# US 11,992,990 B2 · Barrier-enhanced polymeric film structures, methods of preparation, and articles thereof

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- Number: US 11,992,990 B2
- Document ID: US11992990B2
- Status: Granted
- Kind: B2
- Application number: 17/402,908
- Filed: 2021-08-16
- Published: 2022-07-07
- Granted: 2024-05-28
- Earliest claimed: 2020-08-14
- Assignees: Superior Plastics Extrusion Co. Inc.
- Applicants: Superior Plastics Extrusion Co. Inc.
- Inventors: Jimmy A. Shah; Hari Parvatareddy
- Web page: https://patentgrep.com/patent/US11992990B2

## CPC

- B29C 48/022: {characterised by the choice of material}
- B29C 48/08: flexible, e.g. films
- B29C 48/21: the layers being joined at their surfaces
- B32B 5/18: characterised by features of a layer {of} foamed material
- B32B 7/12: using interposed adhesives or interposed materials with bonding properties
- B32B 27/065: {of foam}
- B32B 27/08: of synthetic resin
- B32B 27/18: characterised by the use of special additives
- B32B 27/306: {comprising vinyl acetate or vinyl alcohol (co)polymers}
- B32B 27/32: comprising polyolefins {(comprising vinyl (co)polymers or acrylic (co)polymers B32B27/30)}
- B32B 27/325: {comprising polycycloolefins}
- B32B 27/34: comprising polyamides
- B32B 27/36: comprising polyesters
- C08J 5/18: Manufacture of films or sheets
- C08L 23/08: Copolymers of ethene (C08L23/16 takes precedence)
- C08L 23/12: Polypropene
- C08L 67/00: Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain (of polyester-amides C08L77/12; of polyester-imides C08L79/08); Compositions of derivatives of such polymers
- C08L 77/00: Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain (of polyhydrazides C08L79/06; of polyamideimides or polyamide acids C08L79/08); Compositions of derivatives of such polymers
- B29K 2023/06: {PE, i.e. polyethylene}
- B29K 2023/086: {EVOH, i.e. ethylene vinyl alcohol copolymer}
- B29K 2023/12: {PP, i.e. polypropylene}
- B29K 2067/00: Use of polyesters {or derivatives thereof}, as moulding material
- B29K 2077/00: Use of {PA, i.e.} polyamides, e.g. polyesteramides {or derivatives thereof}, as moulding material
- B29K 2995/0065: Permeability to gases
- B29K 2995/0068: Permeability to liquids; Adsorption
- B29K 2995/0082: Flexural strength; Flexion stiffness
- B32B 2266/0278: Polyurethane
- B32B 2270/00: Resin or rubber layer containing a blend of at least two different polymers
- B32B 2307/54: Yield strength; Tensile strength
- B32B 2307/7244: Oxygen barrier
- B32B 2307/7246: Water vapor barrier
- B32B 2307/7376: Thickness
- B32B 2439/70: Food packaging
- B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00)
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- B29K: INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR {MOULDS, } REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS

## Abstract

This invention generally relates to polyethylene or ethylene/α-olefin copolymer based co-extruded, multi-layer films or sheets—rigid or flexible—for thermoforming into shaped containers such as packaging containers. Inter alia, the rigid films have improved barrier properties, toughness, and snapability. Particularly, the films of the present invention comprise one or more stacks of polypropylene layers. In one embodiment, the polypropylene layers in the stack are provided such that any two adjacent layers have different microstructures that provide a interface or interphase between the two layers with likely different microstructures and/or crystallinity. The overall polypropylene stack structure assists in disrupting the transport of oxygen, thereby providing a laminate or structure, for example a rigid film or sheet, with enhanced oxygen-barrier properties. The invention also relates a process for preparing shaped articles such as containers from such films, and to such shaped articles—rigid or flexible—both filled and unfilled.

## Claims

### Claim 1

A co-extruded multi-layer polymeric film, comprising at least one 2-layer stack A-B1, wherein the first layer of the 2-layer stack is A and the second layer of the 2-layer stack is B1, wherein:
A is a layer comprising predominately polypropylene,
B1 is a layer comprising predominately polypropylene and 50 wt. % or less of a hydrocarbon resin; and
wherein said two layers in said 2-layer stack are contactably adjacent each other; and
wherein the co-extruded multi-layer polymeric film comprises:
(I) an outside layer comprising polyethylene;
(II) a core layer comprising EVOH; and
(III) an inside layer comprising polyethylene;
wherein the outside layer and the inside layer comprise at least one 2-layer stack A-B1 .

### Claim 2 (depends on 1)

The co-extruded multi-layer polymeric film as recited in claim 1, further comprising one layer from the following set of layers, or more than one layer from the following set of layers:
(A) at least one layer comprising predominately polyolefin;
(B) at least one layer comprising predominately polypropylene;
(D) at least one layer comprising predominately polypropylene and 50 wt. % or less of a hydrocarbon resin;
(E) at least one layer comprising predominately polyethylene polymer or interpolymer;
(F) at least one barrier layer comprising EVOH;
(G) at least one barrier layer comprising predominately nylon;
(H) at least one barrier layer, comprising predominately polyester;
(I) at least one tie layer; and
(J) a combination of the above layers.

### Claim 3 (depends on 1)

The co-extruded multi-layer polymeric film as recited in claim 1, comprising three layers in the following order:
(I) a first layer comprising predominately polypropylene;
(II) a second layer comprising
predominately polypropylene and 50 wt. % or less of a hydrocarbon resin,
and
(III) a third layer comprising predominately polypropylene.

### Claim 4 (depends on 1)

A co-extruded multi-layer polymeric film, comprising:
(I) an outside layer stack, comprising one or more layers, wherein:
(A) optionally at least one layer of said outside layer stack comprises polyethylene polymer or polyethylene interpolymer; and
(B) optionally said outside layer stack comprises at least one 2-layer stack as recited in claim 1;
(II) a core layer stack comprising, one or more layers, wherein:
(C) optionally at least one layer of said core layer stack comprises polyethylene polymer or polyethylene interpolymer; and
(D) optionally said core layer stack comprises at least one 2-layer stack;
and
(E) optionally at least one layer of said core layer stack comprises EVOH;
and
(III) an inside layer stack, comprising one or more layers, wherein:
(F) optionally at least one layer of said inside layer stack comprises polyethylene polymer or polyethylene interpolymer; and
(G) optionally said inside layer stack comprises at least one 2-layer stack;
wherein said polyethylene interpolymer comprises:
(a) optionally a first ethylene/α-olefin copolymer fraction having a density in the range of 0.894 to 0.908 g/cm3; a melt index in the range of 0.2 to 1 dg/min; and
(b) optionally a second ethylene/α-olefin copolymer fraction having a density in the range of from about 0.910 to 0.924 g/cm3, a melt index in the range from 0.5 to 2 g/10 min, a zero shear viscosity ratio (ZSVR) in the range of from about 1.15 to 2.5; a molecular weight distribution, expressed as the ratio of the weight average molecular weight to number average molecular weight (Mw/Mn), in the range of 2.0 to 4.0.

### Claim 5 (depends on 1)

The co-extruded multi-layer polymeric film of claim 1, comprising a number of layers selected from the range of 2 layers through 100 layers.

### Claim 6 (depends on 1)

The co-extruded multi-layer polymeric film of claim 1, wherein the weight percent of said EVOH copolymer to that of said co-extruded multi-layer polymeric film is in the range of from about 0.1% to about 10%.

### Claim 7 (depends on 6)

The co-extruded multi-layer polymeric film of claim 6, wherein the mole percent of ethylene in said EVOH copolymer is in the range of from about 10% to about 55%.

### Claim 8 (depends on 1)

The co-extruded multi-layer polymeric film as recited in claim 1, wherein the co-extruded multi-layer polymeric film exhibits a DTUL of 30° C. or more and a flexural secant modulus of 500 MPa or more.

### Claim 9 (depends on 1)

The co-extruded multi-layer polymeric film as recited in claim 1, wherein the thickness of the film ranges from about 5 μm to about 1600 μm.

### Claim 10 (depends on 1)

The co-extruded multi-layer polymeric film as recited in claim 1, wherein the hydrocarbon resin in the second layer B1 comprises an aliphatic hydrocarbon resin, an aliphatic/aromatic hydrocarbon resin, an aromatic hydrocarbon resin, a polyterpene resin, a terpene-phenol resin, a rosin ester, a rosin acid, or a mixture thereof.

### Claim 11 (depends on 1)

The co-extruded multi-layer polymeric film as recited in claim 1, wherein the hydrocarbon resin in the second layer B1 is partially hydrogenated or fully hydrogenated.

### Claim 12 (depends on 1)

The co-extruded multi-layer polymeric film as recited in claim 1, wherein the hydrocarbon resin in the second layer B1 comprises a polycyclopentadiene.

### Claim 13 (depends on 1)

The co-extruded multi-layer polymeric film as recited in claim 1, wherein the hydrocarbon resin in the second layer B1 has a weight average molecular weight of from about 400 g/mol to about 5,000 g/mol.

### Claim 14 (depends on 1)

The co-extruded multi-layer polymeric film as recited in claim 1, wherein the hydrocarbon resin comprises an aromatic C9 hydrogenated resin having a ring and ball softening point of 110° C. or more.

### Claim 15 (depends on 1)

The co-extruded multi-layer polymeric film as recited in claim 1, which is characterized by a water vapor transmission rate of 3.0 cm3/m2/day, or less, and/or an oxygen transmission rate of 60 cm3/100 in2/day, or less.

### Claim 16 (depends on 1)

The co-extruded multi-layer polymeric film as recited in claim 1, wherein the second layer B1 further comprises a nucleating agent selected from sodium benzoate, talc, glycerol alkoxide salts, cyclic carboxylic acid salts, bicyclic carboxylic acid salts, glycerolates, phosphines, phosphates, diols, hexahydrophtalic acid salts, amides, and sugar alcohols.

### Claim 17 (depends on 16)

The co-extruded multi-layer polymeric film as recited in claim 16, wherein said nucleating agent is selected from:
mannitol or mannitol based compounds; sorbitol or sorbitol based compounds;
nonitol or nonitol based compounds, 1,2,3-trideoxy-4,6:5,7-bis-O-((4-propylphenyl) methylene) nonitol;
2,4,8,10-tetra(tert-butyl)-6-hydroxy-12H-dibenzo[d,g][1,3,2]diox-aphosphocin 6-oxide; a salt of 2,4,8, 10-tetra(tert-butyl)-6-hydroxy-12H-dibenzo[d,g][1,3,2]diox-aphosphocin 6-oxide; sodium salt of 2,4,8,10-tetra(tert-butyl)-6-hydroxy-12H-dibenzo[d,g][1,3,2]diox-aphosphocin 6-oxide; hydroxy-bis[2,2′-methylenebis[4,6-di(tert-butyl)phenyl]phosphate; 2,2′-methylenebis(4,6-di-tert-butylphenyl)phosphate;
a salt thereof; a sodium salt thereof; an aluminum salt thereof; a lithium salt thereof;
(1R)-1-[(4R,4aR,8aS)-2,6-bis(3,4-dimethylphenyl)-4,4a,8,8a-tetrahydro-[1,−3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol; 1-[8-propyl-2,6-bis(4-propylphenyl)-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol; N-[3,5-bis(2,2-dimethylpropanoylamino)phenyl]-2,2-dimethylpropanamide); a salt of (1S,2R)-cyclohexane-1,2-dicarboxylate with zinc octadecenoate; a calcium salt of (1S,2R)-cyclohexane-1,2-dicarboxylate with zinc octadecenoate; cis-endo-bicyclo [2,2, 1]heptane-2,3-dicarboxylic acid disodium salt with 13-docosenamide;
amorphous silicon dioxide;
bicycloheptane dicarboxylic acid; bicyclo [2.2.1] heptane dicarboxylate;
cyclohexanedicarboxylic acid; a calcium salt of cyclohexanedicarboxylic acid; a blend of cyclohexanedicarboxylic acid, the calcium salt of cyclohexanedicarboxylic acid, and zinc stearate; and
a mixture of two or more nucleating agents thereof.

### Claim 18 (depends on 1)

A shaped polymeric article comprising the co-extruded multi-layer polymeric film of claim 1.

### Claim 19 (depends on 18)

The shaped polymeric article of claim 18, wherein the shaped polymeric article is a thermoformed shaped polymeric article.

### Claim 20 (depends on 18)

The shaped polymeric article of claim 18, which is a container for packaging food product.

### Claim 21 (depends on 20)

The container as recited in claim 20, wherein, the co-extruded multi-layer polymeric film further comprises one layer from the following set of layers, or more than one layer from the following set of layers:
(A) at least one layer comprising predominately polyolefin;
(B) at least one layer comprising predominately polypropylene;
(D) at least one layer comprising predominately polypropylene and 50 wt. % or less of a hydrocarbon resin;
(E) at least one layer comprising predominately polyethylene polymer or interpolymer;
(F) at least one barrier layer comprising EVOH;
(G) at least one barrier layer comprising predominately nylon;
(H) at least one barrier layer, comprising predominately polyester;
(I) at least one tie layer; and
(J) a combination of the above layers.

### Claim 22 (depends on 20)

The container as recited in claim 20, wherein the co-extruded multi-layer polymeric film comprises three layers in the following order:
(I) a first layer comprising predominately polypropylene;
(II) a second layer comprising:
predominately polypropylene and 50 wt. % or less of a hydrocarbon resin,
and
(III) a third layer comprising predominately polypropylene.

### Claim 23 (depends on 1, 20)

The container as recited in claim 20, wherein the co-extruded multi-layer polymeric film comprises:
(I) an outside layer stack, comprising one or more layers, wherein:
(A) optionally at least one layer of said outside layer stack comprises polyethylene polymer or polyethylene interpolymer; and
(B) optionally said outside layer stack comprises at least one 2-layer stack as recited in claim 1;
(II) a core layer stack comprising, one or more layers, wherein:
(C) optionally at least one layer of said core layer stack comprises polyethylene polymer or polyethylene interpolymer; and
(D) optionally said core layer stack comprises at least one 2-layer stack;
and
(E) optionally at least one layer of said core layer stack comprises EVOH;
and
(III) an inside layer stack, comprising one or more layers, wherein:
(F) optionally at least one layer of said inside layer stack comprises polyethylene polymer or polyethylene interpolymer; and
(G) optionally said inside layer stack comprises at least one 2-layer stack;
wherein said polyethylene interpolymer comprises:
(a) optionally a first ethylene/α-olefin copolymer fraction having a density in the range of 0.894 to 0.908 g/cm3; a melt index in the range of 0.2 to 1 dg/min; and
(b) optionally a second ethylene/α-olefin copolymer fraction having a density in the range of from about 0.910 to 0.924 g/cm3, a melt index in the range from 0.5 to 2 g/10 min, a zero shear viscosity ratio (ZSVR) in the range of from about 1.15 to 2.5; a molecular weight distribution, expressed as the ratio of the weight average molecular weight to number average molecular weight (Mw/Mn), in the range of 2.0 to 4.0.

### Claim 24 (depends on 20)

The container as recited in claim 20, wherein the co-extruded multi-layer polymeric film comprises a number of layers selected from the range of 2 layers through 100 layers.

### Claim 25 (depends on 21)

The container as recited in claim 21, wherein the weight percent of said EVOH copolymer to that of said co-extruded multi-layer polymeric film is in the range of from about 0.1% to about 10%.

### Claim 26 (depends on 25)

The container as recited in claim 25, wherein the mole percent of ethylene in said EVOH copolymer is in the range of from about 10% to about 55%.

### Claim 27 (depends on 1)

A process for preparing a co-extruded multi-layer polymeric film as recited in claim 1, comprising the steps of:
(I) providing the layer A, and
(II) providing the layer comprising B1 ;
wherein said A and said B1 form an interface or interphase at their adjacent boundaries such that the interphase provides discontinuity in properties between the two layers to provide improvement in barrier properties of the co-extruded multi-layer polymeric film.

### Claim 28 (depends on 27)

A container for packaging food product prepared from a rigid co-extruded multi-layer polymeric film prepared by the process of claim 27.

### Claim 29 (depends on 17)

A shaped polymeric article comprising the co-extruded multi-layer polymeric film of claim 17.

### Claim 30 (depends on 29)

The shaped polymeric article of claim 29, wherein the shaped polymeric article is a thermoformed shaped polymeric article.

### Claim 31

A laminated structure comprising a co-extruded multi-layer polymeric film, the polymeric film comprising at least one 2-layer stack A-B1, wherein:
the first layer of the 2-layer stack is A and the second layer of the 2-layer stack is B1 ;
A is a layer comprising predominately polypropylene;
B1 is a layer comprising predominately polypropylene and 50 wt. % or less of a hydrocarbon resin;
said two layers in said 2-layer stack are contactably adjacent each other; and
wherein the laminate structure thickness is in the range of 5 μm to 1600 μm.