw/Mn, greater than 1.3; and/or(G) average block index greater than zero and up to 1.0 and a molecular weight distribution, Mw/Mn greater than 1.3.

It is understood that the ethylene/α-olefin multi-block copolymer may have one, some, all, or any combination of properties (A)-(G). Block Index can be determined as described in detail in U.S. Pat. No. 7,608,668 herein incorporated by reference for that purpose. Analytical methods for determining properties (A) through (G) are disclosed in, for example, U.S. Pat. No. 7,608,668, col. 31 line 26 through col. 35 line 44, which is herein incorporated by reference for that purpose.

In an embodiment, the ethylene/α-olefin multi-block copolymer has hard segments and soft segments, is styrene-free, consists of only (i) ethylene and (ii) a C4-C8α-olefin (and optional additives), and is defined as having a Mw/Mn from 1.7 to 3.5, at least one melting point, Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter, wherein the numerical values of Tm and d correspond to the relationship:
Tm>−2002.9+4538.5(d)−2422.2(d)2,
where the density, d, is from 0.850 g/cc, or 0.860 g/cc, or 0.870 g/cc to 0.875 g/cc, or 0.877 g/cc, or 0.880 g/cc, or 0.890 g/cc; and the melting point, Tm, is from 110° C., or 115° C., or 120° C. to 125° C., or 130° C., or 135° C.

In an embodiment, the ethylene/α-olefin multi-block copolymer is an ethylene/1-octene multi-block copolymer (consisting only of ethylene and octene comonomer) and has one, some, or all of the following properties:(i) a Mw/Mn from 1.7, or 1.8 to 2.2, or 2.5, or 3.5; and/or(ii) a density from 0.860 g/cc, or 0.865 g/cc, or 0.870 g/cc, or 0.877 g/cc, or 0.880 g/cc; and/or(iii) a melting point, Tm, from 115° C., or 118° C., or 119° C., or 120° C. to 120° C., or 123° C., or 125° C.; and/or(iv) a melt index (MI) from 0.1 g/10 min, or 0.5 g/10 min to 1.0 g/10 min, or 2.0 g/10 min, or 5 g/10 min, or 10 g/10 min; and/or(v) 50-85 wt % soft segment and 40-15 wt % hard segment; and/or(vi) from 10 mol %, or 13 mol %, or 14 mol %, or 15 mol % to 16 mol %, or 17 mol %, or 18 mol %, or 19 mol %, or 20 mol % C4-C12α-olefin in the soft segment; and/or(vii) from 0.5 mol %, or 1.0 mol %, or 2.0 mol %, or 3.0 mol % to 4.0 mol %, or 5 mol %, or 6 mol %, or 7 mol %, or 9 mol % octene in the hard segment; and/or(viii) an elastic recovery (Re) from 50%, or 60% to 70%, or 80%, or 90%, at 300% 300% min1deformation rate at 21° C. as measured in accordance with ASTM D 1708; and/or(ix) a polydisperse distribution of blocks and a polydisperse distribution of block sizes.

In an embodiment, the ethylene/α-olefin multi-block copolymer is an ethylene/octene multi-block copolymer. The ethylene/octene multi-block copolymer is sold under the tradename INFUSE™, available from The Dow Chemical Company, Midland, Michigan, USA.

The ethylene/α-olefin multi-block copolymers can be produced via a chain shuttling process such as described in U.S. Pat. No. 7,858,706, which is herein incorporated by reference. In particular, suitable chain shuttling agents and related information are listed in col. 16 line 39 through col. 19 line 44. Suitable catalysts are described in col. 19 line 45 through col. 46 line 19 and suitable co-catalysts in col. 46 line 20 through col. 51 line 28. The process is described throughout the document, but particularly in col. 51 line 29 through col. 54 line 56. The process is also described, for example, in the following: U.S. Pat. Nos. 7,608,668; 7,893,166; and 7,947,793.

The ethylene/α-olefin multi-block copolymer may comprise two or more embodiments disclosed herein.

In an embodiment, the backing layer has a thickness from 1 μm to 30 μm, or from 5 μm to 25 μm.

In an embodiment, the backing layer has a thickness from 1 μm to 30 μm, or from 5 μm to 25 μm, or from 1 μm to 20 μm, or from 2 μm to 18 μm, or from 3 μm to 16 μm, or from 3 μm to 14 μm, or from 5 μm to 12 μm, or from 6 μm to 10 μm, or from 7 μm to 12 μm, or from 8 μm to 14 μm, or from 9 μm to 16 μm, or from 10 μm to 15 μm, or from 12 μm to 20 μm, or from 14 μm to 25 μm.

In an embodiment, the backing layer has a thickness from 10 μm to 25 μm, or from 14 μm to 25 μm.

The flexible multilayer film includes a tie layer. The tie layer is in direct contact with a backing layer. The flexible multilayer film may include more than one tie layer.

The tie layer may be composed of one or more polymeric materials. Nonlimiting examples of suitable polymeric materials for tie layer include functionalized ethylene-based polymers such as ethylene-vinyl acetate (EVA) copolymer; polymers with maleic anhydride-grafted to polyolefins such as any polyethylene, ethylene-copolymers, or polypropylene; ethylene acrylate copolymers such an ethylene methyl acrylate (EMA); glycidyl containing ethylene copolymers; propylene and ethylene based olefin block copolymers such as INFUSE™ (ethylene-based Olefin Block Copolymers available from the Dow Chemical Company) and INTUNE™ (PP-based Olefin Block Copolymers available from The Dow Chemical Company); and low density polyethylene (LDPE) resins such Dowlex™ GM 8070 (polyethylene resin available from the Dow Chemical Company) and LDPE 132i (low density polyethylene resin available from the Dow Chemical Company); anhydride-modified, linear low-density polyethylene (LLDPE) such as BYNEL™ 41E70 (linear low density polyethylene resin available from Dow Chemical Company and blends thereof.

The tie layer has a thickness from 1 μm to 20 μm, or from 2 μm to 18 μm, or from 3 μm to 16 μm, or from 3 μm to 14 μm, or from 5 μm to 12 μm, or from 6 μm to 10 μm.

In an embodiment, the tie layer has a thickness from 5 μm to 12 μm.

In an embodiment, the flexible multilayer film includes a barrier layer. The barrier layer is in direct contact with the tie layer. The flexible multilayer film includes one barrier layer or more than one barrier layer.

Nonlimiting examples of suitable materials for the barrier layer include one or more polyamides (nylons), ethylene vinyl alcohol copolymers (EVOH), polyvinylidene chloride, polyamide, or combination of two or more thereof and can include a scavenger materials and compounds of heavy metals like cobalt with MXD6 nylon.

The barrier layer has a thickness from 1 μm to 20 μm, or from 2 μm to 18 μm, or from 3 μm to 16 μm, or from 3 μm to 14 μm, or from 5 μm to 12 μm, or from 6 μm to 10 μm, or from 7 μm to 12 μm, or from 8 μm to 14 μm, or from 9 μm to 16 μm, or from 10 μm to 18 μm, or from 10 μm to 20 μm, or from 10 μm to 25 μm.

In an embodiment, the barrier layer has a thickness of from 8 μm to 14 μm.

The flexible multilayer film includes an outer layer which is the furthest layer from the seal layer. In an embodiment, the flexible multilayer film may include one or more inner layers disposed between the seal layer and the outer layer. The outer layer may be composed of one or more polymeric materials. Nonlimiting examples of suitable polymeric material for the outer layer include those used to make biaxially or monoaxially oriented films for lamination as well as coextruded films. Nonlimiting polymeric material for the outer layer include biaxially oriented polyethylene terephthalate (OPET), monoaxially oriented nylon (MON), biaxially oriented nylon (BON), biaxially oriented polypropylene (BOPP), and biaxially or monoaxially oriented polyethylene (BOPE and MDO PE). Other polymeric materials useful in constructing film layers for structural benefit are polypropylenes (such as propylene homopolymer, random propylene copolymer, propylene impact copolymer, thermoplastic polypropylene (TPO) and the like, propylene-based plastomers (e.g., VER-SIFY™ or VISTAMAX™)), polyamides (such as Nylon 6; Nylon 6,6; Nylon 6,66; Nylon 6,12; Nylon 12; etc.), polyethylene norbornene, cyclic olefin copolymers, polyacrylonitrile, polyesters, copolyesters (such as polyethylene terephthlate (PET)), cellulose esters, polyethylene and copolymers of ethylene (e.g., LLDPE based on ethylene octene copolymer such as DOWLEX™), blends thereof, and multilayer combinations thereof.

The outer layer has a thickness from 1 μm to 20 μm, from 2 μm to 18 μm, from 3 μm to 16 μm, from 4 to 14 μm, from 5 μm to 12 μm, from 6 μm to 10 μm, from 7 μm to 11 μm, from 8 μm to 12 μm, from 9 μm to 12 μm, 10 μm to 13 μm, and from 11 μm to 14 μm; and from 12 μm to 15 μm.

In an embodiment, the outer layer thickness is from 12 μm to 15 μm.

The flexible multilayer film may include additional layers which may contribute to the structural integrity or provide specific properties. The additional layers may be added by direct means (coextrusion, for example) or by using appropriate tie layers to the adjacent polymer layers. Polymers which may provide additional performance benefits such as stiffness, toughness or opacity, as well polymers which may offer gas barrier properties or chemical resistance can be added to the structure.

The present flexible multilayer film has 3, or 4, or 5, of 6, or 7, or 8, or 9, or 10, or 11, or more layers. Nonlimiting examples of layer structures for the present multilayer flexible film are provided below wherein “/” represents layer interface:seal/backing/tie/barrier/tie/outer,seal/backing/tie/barrier/tie/barrier/tie/outer,seal/backing/tie/barrier/barrier/tie/outer,seal/backing/tie/barrier/tie/barrier/barrier/tie/outer, andseal/backing/tie/barrier/tie/inner/outer

The present disclosure provides another flexible multilayer film. In an embodiment, the flexible multilayer film has at least three layers. The flexible multilayer film includes a seal layer and a backing layer. The seal layer includes an ionomer. The backing layer is in direct contact with the seal layer. The backing layer includes a first ethylene composition which comprises at least one ethylene-based polymer, having (i) a molecular weighted comonomer distribution index (TMWCDI″) value greater than 1.2 and (ii) a melt index ratio (I10/I2) that meets the following equation: I10/I2≥7.0−1.2×log (I2) (hereafter referred to as “first composition 1”).

The flexible multilayer film has the layer structure/composition of any flexible multilayer film previously disclosed herein and includes first composition 1 in the backing layer, alone, or in combination with, the ethylene/α-olefin multi-block copolymer.

First composition 1 contains two-ethylene-octene copolymers. First composition 1 is prepared, via solution polymerization, in a dual series loop reactor system according to International Patent Publication No. WO2019/005930, filed on 27 Jun. 2018, the entire content of which is incorporated by reference herein.

In an embodiment, first composition 1 includes one, some, or all of the following properties:(i) a density from 0.910 g/cc to 0.920 g/cc; and/or(ii) I2from 0.5 g/10 min to 1.0 g/10 min; and/or(iii) I10/I2from 8.0 to 8.5; and/or(iv) MWCDI from 2.5 to 3.0.

In an embodiment, first composition 1 has the properties in Table A below.

TABLE AProperties of First Composition 1PropertiesUnitFirst Composition 1Densityg/cc0.9117I2g/10 min0.86I10/I28.147.0 − 1.2 × log(I2)7.08Mn (conv. gpc)g/mol30,406Mw (conv. gpc)115,271Mz (conv. gpc)273,416Mw/Mn (conv. gpc)3.79Mz/Mw (conv. gpc)2.37Eta* (0.1 rad/s)Pa · s11,139Eta* (1.0 rad/s)Pa · s8,215Eta* (10 rad/s)Pa · s4,704Eta* (100 rad/s)Pa · s1,715Eta*0.1/Eta*1006.5Eta zeroPa · s13568MWCDI2.86VinylsPer 1000 totalNot MeasuredCarbonsZSVR2.0

In an embodiment, the flexible multilayer film includes a seal layer composed of a metal ionomer and a backing layer in direct contact with the seal layer, the backing layer composed of first composition 1. The flexible multilayer film includes a tie layer in direct contact with the backing layer. The tie layer can be any tie layer as previously disclosed herein. The flexible multilayer film includes a barrier layer in direct contact with the tie layer. The barrier layer can be any barrier layer as previously disclosed herein. The seal layer, backing layer, tie layer, and barrier layer have the same respective thickness as previously disclosed herein for the flexible multilayer film having backing layer composed of an ethylene/α-olefin multi-block copolymer.

In an embodiment, the backing layer is composed of a sole polymer material, namely first composition 1.

2. Flexible Pouch

The present disclosure provides a flexible pouch. In an embodiment, the flexible pouch includes opposing flexible multilayer films superimposed on one another so as to define a common peripheral edge. Each flexible multilayer film has at least three layers. Each flexible multilayer film includes a seal layer and a backing layer. The seal layer includes an ionomer. The backing layer is in direct contact with the seal layer. The backing layer includes an ethylene/α-olefin multi-block copolymer and/or first composition 1. The flexible pouch includes a peripheral seal extending along at least a portion of the common peripheral edge. The peripheral seal forms a closed flexible pouch having a storage compartment.

Each flexible multilayer film is any flexible multilayer flexible film as previously disclosed herein (i.e., multilayer film having at least three layers with ionomer seal layer and ethylene/α-olefin multi-block copolymer and/or first composition 1 backing layer). The structure and composition of each flexible multilayer film may be the same or may be different. The opposing flexible multilayer films may be two discrete, or two individual films, superimposed on each other. Alternatively, the opposing flexible multilayer films are two different portions of the same film, or single film, wherein the single film is folded so that portions of the single film oppose each other so that the seal layers oppose each other.

The opposing flexible multilayer films are superimposed on each other and form the common peripheral edge. The common peripheral edge defines a perimeter shape for the flexible pouch. The perimeter shape for the flexible pouch can be a polygon (such as triangle, square, rectangle, diamond, pentagon, hexagon, heptagon, octagon, etc.) or an ellipse (such as an ovoid, an oval, or a circle).

A peripheral seal extends along at least a portion of the common peripheral edge to form a storage compartment within the flexible pouch. In an embodiment, the peripheral seal extends along the entire common peripheral edge. The peripheral seal forms a storage compartment within the flexible pouch.

The peripheral seal seals, or otherwise adheres, flexible multilayer film to flexible multilayer film. The peripheral seal is formed by way of ultrasonic seal, heat seal, adhesive seal, and combinations thereof. The peripheral seal includes opposing seal layers (opposing ionomer layers) of each flexible multilayer film, in direct contact with each other.

In an embodiment, the peripheral seal is formed by way of a heat sealing procedure. The term “heat sealing,” as used herein, is the act of placing two or more films of polymeric material between opposing heat seal bars, the heat seal bars moved toward each other, sandwiching the films, to apply heat and pressure to the films such that opposing interior surfaces (seal layers) of the films contact, melt, and form a heat seal, or a weld, to attach the films to each other. Heat sealing includes suitable structure and mechanism to move the seal bars toward and away from each other in order to perform the heat sealing procedure.

The peripheral seal has a seal strength from 9 N/25.4 mm to 25 N/25.4 mm, or from 12 N/25.4 mm to 20 N/25.4 mm.

The opposing seal layers can also be corona treated to improve wettability and adhesion to the comestible packaged inside.

In an embodiment, the flexible pouch includes a comestible in the storage compartment. The comestible is in direct contact with one, or both, of the opposing seal layers (ionomer). The comestible may be a solid substance and/or a liquid substance. Nonlimiting examples of suitable liquid comestibles include sauces, condiments (ketchup, mustard, mayonnaise), butter, and baby food. Nonlimiting examples of suitable solid comestibles include powders, grains, meat, granular solids, animal feed, and pet food, cooked ham, cured meats, etc.

Applicant discovered that the combination of (i) the backing layer composed of a single polymer (not a polymer blend) that is the ethylene/α-olefin multi-block copolymer (and/or first composition 1) (ii) in direct contact (iii) with the seal layer that is metal ionomer (and zinc ionomer in particular) unexpectedly results in an increased seal strength of the peripheral seal to prevent leaking or damage during the cooking process. The increase in seal strength advantageously enables the production of multilayer films with thinner backing layer (ethylene/α-olefin multi-block copolymer and/or first composition 1) and/or thinner seal layer (ionomer).

By way of example, and not limitation, some embodiments of the present disclosure will now be described in detail in the following Examples.

EXAMPLES

Materials used in the examples are provided in Table 2 below.

TABLE 2Material/DescriptionPropertiesSourceINFUSE ™ 9000ethylene/octene multi-block copolymerThe Dow Chemical Co.d = 0.877 g/cc; Tm= 120° C.;I2 = 0.5 g/10 minINFUSE ™ 9130.05ethylene/octene multi-block copolymerThe Dow Chemical Co.d = 0.888 g/cc; Tm= 120° C.I2 = 1.5 g/10 minINFUSE ™ 9100ethylene/octene multi-block copolymerThe Dow Chemical Co.d = 0.877 g/cc; Tm= 121° C.I2 = 0.5 g/10 minfirst composition 1ethylene/octene copolymerThe Dow Chemical Co.d = 0.9117 g/cc; Tm= 123° C.I2= 0.86 g/10 minI10/I2= 8.14MWCDI = 2.86Versify ™ 2000Propylene-ethylene copolymerThe Dow Chemical Co.d = 0.888 g/cc; Tm=I2 = 2 g/10 minDOWLEX ™ GM 8070Polyethylene resinThe Dow Chemical Co.(GM 8070)d = 0.917 g/cc; Tm= 123° C.I2 = 0.9 g/10 minBYNEL ™ 41E687Anhydride-modified, linear low-densityThe Dow Chemical Co.polyethylene (LLDPE) resind = 0.91 g/cc; Tm= 119° C.I2 = 1.7 g/10 minSURLYN ™ 1650a zinc salt of ethylene and methacrylicThe Dow Chemical Co.(SUR 1650)acid copolymerd = 0.94 g/cc; Tm= 97° C.I2 = 1.8 g/10 minLDPE 132ILow density polyethylene resinThe Dow Chemical Co.(132i)d = 0.921 g/cc; Tm= 110° C.I2 = 0.25 g/10 minATTANE ™ 4203Ultra low density polyethylene resinThe Dow Chemical Co.d = 0.905 g/cc; Tm= 123° C.I2 = 0.8 g/10 minPAPolyamide - copolyamide 6/66 grade of highviscosityd = 1.12 g/cc; Tm = 194° C.Viscosity Measurement: 3.87 to 4.17BASF - Ultramid C40EVOHEthylene vinyl alcohol - 38%d = 1.17 g/cc; Tm = 173° C.I2 = 4.0 g/10 min (210° C./2160 g)NIPPON GOHSEI - Sarnol ET3803RBPPPolypropylene-based polymer - homopolymerd = 0.905 g/cc; Tm = 148° C.I2 = 7.5 g/10 minBRASKEM PP H401Mor-free ™ 980Polyurethane adhesiveThe Dow Chemical Co.d = 1.14 g/ccElite ™ 5401G (5401)Polyethylene resinThe Dow Chemical Co.d = 0.918 g/cc; Tm = 123° C.I2 = 18/10 min

Example 1—Preparation of Film 1

A Dr. Colin blown film coextruder was used with a seven layer line and a die of 60 mm diameter to produce the seven layer film described in Table 3. The blown film coextruder has a blow-up ratio of 2.5. A PET outer layer is subsequently laminated to the seven layer top film. The top film is laminated to the PET outer layer via an adhesive layer. The PET outer layer is 12 microns thick. The adhesive layer is 3 microns thick and made of Morfree 980/CR 137.

The composition and structure of Film 1 (top film without PET laminate) are shown in Table 3 below.

TABLE 3Comparative 1aComparative 2bInventive 1aInventive 2aThick.Thick.Thick.Thick.LayerLayer Comp.(μm)Layer Comp.(μm)Layer Comp.(μm)Layer Comp.(μm)120% 132i +2020% 132i +2020% 132i +2020% 132i +2080% GM 807080% GM 807080% GM 807080% GM 8070220% 132i +20Attane ™420320First20Infuse 9130.052050% GM 8070 +composition 130% 54013Tie layer5Tie layer5Tie layer5Tie layer54 (Barrier)EVOH10EVOH10EVOH10EVOH105 (Tie)Tie layer5Tie layer5Tie layer5Tie layer56 (Backing)BYNEL 41E68720Attane ™420320First20Infuse 9130.0520composition 17 (Seal)SUR 165010SUR 165010SUR 165010SUR 165010

Example 2—Preparation of Film 2

A Dr. Colin blown film coextruder was used with a seven layer line and a die of 60 mm diameter, to produce the seven layer film shown in table 4. The blown film coextruder has a blow-up ratio of 2.5.

The composition and structure of Film 2 (bottom film) are shown in Table 4 below.

TABLE 4Comparative 1bComparative 2bInventive 1bInventive 2bThick.Thick.Thick.Thick.LayerLayer Comp.(μm)Layer Comp.(μm)Layer Comp.(μm)Layer Comp.(μm)1PP40PP40PP40PP40220% 132i +15Attane ™ 420325First25Infuse 9130.052550% GM 8070 +composition 130% 54013Tie layer10tie layer10tie layer10tie layer104 (Barrier)PA25PA25PA25PA255 (Tie)tie layer10tie layer10tie layer10tie layer106 (Backing)BYNEL 41E68720Attane ™ 420325First25Infuse 9130.0525composition 17 (Seal)SUR 165030SUR 165015SUR 165015SUR 165015

Example 3—Pouch Preparation

Pouches for cook in applications are made using a thermoforming packaging line and a HSG-C Brugger Sealer with flat seal bars of 150 mm×5 mm covered with a Teflon tape in order to prevent the multilayer flexible films from sticking on the bar. Flexible pouches are prepared with one top film (from Table 3) and one bottom film (from Table 4) placed in opposing relation to each other to define a common peripheral edge, the top film and bottom film mated in the following pairs:Comparative 1a/comparative 1b—to form pouches Comp 2A and Comp 2B;Comparative 2a/comparative 2b—to form pouches Comp 3A and Comp 3B;Inventive 1a/inventive 1b—to form inventive pouches Inventive 2A and Inventive 2B; andInventive 2a/inventive 2b—to form inventive pouches Inventive 3A and inventive 3B.

Each flexible pouch is prepared by sealing the top film and the bottom film to each other so that the seal layers of each film are in direct contact with one another. The HSG-C Brugger Sealer (with flat seal bars of 150 mm—5 mm covered with a Teflon tape in order to prevent the film sticking on the bar) is used to form heat seals along the common peripheral edge of the top/bottom films. The pouches were tested over a range of heat sealing temperatures from 140° C. to 200° C., and heat sealing pressures 210 psi and 420 psi. Heat sealing dwell time is 0.5 seconds. Sealed films were cut into 25.4 mm width and pulled in a universal testing machine, following conditions described at ASTM F88. The results of the seal strength testing are shown in table 5, below.

TABLE 5Pressure 210psi/dwellComp -2AComp - 3AInventive - 2AInventive - 3Atime 0.5 s(N/25.4 mm)(N/25.4 mm)(N/25.4 mm)(N/25.4 mm)140° C.11.23.311.213.7160° C.10.83.28.915.3180° C.11.24.212.215.8200° C.10.93.513.612.5Pressure 420psi/dwellComp - 2BComp - 3BInventive - 2BInventive - 3Btime 0.5 s(N/25.4 mm)(N/25.4 mm)(N/25.4 mm)(N/25.4 mm)140° C.9.13.214.017.2160° C.10.52.015.119.1180° C.10.22.613.617.1200° C.10.02.414.614.6

Comparative flexible pouches, Comp 2A and Comp 2B, with thick seal layer in the bottom film (30 μm) show weaker seal strength at every heat seal condition when compared to inventive flexible pouches: Inventive 2A and Inventive 3B. Each inventive flexible pouch (Inventive 2A, 2B, 3A, 3B) has a thinner ionomer layer in the bottom film (15 μm) compared to 30 μm ionomer film layer for Comp 2A bottom film.

Inventive 2A/3A each exhibit stronger seal strength at every heat seal condition when compared to flexible pouch Comp 3A, having Attane™ 4203 as a backing layer.

Applicant discovered that a backing layer composed of a single polymeric material that is ethylene/α-olefin multi-block copolymer or first composition 1, in direct contact with a zinc ionomer seal layer surprisingly exhibits higher seal strength (12-20 N/25.4 mm) at the same, or thinner, ionomer seal layer thickness (10-15 μm) compared to films with thicker ionomer seal layer and/or conventional backing layer material.

It is specifically intended that the present disclosure not be limited to the embodiments and illustrations contained herein, but include modified forms of those embodiments including portions of the embodiments and combinations of elements of different embodiments as come within the scope of the following claims.