EP3089875A1 - Oxygen scavenging film containing moisture regulator - Google Patents
Oxygen scavenging film containing moisture regulatorInfo
- Publication number
- EP3089875A1 EP3089875A1 EP13900800.7A EP13900800A EP3089875A1 EP 3089875 A1 EP3089875 A1 EP 3089875A1 EP 13900800 A EP13900800 A EP 13900800A EP 3089875 A1 EP3089875 A1 EP 3089875A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- moisture
- film
- polymer
- regulator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000001301 oxygen Substances 0.000 title claims abstract description 46
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 46
- 230000002000 scavenging effect Effects 0.000 title abstract description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229940123973 Oxygen scavenger Drugs 0.000 claims abstract description 43
- 229910052742 iron Inorganic materials 0.000 claims abstract description 30
- 229920000642 polymer Polymers 0.000 claims description 43
- 239000002245 particle Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 239000000741 silica gel Substances 0.000 claims description 20
- 229910002027 silica gel Inorganic materials 0.000 claims description 20
- 239000002808 molecular sieve Substances 0.000 claims description 19
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 19
- 229920001684 low density polyethylene Polymers 0.000 claims description 14
- 239000004702 low-density polyethylene Substances 0.000 claims description 14
- 229940099514 low-density polyethylene Drugs 0.000 claims description 14
- -1 polypropylene Polymers 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000004927 clay Substances 0.000 claims description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 9
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 9
- 239000002071 nanotube Substances 0.000 claims description 8
- 150000002926 oxygen Chemical class 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000012802 nanoclay Substances 0.000 claims description 6
- 239000005373 porous glass Substances 0.000 claims description 6
- 239000010457 zeolite Substances 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 229920001903 high density polyethylene Polymers 0.000 claims description 4
- 239000004700 high-density polyethylene Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 229920001222 biopolymer Polymers 0.000 claims description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 150000008040 ionic compounds Chemical class 0.000 claims description 2
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 2
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 claims description 2
- 239000004626 polylactic acid Substances 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000002516 radical scavenger Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 2
- 230000000996 additive effect Effects 0.000 claims 1
- 235000013305 food Nutrition 0.000 abstract description 12
- 239000000565 sealant Substances 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 62
- 239000000463 material Substances 0.000 description 14
- 239000002594 sorbent Substances 0.000 description 14
- 238000011068 loading method Methods 0.000 description 13
- 229910010272 inorganic material Inorganic materials 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000011147 inorganic material Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229920000858 Cyclodextrin Polymers 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000012792 core layer Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000012858 packaging process Methods 0.000 description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- 238000003855 Adhesive Lamination Methods 0.000 description 1
- 229920003345 Elvax® Polymers 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000009456 active packaging Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- BFMKFCLXZSUVPI-UHFFFAOYSA-N ethyl but-3-enoate Chemical compound CCOC(=O)CC=C BFMKFCLXZSUVPI-UHFFFAOYSA-N 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 235000021485 packed food Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/101—Glass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/102—Oxide or hydroxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/107—Ceramic
- B32B2264/108—Carbon, e.g. graphite particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7244—Oxygen barrier
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/40—Closed containers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
Definitions
- Moisture is known to trigger the oxygen scavenging reaction and enhance the oxygen absorption rate.
- moisture needs to be readily available, but water vapor transmission rate through polymers at refrigerated temperatures is typically slow.
- oxygen scavenging films are generally known for use both as oxygen absorbers and as oxygen barriers, it has long been understood that such films become less effective as the temperature of the environment in which they are used is reduced.
- Porous inorganic materials such as silica gel, molecular sieve, activated carbon, clay, carbon nanotube and others, known as sorbents, in fine particle format can absorb and release moisture depending on the surrounding environment.
- FIG. 1 is a diagrammatic view of a three layer coextruded film in accordance with an embodiment of this invention.
- FIG. 2 is a diagrammatic view of another three layer coextruded film in accordance with an embodiment of the invention.
- FIG. 3 is a diagrammatic view of a five layer film in accordance with an embodiment of the invention.
- FIG 4 is a graph of the oxygen absorption versus time for the films constructed in accordance with embodiment of this disclosure.
- sorbents can serve as moisture regulators that absorb and release moisture to facilitate oxygen scavenging rate for the package.
- the presence of a moisture regulator in a film improves the rate of oxygen absorption, particularly at refrigerated temperatures.
- a single or multilayer film can be used as a wrap, as a base film, or as a sealant film to be laminated onto a substrate. Laminates thus formed can be converted into food packages for enhancing the freshness of food contained therein. Moisture regulators can be included in any or all of these layers.
- One aspect of this disclosure provides techniques to facilitate water vapor transport, thus improving oxygen scavenging rate. This is particularly beneficial for refrigerated conditions, in which enhanced activation is desired.
- a method and apparatus are provided to enhance the oxygen scavenging rate of iron-based oxygen scavengers in an extruded article such as a film or sheet.
- a moisture absorbing and emitting material is included with an oxygen scavenger in the article.
- the moisture absorbing and emitting material is preferably in fine particle form and distributed in close proximity with the oxygen scavenger.
- the moisture absorbing and emitting material is a moisture regulator.
- the moisture regulator may be a porous inorganic material. Examples of suitable moisture regulators include, but are not limited to, silica gel, activated carbon, molecular sieve, clay, nanotubes, and other inorganic compounds that have a desirable porosity.
- the inorganic material may also absorb oxygen but its main function is to absorb and emit moisture.
- a moisture regulator is a material that both absorbs and releases moisture, usually but not necessarily in the form of water vapor, to maintain the relative humidity surrounding it at a predetermined desired level. The level need not be maintained precisely, it may vary over a range of relative humidities. The moisture regulator will, when the ambient relative humidity is sufficiently low, release moisture to raise the relative humidity.
- Other aspects of this disclosure provide single and multilayer films that include an iron-based oxygen scavenger and moisture regulator in one or more of the layers.
- the moisture regulator facilitates water vapor transport from the foodstuff and/or from the ambient atmosphere into the oxygen scavenger to enhance the rate of oxygen scavenging.
- the moisture regulator may be a porous sorbent such as silica gel, molecular sieve or activated carbon dispersed in some part of the film. In some embodiments, the extruded film exhibits some porosity due to the embedded moisture regulator.
- a multilayer moisture regulating and oxygen scavenging package for a food product includes a sealant layer formed from a first polymer and having a plurality of moisture regulating particles dispersed therein, a core layer formed from a second polymer that may or may not be different from the first polymer and having a plurality of moisture activated oxygen absorbing particles dispersed therein, and a skin layer formed from a third polymer that may be the same as or different from the first and second polymers. Additional layers such as metalized, barrier, or print layers, depending on the eventual end use, may be added.
- a fabricated article contains an iron-based oxygen scavenger and a moisture regulator that provides enhanced rate of oxygen scavenging.
- a multilayer film, its laminates and converted bag, pouch, or containers made therefrom contain an iron-based oxygen scavenger and a moisture regulator.
- the converted products possess enhanced oxygen scavenging rate suitable for use at refrigerated
- an oxygen scavenging article that contains a moisture regulator that facilitates water vapor transport into the film to enhance the oxygen scavenging rate is described.
- a multilayer film structure includes an iron based oxygen scavenger and a moisture regulator that are distributed in selected layers to give enhanced oxygen scavenging rate.
- the moisture regulator includes one or more of silica gel, activated carbon, molecular sieve or any other porous sorbent particles.
- a multilayer polymer film includes an iron-based oxygen scavenger in a core layer that is sandwiched by other layers that include a porous inorganic material including one or more of silica gel, activated carbon, molecular sieve, clays or other materials.
- a method to enhance the oxygen scavenging rate of iron based oxygen scavenger in an extruded article such as film or sheet is described.
- a moisture absorbing and emitting material is included with the oxygen scavenger in the article.
- the moisture absorbing and emitting material is in fine particle form and distributed in close proximity with the oxygen scavenger.
- the moisture absorbing and emitting material is a moisture regulator.
- the moisture regulator is a porous inorganic material. Examples of the moisture regulator include silica gel, activated carbon, molecular sieve, clay, nanotubes and other inorganic compounds that contain porosity.
- the inorganic material may absorb oxygen but its main function is to absorb and emit moisture.
- Organic moisture absorbing materials such as hydrophilic resin, super-absorbent polymer, and water-soluble polymers, and the different types of cyclodextrin can also be included
- a three layer coextmded film 100 in accordance with this an embodiment of this disclosure is shown in Figure 1.
- the film includes a first layer 102, a second layer 104, and a third layer 106.
- the first layer 102 is a skin layer
- the second layer 104 contains an iron-based oxygen scavenger 108
- the third layer 106 is contains a moisture regulator 110.
- the moisture regulator 110 is preferably silica gel or molecular sieve in fine particle form.
- the third Layer 106 may also be a sealant layer suitable for contacting with the packaged foods.
- the first layer 102 is a skin layer, which may be suitable for laminating to a substrate, and the second layer 104 scavenges oxygen.
- a first layer 202 is a skin layer, e.g., for lamination
- a second layer 204 includes both an oxygen scavenger 108 and a moisture regulator 1 10
- a third layer 206 includes the moisture regulator 110.
- the film may be embodied in a single layer, i.e., in which a single polymer layer includes both the oxygen scavenger and the moisture regulator or it may be embodied, or in two layers, e.g., by removing the first layers 102, 202 in the Examples of Figures 1 and 2 or by maintaining the first layer 202, but by removing the third layer 206 in the example of Figure 2.
- the film may be embodied in four or more layers.
- the iron-based oxygen scavenger may be located in selected layers and the moisture regulator may be distributed in one or more layers in a gradient manner such that the moisture regulator is more abundant toward a sealant side (i.e., the bottom in the examples illustrated in the Figures) and less abundant on the lamination side (i.e., the top in examples illustrated in the Figures).
- Figure 3 is one such example of a five layer film 300.
- first through fifth layers 302, 304, 306, 308, 310, respectively, are provided.
- the first layer 302 may be a skin layer.
- the iron-based oxygen scavenger 108 is located in the second and fourth layers 304,308 and the moisture regulator 110 is dispersed in the third, fourth and fifth layers 306, 308, 310.
- the structure provides an oxygen scavenging rate that is suitable to meet both short and long term oxygen scavenging needs. The loadings of these ingredients can be experimentally determined to fit specific application.
- the oxygen scavenger 108 and the moisture regulator 110 may be used in the same or different layers, or the same material having different characteristics may be used in the same or different layers.
- the oxygen scavenger 108 used in each of the second and fourth layers 304, 308 may be iron-based, but the iron particles may be differently sized or differ based on other characteristics.
- the fifth layer 210 may contain silica gel as the moisture regulator 110, and layers 206 and 208 may contain molecular sieve as the moisture regulator.
- one or all of the layers may contain both silica gel and molecular sieve as moisture regulators.
- Films prepared in accordance with this invention can be converted into flexible, semi-rigid and rigid packages for food packaging applications.
- the packages possess enhanced oxygen scavenging rates.
- One example conversion includes laminating the films that contain the iron based oxygen scavenger and moisture regulator onto a substrate such as PET, metalized-PET, nylon, or a composite film containing PET.
- the method can be based on any conventional adhesive lamination processes.
- the laminated film or sheet may subsequently be formed into bags, pouches or containers, for example, using conventional Vertical Form Fill and Seal (VFFS), Horizontal Form Fill and Seal (HFFS), or thermoforming process methodologies such as those used with moist foods.
- VFFS Vertical Form Fill and Seal
- HFFS Horizontal Form Fill and Seal
- thermoforming process methodologies such as those used with moist foods.
- Bags or pouches produced from this method can provide a higher oxygen scavenging rate compared to packages made without the moisture regulator. Packages in accordance with the teachings of this disclosure may be particularly useful for refrigerated products.
- a moisture regulator can be any inorganic sorbent, including but not limited to silica gel, molecular sieve, activated carbon, porous glass, silicon dioxide, clay, nanoclay, nano tubes and other porous inorganic materials.
- the sorbents are preferably capable of absorbing and releasing moisture.
- silica gel with pore size of 2 nm or larger can be used. Wide pore types (>2 nm) are preferred.
- silica gel has variable pore size within a structure and is capable of both absorbing and releasing moistures. It is a suitable material for use as a moisture regulator in accordance with this disclosure.
- Molecular sieve may also be used. In general, pores are uniform in size for molecular sieve, and larger pores are generally desirable. Zeolite, a type of synthetic molecular sieve, can have different pore sizes, but are typically classified as microporous ( ⁇ 2 nm), mesoporous (2 - 50 nm) and macroporous (>50 nm).
- the particle size of the moisture regulator can range from 0.005 to 30 micron, preferably 0.05 to 15 micron, more preferably 0.1 to 10 micron. Particle size is an important consideration as it determines the overall loading of the moisture regulator in the film. The larger the particles, the less loading can take place, since larger particles take up more space within the resin matrix. Additionally the size of the particles must be smaller than the depth of the resin film that they are embedded in; otherwise they will be exposed through the surface the film.
- the volume percentage of the moisture regulator can range from 0.5 to 50% of the volume of the extruded article, preferably 1 to 30%, more preferably 5 to 20% of the extruded article.
- the loading range determines the overall processability of the compounded resin and its overall aesthetic appearance. At loadings of about 20% or higher, it is more difficult to run compounded resins through the extruders, putting more wear and tear on the machines and heads, and the final resin film itself becomes quite dark, and almost unusable for any packaging process. Therefore it is important to determine the point where the loading achieves maximum effect for the minimum amount of loading.
- Organic moisture absorbing materials such as hydrophilic resin, super-absorbent polymer water-soluble polymers, and the different types of cyclodextrin can also be included.
- Sorbents in powder or particulate form are preferably compounded with a polymer to form a master batch in pellet form before being used in film making.
- the sorbent-polymer pellet is dried preferably in a hot air oven at 90°C for 10 to 72 hours depending on the residual moisture content. It is preferred that the residual moisture in the compounds is below 200 ppm, more preferably below 60 ppm before being used in film extrusion.
- Polymers useful for making the oxygen scavenging articles include common polyolefms such as polypropylene (PP), low-density polyethylene (LDPE), high density polyethylene (HDPE), polyethylene (PE) and their derivatives or copolymers, polyesters such as polyethylene terephthalate (PET), polyethylene terephthalate glycol-modified (PETG), polyethylene naphthalate (PEN), styrene- based polymers such as polystyrene, rubber-modified polystyrene, biopolymers such as polylactic acid (PLA), polyhydroxyalkanoate (PHA), starch polymers and copolymers, and other types of common polymers.
- PP polypropylene
- LDPE low-density polyethylene
- HDPE high density polyethylene
- PE polyethylene
- PET polyethylene terephthalate glycol-modified
- PEN polyethylene naphthalate
- styrene- based polymers such as polyst
- the iron-based oxygen scavenger is a reduced iron powder.
- the powder may have a 0.1-200 ⁇ mean particle size, more preferably 1-50 ⁇ mean particle size and most preferably 1-10 ⁇ mean particle size.
- the iron can be mixed with salt or a combination of different electrolytic and acidifying components.
- the iron particles can also be coated with salt. The combination and relative fraction of activating electrolytic and acidifying
- components coated onto the iron particles can be selected according to the teachings of United States Patent No. 6,899,822, United States Patent Application Publication No. 2005/0205841, and/or United States Patent Application Publication No.
- the coating technique is preferably a dry coating process as described in the references above.
- the loading of the iron-based oxygen scavenger is preferably from 1-30%, more preferably 2-15%, and is selected based on the application requirements. If the use is in refrigerated conditions, the scavenger content may need to be higher. Again, the percentage of loading is critical to consider for the same reasons considered when determining the loading of the moisture regulator, with around 20% loading by weight being the point where processability and appearance become deleterious.
- the salt can be any inorganic salt such as sodium, potassium or calcium based ionic compounds that are soluble in water. Typical examples include NaCl, KC1, Na 2 HPO 4 and others. A mixture of separate electrolytic and acidifying salt components may be used in the formulation.
- Articles made in accordance with this disclosure can be films or sheets, single or multilayer, and include iron-based oxygen scavengers and moisture regulators.
- the films or sheets can be laminated, thermoformed into food packages, or die-cut by conventional die cutting tool, for example, to be used as a labeling product. They can also be die cut inline to fit a specific packaging process.
- the films may also include electrolytes (US 2010/0255231A1, 10/7/2010, App #: 12/416685, filed 4/1/09).
- a control material without a moisture regulator was formulated by blending Dow 6401 LDPE resin with FreshblendTM oxygen scavenger (available from Multisorb Technologies, Inc. of Buffalo NY) in fine powder format and extruded in a twin screw extruder to make pellets.
- Freshblend oxygen scavenger were used as concentrate in a coextrusion film run.
- a first group of test materials with different sorbent loadings was then formulated by compounding silica gel (used was Syloid 7000 obtained from WR Grace) and andmolecular sieve (used was Type 4A obtained from UOP) with LDPE with 15 to 40% loading, and extruded as pellets to be used as concentrate. These sorbent-containing compounds were dried in a desiccant dryer at 90°C for 16 hrs. prior to use in film extrusion.
- the films include Test 1 and Test 2, made according to aspects of this disclosure. They were extruded from a coextrusion line that consists of three extruders, a feedblock, and a 10" die. Films approximately 3-5 mil thick and 9" in width were extruded at approximately 220°C extruder barrel and die temperature.
- Test 1 and Test 2 films the A layer contains LDPE with a chosen sorbent in it.
- the B layer contains LDPE with Freshblend oxygen scavenger and a chosen sorbent, and the C layer contains LDPE only.
- DuPont Elvax 3170 EVA was used in certain blends used in the A layer, for example, when Layer A constitutes a sealing layer. Of course, design choice may dictate the use of EVA and/or other additives in any layers and for any purposes.
- the extruded films were uniform and collected on a roll. [0050] The films were tested for their oxygen scavenging properties. Film samples of 14"x7" were weighed and heat laminated to a PE coated foil by using a heat laminator with the C layer heat laminated to the coated surface of the foil.
- Pouches with approximately 7"x7" net film surface were made and 300 cc of air was injected into the pouch.
- the pouches contain blotted paper that contains approximately 4 gm. of water as moisture source to activate the oxygen scavenger.
- the pouches were stored in a 4°C refrigerator.
- the oxygen concentration was measured by using a MOCON Pac Check Model 650 head space analyzer over time.
- the description of the films and oxygen absorption data are listed in Table- 1.
- Test 1 and Test 2 films having sorbents loaded in the A and B layers showed enhanced oxygen absorption rate compared with the Control film.
- the enhancement was obvious for silica gel loaded sample (Test 1) after only a short time. Over a longer time period, both the sorbent-loaded films provided much enhanced oxygen absorption.
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Laminated Bodies (AREA)
- Wrappers (AREA)
Abstract
Description
Claims
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PCT/US2013/078481 WO2015102614A1 (en) | 2013-12-31 | 2013-12-31 | Oxygen scavenging film containing moisture regulator |
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EP3089875A1 true EP3089875A1 (en) | 2016-11-09 |
EP3089875A4 EP3089875A4 (en) | 2017-08-09 |
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EP13900800.7A Withdrawn EP3089875A4 (en) | 2013-12-31 | 2013-12-31 | Oxygen scavenging film containing moisture regulator |
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WO (1) | WO2015102614A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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EP3356142B1 (en) * | 2015-09-29 | 2020-05-20 | Philip Morris Products S.a.s. | Moisture control packaging materials |
US11932000B2 (en) | 2021-03-23 | 2024-03-19 | Whirlpool Corporation | Refrigerator having a membrane |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
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AU623398B2 (en) * | 1988-04-30 | 1992-05-14 | Toyo Seikan Kaisha Ltd. | Multilayered plastic container |
US6209289B1 (en) * | 1992-01-30 | 2001-04-03 | Multisorb Technologies, Inc. | Composition for and method of absorbing oxygen in an oxygen/carbon dioxide environment |
CN1235956C (en) * | 1996-03-07 | 2006-01-11 | 克里奥瓦克公司 | Sealing composition |
US5977212A (en) * | 1997-11-21 | 1999-11-02 | W. R. Grace & Co.-Conn. | Oxygen scavenging compositions |
EP0941836B1 (en) * | 1998-03-12 | 2005-06-08 | Mitsubishi Gas Chemical Company, Inc. | Oxygen-absorbing multi-layer laminate, production method thereof and packaging container |
US20060069197A1 (en) * | 2004-09-27 | 2006-03-30 | Tammaji Kulkarny S | Oxygen scavenging composition |
US9174408B2 (en) * | 2010-03-15 | 2015-11-03 | Winpak Portion Packaging | Multilayered packaging material |
-
2013
- 2013-12-31 EP EP13900800.7A patent/EP3089875A4/en not_active Withdrawn
- 2013-12-31 WO PCT/US2013/078481 patent/WO2015102614A1/en active Application Filing
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EP3089875A4 (en) | 2017-08-09 |
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