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US 2025/0360698 A1Published application
High-Shrink, High-Strength Packaging Article Exhibiting Directional Tear
AssigneeCryovac, Inc.
InventorsAshley Wynne, Kelly Ahlgren, Miles Johnston, Rebecca Higginbotham
Life of this patent
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Abstract
A heat-shrinkable film having a total free shrink at 85° C. of at least 90%. The film has an inside seal layer, an outside polyester layer, and an inner oxygen barrier layer. A portion of the film contains a crosslinked polymer network. At least one film layer comprises an incompatible polymer blend. The film has an instrumented impact energy-to-break of at least 0.65J/mil, and/or an instrumented impact peak load strength of at least 66 Newtons/mil, and/or Truburst strength of at least 8 psi/mil.
Claims20
1:
- A multilayer, heat-shrinkable film comprising:
- A) a first film portion comprises a first layer which is a first outer layer and which is an inside layer of the multilayer, heat-shrinkable film and which serves as a heat-seal layer, the first film portion comprising a cross-linked polymer network;
- B) a second film portion comprises (b)(i) a second layer which is a second outer layer and which comprises polyester, the second outer layer being an outside layer of the multilayer, heat-shrinkable film, and (b)(ii) a third layer which is an oxygen barrier layer comprising at least one member selected from the group consisting of polyvinylidene chloride, saponified ethylene/vinyl acetate copolymer, polyamide, polyester, polypropylene, ethylene homopolymer, polyethylene naphthalate, polytrimethylene terephthalate, liquid crystal polymer, and O2-scavenger, the third layer being between the first layer and the second layer;
- C) the multilayer, heat-shrinkable film further comprises an ethylene/alpha-olefin plastomer having peak melt point of less than 90° C., the ethylene/alpha-olefin plastomer being present in the first film portion or the second film portion, the ethylene/alpha-olefin plastomer being present in the multilayer, heat-shrinkable film in an amount of at least 3 wt %, based on total film weight;
- D) the multilayer, heat-shrinkable film further comprises an incompatible polymer blend comprising at least one member selected from the group consisting of:
- (c)(i) a blend of from 90 to 30 wt % ethylene homopolymer and/or ethylene/alpha-olefin copolymer with from 10 to 70 wt % ethylene/unsaturated ester copolymer having an unsaturated ester content of at least 10 wt %,
- (c)(ii) a blend of ionomer resin with ethylene/unsaturated ester copolymer, and/or polybutylene, and/or propylene homopolymer and/or propylene copolymer,
- (c)(iii) a blend of homogeneous ethylene/alpha-olefin copolymer with recycled polymer blend comprising ethylene homopolymer, propylene homopolymer, ethylene copolymer, propylene copolymer, polyamide, ethylene/vinyl alcohol copolymer, ionomer resin, and anhydride-modified ethylene/alpha-olefin copolymer,
- (c)(iv) a blend of from 10 to 75 wt % ethylene/unsaturated ester copolymer with from 90 to 15 wt % polypropylene and/or propylene/ethylene copolymer, and/or polybutylene, and/or modified ethylene/alpha-olefin copolymer, and/or styrene homopolymer, and/or styrene/butadiene copolymer,
- (c)(v) a blend of ethylene/norbornene copolymer with ethylene/unsaturated ester copolymer and/or polypropylene and/or polybutylene,
- (c)(vi) a blend of from 90 to 15 wt % ethylene/alpha-olefin copolymer with from 10 to 75 wt % polypropylene and/or polybutylene and/or ethylene/norbornene,
- (c)(vii) a blend of from 90 to 25 wt % homogeneous propylene homopolymer and/or homogeneous propylene copolymer with from 10 to 75 wt % homogeneous ethylene/alpha-olefin copolymer and/or ethylene/unsaturated ester copolymer,
- (c)(viii) a blend of propylene homopolymer and/or propylene/ethylene copolymer and/or polybutylene with ethylene/methyl acrylate copolymer and/or ethylene/acrylic acid copolymer and/or ethylene/butyl acrylate copolymer,
- (c)(ix) a blend of polyamide with polystyrene and/or ethylene/alpha-olefin copolymer and/or ethylene/vinyl acetate copolymer and/or styrene/butadiene copolymer, and
- (c)(x) a blend of polyamide 6 and polyamide 6I6T,
- with the incompatible polymer blend being in the first film portion or the second film portion, the incompatible polymer blend being present in the multilayer, heat-shrinkable film in an amount of at least 10 wt %, on a total film weight basis;
- and
- the multilayer film has a total free shrink at 85° C. of at least 90% measured in accordance with ASTM D2732, and an instrumented impact energy-to-break of at least 0.65 J/mil, measured in accordance with ASTM D3763.
15 more elements
2:
- The multilayer, heat-shrinkable film according to claim 1, wherein the ethylene/alpha-olefin plastomer is present in the seal layer.
3:
- The multilayer, heat-shrinkable film according to claim 1, wherein the film has a total thickness, before shrinking, of from 1.3 mils to 2 mils.
4:
- The multilayer, heat-shrinkable film according to claim 1, wherein the multilayer film further comprises a tie layer between oxygen barrier layer and the outside layer, the tie layer comprising at least one member selected from the group consisting of anhydride-functional polyolefin, anhydride-functional ethylene/unsaturated acid copolymer, anhydride-functional olefin/unsaturated ester copolymer, cyclic olefin copolymer, acrylate-based polymer, polyurethane, styrene-based polymer.
5:
- The multilayer, heat-shrinkable film according to claim 1, wherein the crosslinked polymer network is formed by irradiating the first film portion at a level of from 30 to 120 kGy.
6:
- The multilayer, heat-shrinkable film according to claim 1, wherein the multilayer film exhibits a post-shrink specular gloss at 60 degrees of at least 110 gloss units, measured in accordance with ASTM D2457.
7:
- The multilayer, heat-shrinkable film according to claim 1, wherein the multilayer film exhibits a total free shrink at 85° C. of at least 95%, measured in accordance with ASTM D2732.
8:
- The multilayer, heat-shrinkable film according to claim 1, wherein the ethylene/alpha-olefin plastomer has a peak melting point of from 50° C. to 85° C.
9:
- The multilayer, heat-shrinkable film according claim 1, wherein the ethylene/alpha-olefin plastomer has a density ≤0.908 g/cc3.
10:
- The multilayer, heat-shrinkable film according to claim 1, wherein the multilayer film has an instrumented impact energy-to-break of at least 0.70 J/mil measured in accordance with ASTM D3763, and the ethylene/alpha-olefin plastomer has a melt index of ≤1.1 grams/10 min, measured in accordance with ASTM D1238.
11:
- The multilayer, heat-shrinkable film according to claim 1, wherein the multilayer, heat-shrinkable film is formed into a form-fill-seal packaging article having a fin seal running the length of the package and first and second end seals, with the form-fill-seal packaging article enclosing a product therein.
12:
- The multilayer, heat-shrinkable film according to claim 1, wherein the multilayer, heat-shrinkable film article has a patch adhered thereto, the patch comprising a patch film.
13:
- The multilayer, heat-shrinkable film according to claim 1, wherein the crosslinked polymer network has been strained by solid state orientation.
14:
- The multilayer, heat-shrinkable film according to claim 1, wherein the multilayer film comprises polyamide in an amount of from 0.1 to 10 wt %, based on total film weight.
15:
- The multilayer, heat-shrinkable film according to claim 1, wherein the multilayer film does not comprise polyamide.
16:
- A multilayer, heat-shrinkable film comprising:
- A) a first film portion comprises a first layer which is a first outer layer and which is an inside layer of the multilayer, heat-shrinkable film and which serves as a heat-seal layer, the first film portion comprising a cross-linked polymer network;
- B) a second film portion comprises (b)(i) a second layer which is a second outer layer and which comprises polyester, the second outer layer being an outside layer of the multilayer, heat-shrinkable film, and (b)(ii) a third layer which is an oxygen barrier layer comprising at least one member selected from the group consisting of polyvinylidene chloride, saponified ethylene/vinyl acetate copolymer, polyamide, polyester, polypropylene, ethylene homopolymer, polyethylene naphthalate, polytrimethylene terephthalate, liquid crystal polymer, and O2-scavenger, the third layer being between the first layer and the second layer;
- C) the multilayer, heat-shrinkable film further comprises an ethylene/alpha-olefin plastomer having peak melt point of less than 90° C., the ethylene/alpha-olefin plastomer being present in the first film portion or the second film portion, the ethylene/alpha-olefin plastomer being present in the multilayer, heat-shrinkable film in an amount of at least 3 wt %, based on total film weight;
- D) the multilayer, heat-shrinkable film further comprises an incompatible polymer blend comprising at least one member selected from the group consisting of:
- (c)(i) a blend of from 90 to 30 weight percent ethylene homopolymer and/or ethylene/alpha-olefin copolymer with from 10 to 70 weight percent ethylene/unsaturated ester copolymer having an unsaturated ester content of at least 10 weight percent,
- (c)(ii) a blend of ionomer resin with ethylene/unsaturated ester copolymer, and/or polybutylene, and/or propylene homopolymer and/or propylene copolymer,
- (c)(iii) a blend of homogeneous ethylene/alpha-olefin copolymer with recycled polymer blend comprising ethylene homopolymer, propylene homopolymer, ethylene copolymer, propylene copolymer, polyamide, ethylene/vinyl alcohol copolymer, ionomer resin, and anhydride-modified ethylene/alpha-olefin copolymer,
- (c)(iv) a blend of from 10 to 75 weight percent ethylene/unsaturated ester copolymer with from 90 to 15 weight percent polypropylene and/or propylene/ethylene copolymer, and/or polybutylene, and/or modified ethylene/alpha-olefin copolymer, and/or styrene homopolymer, and/or styrene/butadiene copolymer,
- (c)(v) a blend of ethylene/norbornene copolymer with ethylene/unsaturated ester copolymer and/or polypropylene and/or polybutylene,
- (c)(vi) a blend of from 90 to 15 weight percent ethylene/alpha-olefin copolymer with from 10 to 75 weight percent polypropylene and/or polybutylene and/or ethylene/norbornene,
- (c)(vii) a blend of from 90 to 25 weight percent homogeneous propylene homopolymer and/or homogeneous propylene copolymer with from 10 to 75 weight percent homogeneous ethylene/alpha-olefin copolymer and/or ethylene/unsaturated ester copolymer,
- (c)(viii) a blend of propylene homopolymer and/or propylene/ethylene copolymer and/or polybutylene with ethylene/methyl acrylate copolymer and/or ethylene/acrylic acid copolymer and/or ethylene/butyl acrylate copolymer,
- (c)(ix) a blend of polyamide with polystyrene and/or ethylene/alpha-olefin copolymer and/or ethylene/vinyl acetate copolymer and/or styrene/butadiene copolymer, and
- (c)(x) a blend of polyamide 6 and polyamide 6I6T,
- with the incompatible polymer blend being in the first film portion or the second film portion, the incompatible polymer blend being present in the multilayer, heat-shrinkable film in an amount of at least 10 wt %, on a total film weight basis;
- and
- the multilayer film has a total free shrink at 85° C. of at least 90% measured in accordance with ASTM D2732, and an instrumented impact peak load strength of at least 66 Newtons/mil, measured in accordance with ASTM D3763.
15 more elements
17:
- The multilayer, heat-shrinkable film according to claim 16, wherein the ethylene/alpha-olefin plastomer is present in the seal layer.
18:
- The multilayer, heat-shrinkable film according to claim 16, wherein the crosslinked polymer network has been strained by solid state orientation.
19:
- A multilayer, heat-shrinkable film comprising:
- A) a first film portion comprises a first layer which is a first outer layer and which is an inside layer of the multilayer, heat-shrinkable film and which serves as a heat-seal layer, the first film portion comprising a cross-linked polymer network;
- B) a second film portion comprises (b)(i) a second layer which is a second outer layer and which comprises polyester, the second outer layer being an outside layer of the multilayer, heat-shrinkable film, and (b)(ii) a third layer which is an oxygen barrier layer comprising at least one member selected from the group consisting of polyvinylidene chloride, saponified ethylene/vinyl acetate copolymer, polyamide, polyester, polypropylene, ethylene homopolymer, polyethylene naphthalate, polytrimethylene terephthalate, liquid crystal polymer, and O2-scavenger, the third layer being between the first layer and the second layer;
- C) the multilayer, heat-shrinkable film further comprises an ethylene/alpha-olefin plastomer having peak melt point of less than 90° C., the ethylene/alpha-olefin plastomer being present in the first film portion or the second film portion, the ethylene/alpha-olefin plastomer being present in the multilayer, heat-shrinkable film in an amount of at least 3 wt %, based on total film weight;
- D) the multilayer, heat-shrinkable film further comprises an incompatible polymer blend comprising at least one member selected from the group consisting of:
- (c)(i) a blend of from 90 to 30 weight percent ethylene homopolymer and/or ethylene/alpha-olefin copolymer with from 10 to 70 weight percent ethylene/unsaturated ester copolymer having an unsaturated ester content of at least 10 weight percent,
- (c)(ii) a blend of ionomer resin with ethylene/unsaturated ester copolymer, and/or polybutylene, and/or propylene homopolymer and/or propylene copolymer,
- (c)(iii) a blend of homogeneous ethylene/alpha-olefin copolymer with recycled polymer blend comprising ethylene homopolymer, propylene homopolymer, ethylene copolymer, propylene copolymer, polyamide, ethylene/vinyl alcohol copolymer, ionomer resin, and anhydride-modified ethylene/alpha-olefin copolymer,
- (c)(iv) a blend of from 10 to 75 weight percent ethylene/unsaturated ester copolymer with from 90 to 15 weight percent polypropylene and/or propylene/ethylene copolymer, and/or polybutylene, and/or modified ethylene/alpha-olefin copolymer, and/or styrene homopolymer, and/or styrene/butadiene copolymer,
- (c)(v) a blend of ethylene/norbornene copolymer with ethylene/unsaturated ester copolymer and/or polypropylene and/or polybutylene,
- (c)(vi) a blend of from 90 to 15 weight percent ethylene/alpha-olefin copolymer with from 10 to 75 weight percent polypropylene and/or polybutylene and/or ethylene/norbornene,
- (c)(vii) a blend of from 90 to 25 weight percent homogeneous propylene homopolymer and/or homogeneous propylene copolymer with from 10 to 75 weight percent homogeneous ethylene/alpha-olefin copolymer and/or ethylene/unsaturated ester copolymer,
- (c)(viii) a blend of propylene homopolymer and/or propylene/ethylene copolymer and/or polybutylene with ethylene/methyl acrylate copolymer and/or ethylene/acrylic acid copolymer and/or ethylene/butyl acrylate copolymer,
- (c)(ix) a blend of polyamide with polystyrene and/or ethylene/alpha-olefin copolymer and/or ethylene/vinyl acetate copolymer and/or styrene/butadiene copolymer, and
- (c)(x) a blend of polyamide 6 and polyamide 6I6T,
- with the incompatible polymer blend being in the first film portion or the second film portion, the incompatible polymer blend being present in the multilayer, heat-shrinkable film in an amount of at least 10 wt %, on a total film weight basis;
- and
- the multilayer film has a total free shrink at 85° C. of at least 90% measured in accordance with ASTM D2732, and Truburst strength of at least 8 psi/mil, measured in accordance with ASTM D3786.
15 more elements
20:
- The multilayer, heat-shrinkable film according to claim 19, wherein the ethylene/alpha-olefin plastomer is present in the seal layer.