CA2165340C - Pouch for packaging flowable materials - Google Patents
Pouch for packaging flowable materials Download PDFInfo
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- CA2165340C CA2165340C CA002165340A CA2165340A CA2165340C CA 2165340 C CA2165340 C CA 2165340C CA 002165340 A CA002165340 A CA 002165340A CA 2165340 A CA2165340 A CA 2165340A CA 2165340 C CA2165340 C CA 2165340C
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- Prior art keywords
- pouch
- ethylene
- alpha
- linear ethylene
- substantially linear
- 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.)
- Expired - Lifetime
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Classifications
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D75/00—Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes, or webs of flexible sheet material, e.g. in folded wrappers
- B65D75/008—Standing pouches, i.e. "Standbeutel"
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- 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
- B32B2323/00—Polyalkenes
- B32B2323/04—Polyethylene
-
- 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
- B32B2323/00—Polyalkenes
- B32B2323/04—Polyethylene
- B32B2323/046—LDPE, i.e. low density polyethylene
-
- 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
- B32B2439/46—Bags
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- 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
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
- B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1328—Shrinkable or shrunk [e.g., due to heat, solvent, volatile agent, restraint removal, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31913—Monoolefin polymer
- Y10T428/3192—Next to vinyl or vinylidene chloride polymer
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Bag Frames (AREA)
- Wrappers (AREA)
- Containers And Plastic Fillers For Packaging (AREA)
Abstract
An environmentally friendly polymer film pouch made from a homogeneosly branched substantially linear ethylene interpolymer film structure for the packaging of flowable materials such as milk, is disclosed. A pouch made from a multilayer film structure such as a two-layer or a three-layer coextruded film containing at least one seal layer of a homogeneously branched substantially linear poloyethylene is also disclosed. A process for making a pouch for packaging flowable materials using a homogeneously branched substantially linear ethylene interpolymer film structure is also disclosed.
Description
WO 95!00587 216 5 3 4 0 PCT/US94/06730 POUCH FOR PACKAGING FLOWABLE MATERIALS
This invention relates to a pouch used in consumer packaging useful for packaging flowable materials, (for example, liquids such as milk). The pouch is made from certain film structures comprising at least one homogeneously branched substantially linear ethylene interpolymer.
U.S. Patent Nos. 4,503,102 and 4,521,437 disclose the preparation of a polyethylene film for use in the manufacture of a disposable pouch for packaging of liquids such as milk. U.S. Patent No.
io 4,503,102 discloses pouches made from a blend of a linear ethylene -copolymer copolymerized from ethylene and an alpha-olefin at the C4-C10 range and an ethylene-vinyl acetate polymer copolymerized from ethylene and vinyl acetate. The linear polyethylene copolymer has a density of from 0.916 to 0.930 grams/cubic centimeter (glcm3) and a melt index of i5 from 0.3 to 2.0 grams/10 minutes (g/10 min). The ethylene-vinyl acetate polymer has a weight ratio of ethylene to vinyl acetate from 2.2:1 to 24:1 and a melt index of from 0.2 to 10 g/10 min. The blend disclosed in U.S.
Patent No. 4,503,102 has a weight ratio of linear low density polyethylene to ethylene-vinyl acetate polymer of from 1.2:1 to 4:1. U.S. Patent No.
20 4,503,102 also discloses laminates having as a sealant film the aforementioned blend.
U.S. Patent No. 4,521,437 describes pouches made from a sealant film which is from 50 to 100 parts of a linear copolymer of ethylene and octene-1 having a density of from 0.916 to 0.930 g/cm3 and a 25 melt index of 0.3 to 2.0 g/10 min and from 0 to 50 parts by weight of at least one polymer selected from the group consisting of a linear copolymer of ethylene and a C1-Cl0 alpha-olefin having a density of from 0.916 to 0.930 g/cm3 and a melt index of from 0.3 to 2.0 g/10 min, a high-pressure polyethylene having a density of from 0.916 to 0.924 g/cm3 and a melt 3o index of from 1 to 10 g/10 min and blends thereof. The sealant film disclosed in the U.S. Patent No. 4,521,437 is selected on the basis of providing (a) pouches with an M-test value substantially smaller, at the same film thickness, than that obtained for pouches made with film of a blend of 85 parts of a linear ethylene/butene-1 copolymer having a density s5 of about 0.919 g/cm3 and a melt index of about 0.75 g/10 min and 15 parts WO 95/00587 216 5 3 4 0 PCT~S9.~106730 of a high pressure polyethylene having a density of about 0.918 g/cm3 and a melt index of 8.5 g/10 min, or (b) an M(2)-test value of less than about 12 percent, for pouches having a volume of from greater than 1.3 to 5 liters, or (c) an M(1.3)-test value of less than about 5 percent for pouches having a volume of from 0.1 to 1.3 liters. The M, M(2) and M(1.3)-tests are defined pouch drop tests in U.S. Patent No. 4,521,437.
The pouches may also be made from composite films in which the sealant film forms at least the inner layer.
The polyethylene pouches known in the prior art have some io deficiencies. The problems associated with the prior art known films relate to the sealing properties and performance properties of the film for preparing pouches. In particular, prior art films made into pouches have a high incident of "leakers", that is, seal defects such as pinholes which develop at or near the seal in which flowable material, for example i5 milk, escapes from the pouch. Although the seal and performance properties of the prior art films have been satisfactory, there is still a need in the industry for better seal and performance properties in films for manufacture of hermetically sealed pouches containing flowable materials. More particularly, there is a need for improved sealing 2o properties of the film such as hot tack and heat seal initiation temperature in order to improve the processability of the film and to improve pouches made from the films.
For example, the line speed of known packaging equipment used for manufacturing pouches such as form, fill and seal machines, is z5 currently limited by the sealing properties of the film used in the machines. Prior art polyethylene films have high hot tack seal initiation temperatures and a narrow sealing range. Therefore, the rate at which a form, fill and seal machine can produce pouches is limited. If the heat seal temperature range where one could obtain strong seals is broadened, 3o then the speed of a form, fill and seal machine can be increased and, thus, the rate at which pouches can be produced can be increased. Until the present invention, many have attempted to broaden the heat seal temperature range of pouch film without success.
It is desired to provide a polyethylene film structure for a 35 pouch container having a broad heat sealing range with performance properties as good or better than the known prior art pouch films.
This invention relates to a pouch used in consumer packaging useful for packaging flowable materials, (for example, liquids such as milk). The pouch is made from certain film structures comprising at least one homogeneously branched substantially linear ethylene interpolymer.
U.S. Patent Nos. 4,503,102 and 4,521,437 disclose the preparation of a polyethylene film for use in the manufacture of a disposable pouch for packaging of liquids such as milk. U.S. Patent No.
io 4,503,102 discloses pouches made from a blend of a linear ethylene -copolymer copolymerized from ethylene and an alpha-olefin at the C4-C10 range and an ethylene-vinyl acetate polymer copolymerized from ethylene and vinyl acetate. The linear polyethylene copolymer has a density of from 0.916 to 0.930 grams/cubic centimeter (glcm3) and a melt index of i5 from 0.3 to 2.0 grams/10 minutes (g/10 min). The ethylene-vinyl acetate polymer has a weight ratio of ethylene to vinyl acetate from 2.2:1 to 24:1 and a melt index of from 0.2 to 10 g/10 min. The blend disclosed in U.S.
Patent No. 4,503,102 has a weight ratio of linear low density polyethylene to ethylene-vinyl acetate polymer of from 1.2:1 to 4:1. U.S. Patent No.
20 4,503,102 also discloses laminates having as a sealant film the aforementioned blend.
U.S. Patent No. 4,521,437 describes pouches made from a sealant film which is from 50 to 100 parts of a linear copolymer of ethylene and octene-1 having a density of from 0.916 to 0.930 g/cm3 and a 25 melt index of 0.3 to 2.0 g/10 min and from 0 to 50 parts by weight of at least one polymer selected from the group consisting of a linear copolymer of ethylene and a C1-Cl0 alpha-olefin having a density of from 0.916 to 0.930 g/cm3 and a melt index of from 0.3 to 2.0 g/10 min, a high-pressure polyethylene having a density of from 0.916 to 0.924 g/cm3 and a melt 3o index of from 1 to 10 g/10 min and blends thereof. The sealant film disclosed in the U.S. Patent No. 4,521,437 is selected on the basis of providing (a) pouches with an M-test value substantially smaller, at the same film thickness, than that obtained for pouches made with film of a blend of 85 parts of a linear ethylene/butene-1 copolymer having a density s5 of about 0.919 g/cm3 and a melt index of about 0.75 g/10 min and 15 parts WO 95/00587 216 5 3 4 0 PCT~S9.~106730 of a high pressure polyethylene having a density of about 0.918 g/cm3 and a melt index of 8.5 g/10 min, or (b) an M(2)-test value of less than about 12 percent, for pouches having a volume of from greater than 1.3 to 5 liters, or (c) an M(1.3)-test value of less than about 5 percent for pouches having a volume of from 0.1 to 1.3 liters. The M, M(2) and M(1.3)-tests are defined pouch drop tests in U.S. Patent No. 4,521,437.
The pouches may also be made from composite films in which the sealant film forms at least the inner layer.
The polyethylene pouches known in the prior art have some io deficiencies. The problems associated with the prior art known films relate to the sealing properties and performance properties of the film for preparing pouches. In particular, prior art films made into pouches have a high incident of "leakers", that is, seal defects such as pinholes which develop at or near the seal in which flowable material, for example i5 milk, escapes from the pouch. Although the seal and performance properties of the prior art films have been satisfactory, there is still a need in the industry for better seal and performance properties in films for manufacture of hermetically sealed pouches containing flowable materials. More particularly, there is a need for improved sealing 2o properties of the film such as hot tack and heat seal initiation temperature in order to improve the processability of the film and to improve pouches made from the films.
For example, the line speed of known packaging equipment used for manufacturing pouches such as form, fill and seal machines, is z5 currently limited by the sealing properties of the film used in the machines. Prior art polyethylene films have high hot tack seal initiation temperatures and a narrow sealing range. Therefore, the rate at which a form, fill and seal machine can produce pouches is limited. If the heat seal temperature range where one could obtain strong seals is broadened, 3o then the speed of a form, fill and seal machine can be increased and, thus, the rate at which pouches can be produced can be increased. Until the present invention, many have attempted to broaden the heat seal temperature range of pouch film without success.
It is desired to provide a polyethylene film structure for a 35 pouch container having a broad heat sealing range with performance properties as good or better than the known prior art pouch films.
It is also desired to provide a film structure for a pouch container having a heat seal layer such that the film structure has a broader sealing range for pouch conversion and has acceptable physical properties in the finished product.
It is further desired to provide a pouch made from the aforementioned film structures such that the pouch has a reduced failure rate.
We have now discovered that new homogeneously branched substantially linear ethylene/a-olefin interpolym<>rs offer significant io advantages in film structures of pouches. The novel homogeneously branched substantially linear ethylene/a-olefin interpolymers, when used as a seal layer, have good heat sealability at temperatures lower than those necessary for heterogeneously branched linear ethylene/a-olefin interpolymers and are also easily processed on conventional film and heat is seal equipment. Pouches made from film structure_=; comprising the homogeneously branched substantially linear ethyle ne/a-olefin interpolymers, when used as a seal layer or as a core layer, also have surprisingly good bursting performance.
One aspect of the present invention is directed to a pouch 2o made from a film structure in tubular form and having transversely heat sealed ends, the film structure having at least one film layer comprising:
(I) from 10 to 100 percent by weight of at least one homogeneously branched substantially linear ethylene/a-olefin interpolymer characCerized as having:
25 (a) a melt flow ratio, I10/I2, _> 5.63, and (b) a molecular weight distribution, Mw/Mn, defined by the equation. Mw/Mn S (I10/I2) - 9.63; and (II) from 0 to 90 percent by weight of at least one polymer selected from the group consisting of a heterogeneously 3o branched linear ethylene/C3-Clg a-olefin copolymer., a high-pressure low density polyethylene, and an ethylene-vinyl acetate copolymer.
One embodiment of the present invention is a pouch made from a two-layer (that is, A/B) coextruded film containing an outer layer of a heterogeneously branched linear low density polyethylene and an inner seal 35 layer of the aforementioned homogeneously branched substantially linear ethylene interpolymer.
Another embodiment of the present invent:ion is a pouch made from a three-layer (that is, A/B/A or A/B/C) coextruded film containing an outer layer and a core layer comprising heterogeneously branched linear low density polyethylene (either the same or different heterogeneously branched linear low density polyethylenes~) or a high pressure iow density polyethylene and an inner seal layer comprising the aforementioned homogeneou~;ly branched substantially linear ethylene interpolymer.
In these embodiments the outer layer may comprise at least one polymer selected from the group consisting of a heterogeneously branched linear ethylene/C3-C18 a-alefin copolymer, a high-pressure low density polyethylene, and an ethylene/vinyl acetate polymer.
Another aspect of the present invention is a process for preparing the aforementioned pouch.
In one embodiment of this aspect there i.s provided a process of preparing a pouch in a vertical form containing a flowable material comprising the steps of forming a film structure; forming the film structure into a tubular member;
heat-sealing longitudinal edges and first transverse end of the tubular member to form the pouch; filling the pouch with the flowable material; and sealing a second transverse end of the tubular member, the film structure having at least one layer comprising: (a) from 10 to 100 percent by weight of at least one homogeneously branched substantially linear ethylene/a-olefin interpolymer, and (b) from 0 to 90 percent by weight of at least one polymer selected from th.e group consisting of a heterogeneously branched linear ethylene/C3-C18 ~-olefin copolymer, a high-pressure low density polyethylene and an ethylene/vinyl acetate copolymer.
In another embodiment there is provided a process of preparing a pouch in a vertical form containing a flowable material comprising the steps of forming a film structure; forming the film structure into a tubular member;
heat-sealing longitudinal edges and first transverse end of the tubular member to form the pouch; filling the pouch with the flowable material; and sealing a second transverse end of the tubular member, the film structure having at least one layer comprising: (I) (a) from 10 to 100 percent by weight of at least one homogeneously branched substantially linear ethylene/a-olefin interpolymer, and (b) from 0 to 90 percent by weight of at least one polymer selected from the group consisting of a heterogeneously branched linear ethylene/C3-C18 a-olefin copolymer, a high-pressure low density polyethylene and an ethylene/vinyl acetate copolymer; and at least one layer comprising: (II) a heterogeneously branched linear ethylene/C3-C1$ a-olefin copolymer having a density greater than 0.87 g/cm3 and a melt index .from 0.1 to 10 g/10 minutes.
According to another embodiment of the process described above, the film structure includes at least one other layer comprising: a high-pressure low density polyethylene having a density from 0.916 to 0.93 g/cm3 and a melt index from 0.1 to 10 g/10 minutes.
Film structures for the pouches of the present invention have a better seal at lower sealing temperatures and shorter dwell times than currently obtainable with commercially available film. Use of the films for making pouches of the present invention in form, fill and seal machines leads to machine speeds higher than currently obtainable with the use of commercially available film.
-4a-Figure 1 shows a perspective view of a pouch package of the present invention.
Figure 2 shows a perspective view of another pouch package of the present invention.
Figure 3 shows a partial, enlarged cross-sectional view of the film structure of a pouch of the present invention.
Figure 4 shows another partial, enlarged cross-sectional view of another~embodiment of the film structure of a pouch of the present invention.
Figure 5 shows yet another partial, enlarged cross-sectional view of another embodiment of the film structure of a pouch of the present invention.
Figure 6 is a graphical illustration of film hot tack strength versus temperature for resin 7 and comparative resin 1.
-4b-WO 95/00587 216 5 3 4 0 PCT~S94/06730 Figure 7 is a graphical illustration of film hot tack strength versus temperature for resin 6 and comparative resin 2.
Figure 8 is a graphical illustration of film hot tack strength versus temperature for resin 5 and comparative resin 3.
Figure 9 is a graphical illustration of film hot tack strength versus sealing time for resins 5-7 and comparative resins 1-3 and comparative film 8.
io Figure 10 is a graphical illustration of film heat seal strength versus temperature for resin 7 and comparative resin 1.
Figure 11 is a graphical illustration of film heat seal strength versus temperature for resin 6 and comparative resin 2.
Figure 12 is a graphical illustration of film heat seal strength versus temperature for resin 5 and comparative resin 3.
2o Figure 13 is a graphical illustration of film heat seal strength versus sealing time for resins 5-7 and comparative resins 1-3 and comparative film 8.
Figure 14 is a graphical illustration of vertical form-fill-seal film heat seal strength versus temperature for resin 7 and comparative resin 1.
Figure 15 is a graphical illustration of vertical form-fill-seal film heat seal strength versus temperature for resin 6 and 3o comparative resin 2.
Figure 16 is a graphical illustration of vertical form-fill-seal film heat seal strength versus temperature for resin 5 and comparative resin 3.
Firgure 17 is a graphical illustration of maximum Ellen hot tack strength versus resin density for resins 5-7 and comparative resins 1-3.
s The pouch of the present invention, for example as shown in Figures 1 and 2, for packaging tlowable materials i~ manufactured Cror» a monolayer film structure of a polymeric seal layer which is a homogeneously branched substantially linear ethylene/a-olefin interpolymer (referred to hereinafter as "SLEP"l.
lo The SLEP of the present invention is generally an interpolymer of ethylene with at least one a-olefin having from 3 to 2U carbon atoms.
The term "interpolymer" is used herein to indicate a copolymer, or a terpolymer, or the like. That is, at least one other comonomer is polymerized with ethylene to make the interpolymer. For example, a SLEP
~5 terpolymer comprising ethylene!1-octene/1-hexane may be employed in the film structure as the polymeric seal layer.
Copolymers of ethylene and a C3-C20 tx-olefin are especially preferred, for example, the SLEP may be selected from.ethylene/propene, ethylene/1-butane, ethylene/1-pentane, ethylene/~L-methyl-1-pentane, 2o ethylene/1-hexane, ethylenell-heptene, ethylene/7~-octane and ethylene/1-decene copolymers, preferably ethylene/1-octane copolymer.
The term "substantially linear" means that the interpolymer backbone is substituted with 0.01 long chain branches/1000 carbons to 3 long chain branches/1000 carbons, more preferably from 0.01 long chain 25 branches/1000 carbons to 1 long chain branches/1000 carbons,. and especially from 0.05 long chain branches/1000 carbons to Z Tang chain branches/1000 carbons_ Long chain branching is defined herein as a chain length of at least about 6 carbons, above which the length cannot be distinguished 3o using 13C nuclear magnetic resonance spectroscopy. The length of the long chain branch can vary, but can be about as long as the length of the polymer back-bone itself.
Long chain branching is determined by using 1~C nuclear magnetic ,resonance (NMR) spectroscopy and is quantified using the method s5 of Randall ( ev. Macromol. Chem. PhDs-, C29 (2&3), p. 285-297j.
_t-The substantially linear ethylene/a-olefin copolymers and interpolymers of the present invention are herein defined as in USP
5,278,236 and in USP 5,278,272. The substantially linear.
ethylene/a-olefin copolymers and interpolymers useful for forming the s compositions described herein are homogeneously branched (th.st is, the comonomer is randomly distributed within a given interpclymer molecule and wherein substantially all of the interpolymer molecules have the same ethylene/comonomer ratio within that interpolymer).
The SCHDI (Short Chain Branch Distribution Index) or CDBI
~o (Composition Distribution Branch Index) is defined as the weight percent of the polymer molecules having a comonomer content within SO percent of the median total molar comonomer content. The CDBI of a polymer i:~ readily calculated from data obtained from techniques known in the art, such as, for example, temperature rising elution fractionation (abbr.eviated herein is as 'TREF') as described, for example, in Wild et al, Journal of .Polymer Science, ,~oy_r~. ghys. ~, Vol. 20, p. 441 (1982), or in U.S. Patent 4,798,081.
The SCBDI or CDBI for the substantially linear ethylene/oc-olefin interpolymers and copolymers used in the present invention i.s preferably 2o greater than 30 percent, especially greater than 50 percent. The substantially linear ethylene/cx-olefin interpolymers and copolymers used in this invention essentially lack a measurable "high density" fraction as measured by the TREF technique. The "high density" fraction includes linear homopolymer polyethylene. The "high density" polymer fraction can 25 be described as a polymer fraction with a degree of branching less than or equal to 2 methyls~1000 carbons. The terms 'essentially lacks a measurable high density fraction" means that the substantially linear interpolymers and copolymers do not contain a polymer fraction with a degree of branching less than or equal to 2 methyls/1000 carbons.
3a The novel homogeneously branched SLED are easily distinguished from homogeneously branched linear ethylene/oc-olefin interpolymers. The term "linear ethylene/OC-olefin interpolymer" means that the interpolymer does not have long chain branching. That is, the linear ethylene/oc-olefin interpolymer has an absence of long chain branching, as for example the 35 homogeneously branched linear low density polyethylene polymers made using uniform branching distribution polymerization processes (for example, as _;._.
WO 95/00587 216 5 3 4 0 PCT~S94/06730 described in USP 3,645,992 (Elston)). For both the linear and substantially linear interpolymers, however, the term "homogeneously branched" means that the comonomer is randomly distributed within a given interpolymer molecule and wherein substantially alI of the interpolymer , molecules have the same ethylene/comonomer ratio within that interpolymer.
The term "linear ethylene/oc-olefin interpolymer" does not refer to high pressure branched (free-radical polymerized) polyethylene which is known to those skilled in the art to have numerous long chain branches.
The homogeneously branched substantially linear io ethylene/oc-olefin copolymers and interpolymers also have a single melting point, as opposed to traditional Ziegler polymerized (heterogeneously branched) polymers having two or more melting points, as determined using differential scanning calorimetry (DSC) over a temperature range of from -20°C to 150°C. In addition, the novel homogeneously branched i5 substantially linear ethyleneloc-olefin copolymers and interpolymers have melting points which correlate with the density of the copolymer or interpolymer, that is, as the density decreases, the peak melting point of the polymer decreases in a directly linear fashion. Heterogeneously branched ethylene polymers have peak melting points which do not vary 2o substantially with the density of the polymer, primarily due to the presence of a high density polymer fraction which melts at about 122°C
(the melting point of homopolymer linear polyethylene).
The density of the homogeneously branched substantially linear ethylene/oc olefin interpolymers or copolymers (as measured in accordance 25 with ASTM D-792) for use in the present invention is generally less than 0.94 g/cm3 and preferably from 0.85 g/cm3 to 0.94 g/cm3.
Generally, the homogeneously branched substantially linear ethylene/oc-olefin polymer is used alone in the seal layer of the film or film structure. However, the homogeneously branched substantially linear 3o ethylene/oc-olefin polymer can be blended with other polymers for use as the heat seal layer. Generally, the amount of the homogeneously branched substantially linear ethylene/oc-olefin polymer is from 10 percent to 100 percent, by weight of the film structure.
The molecular weight of the homogeneously branched 35 substantially linear ethylene/oc-olefin interpolymers and copolymers for use in the present invention is conveniently indicated using a melt index _g_ measurement according to ASTM D-1238, Condition 190'C/2.16 kg (formerly known as "Condition (E)" and also known as I2). Melt index is inversely proportional to the molecular weight of the polymer. Thus, the higher the molecular weight, the lower the melt index, although the relationship is not linear. The melt index for the homogeneously branched substantially linear ethylene/o:-olefin interpolymers and copolymers useful herein is generally 10 grams/10 minutes (g/10 min) or less, preferably from 0.01 g/10 min to 10 g/10 min.
Another measurement useful in characterizing the molecular to weight of th~= homogeneously branched substantially linear ethylene/0~-olefin interpolymers and copolymers is conveniently indicated using a melt index measurement according to ASTM t:)-1238, Condition 190'C/10 kg (formerly known as "Condition (N)" and also known as I10)-The ratio of these two melt index terms is the melt flow ratio and is is designated as I10/I2. For the homogeneously branched substantially linear ethylene/OC-olefin interpolymers and copolymers used in this invention, the I10/I2 ratio indicates the degree of long chain branching, that is, the higher the I10/I2 ratio, the more long chain branching in the polymer.
Generally, the I10/I2 ratio of the homogeneously branched substantially 20 linear ethylene/CC-olefin interpolymers and copolymers is at least 5.63, preferably at least 7, especially at least 8 or above. Generally, the I10/I2 ratio can be as high as 30, preferably no higher than 20.
The molecular weight distribution (Mw/Mn) of the homogeneously 25 branched substantially linear ethylene/oc-olefin interpolymers and copolymers is analyzed by gel permeation chromatography (GPC) on a Waters 150C high temperature chromatographic unit equipped with three mixed porosity columns (Polymer Laboratories 103, 104, 105, and 106), operating' at a system temperature of 140°C. The solvent is 1,2,4-trichlorobenzene, so from which 0.3 percent by weight solutions of the samples axe prepared for injection. The flow rate is 1.0 milliliters/minute and the injection size is 200 microliters.
The molecular weight determination is deduced by using narrow molecular weight distribution polystyrene standards (from Polymer 35 Laboratories) in conjunction with their elution ~rolumes. The equivalent polyethylene molecular weig'r~ts are determined by using appropriate Mark-*Trade-mark s Houwink coefficients for polyethylene and polystyrene (as described by Williams and Word in journal of Polvme~ Science, Polymer Letters, Vol. 6, (621) 1968.) to derive the following~equation: -Mpolyethylene = a~'' (Mpolystyrene)b- ~ ' ~, -In this equation, a = 0.4316 and b = 1Ø Height average molecular weight, MW. is calculated in the usual manner according to the following ~o formula:'M,~ = E wi° Mi. Where wi-and M~ ire the weight fraction and ' ~ .
molecular'Weight, respectively, o'f the ith Erection eluting from the GPC
column. -For the homogeneously branched substantially linear ethylene/ac-olefin interpolymers and copolymers, the Mw/Mn is preferably a from 1_5 to 2_5, especially 2.
Additives, known to those skilled in the art, such as antioxidants (for example,. hindered phenolics (for. example, Irganox~ 1010 or Irganox~ 1076 made by Ciba Geigy Corp.), phosphites (for exaople, 2o Irgafos~ 168 made by Ciba Geigy Corp.)), cling additives (for example;
polyisobutylene (Pr8)), Standostab P~PQT"' supplied by Sandoz, anti-block additives, slip additives, U~,l stabilizers, pigments, processing aids, can also be added to the polymers from which the pouches of the present invention are made.
The 'theological processing index' (PI) is the apparent viscosity (in kpoise) of a polymer measured by a gas extrusion rheometer (G~R). The gas extrusion rheometer is described by M.vShida, R.N. Shroff and L.V. Cancio in.poly~r_ g.naineerina Science, Vol. 17, no_ 11, p. 770 (1977), and in °Rheometers for Molten Plastics' by John Dealy, published by Van Nostrand Reinhold Co. (1982) on page 97-99. All GER experiments .are perfortaed at a temperature~of 190°C, at nitrogen pressures between .
5250 to S00 psig (36.3 to 3.55 MPA) using a 0_0296 inch (0.752 ~) diameter, 20:1 L/D die with an entrance angle of 180°. For the as homogeneously branched ethylene polymers described herein, the PI is the apparent viscosity (in kpoise) of a material measured by G~R at an -1(1-WO 95/00587 216 5 3 4 0 PCT~S94/06730 apparent shear stress of 2.15 x 106 dyne/cm2. The novel substantially linear ethylene/ot-olefin interpolymers and copolymers described herein preferably have a PI in the range of 0.01 )cpoise to 50 kpoise, more preferably about 15 kpoise or less. The novel substantially linear ethylene/oc--olefin polymers described herein for use in the pouches have a PI less than or equal to about 70 percent of the PI of a linear ethylene/ot-olefin polymer at about the same or substantially the same I2 and Mw/Mn and the same comonomer(s).
An apparent shear stress vs. apparent shear rate plot is used io to identify the melt fracture phenomena. According to Ramamurthy in Journal of Rheo1_oav, 30(2), 337-357, 1986, above a certain critical flow rate, the abserved extrudate irregularities may be broadly classified into two main types: surface melt fracture and gross melt fracture. Surface melt fracture occurs under apparently steady flow conditions and ranges in i5 detail from loss of specular gloss to the more severe form of "sharkskin".
Gross melt fracture occurs at unsteady flow conditions and ranges in detail from regular (alternating rough and smooth, helical, etc.} to random distortions.
Ramamurthy {Journal of Rheoloav) and Moynihan, Baird and zo Ramanathan in Journal of Non-Newtonian Flu,'_d Mechan,'_cs, 36, 255-263 (1990), both disclose that the onset of sharkskin (that is, melt fracture) for linear low density polyethylene {LLDPE) occurs at an apparent shear stress of 1-1.4 x 106 dyne/cm2, which was observed to be coincident with the change in slope of the flow curve. Ramamurthy also discloses that the 25 onset of surface melt fracture or of gross melt fracture for high pressure low density polyethylene (HP-LDPE) occurs at an apparent shear stress of about 0.13 MPa (1.3 x 106 dynes/cm2).
Kalika and Denn in Journal of Rheoloav, 31, 815-834 (1987) confirmed the surface defects or sharkskin phenomena for LLDPE, but the 3o results of their work determined a critical shear stress of 2.3 x 106 dyne/cm2, significantly higher than that found by Ramamurthy and Moynihan et al.
In this disclosure, the onset of surface melt fracture {OSMF) is characterized at the beginning of losing extrudate gloss at 35 which the surface roughness of extrudate can only be detected by 40X
magnification. Surprisingly, the critical shear rate at onset of surface melt fracture for the substantially linear ethylene/a-olefin interpolymers and copolymers is at least 50 percent greater than the critical shear rate at the onset of surface melt fracture of a linear ethyleng/oc-olefin interpolymer or copolymer (either a heterogeneously branched polymer (for , s example, LLDPE) or a homogeneously branched polymer (for example, that described in USP 3,645,992 (Elston)) having about the same or y substantially the same I2 and Mw/Mn and the same comonomer(s).
The critical shear rate and critical shear stress at onset of surface melt fracture (OSMF) and onset of gross melt fracture (OGMF) will 1o be used herein based on the changes of surface roughness and configurations of the extrudates extruded by a GER. In contrast to both LLDPE and high pressure LDPE, the critical shear stress at onset of gross melt fracture for the substantially linear ethylene/oc-olefin interpolymers and copolymers, especially those having a density greater than about 0.9 is g/cm3, is greater than about 4 x 106 dynes/cm2.
The films and film structures disclosed herein can be monolayer or multilayer film structures, with the proviso that the homogeneously branched substantially linear ethylene/oc-olefin copolymers 2o and interpolymers be used as at least one layer, preferably the seal layer. The thickness of the seal layer may be from at least about 0.1 mil (2.5 microns) and greater, preferably from 0.2 mil (5 microns) to 10 mil (254 microns) and more preferably from 0.4 mil (10 microns) to 5 mil (127 microns).
25 A surprising feature of the pouch's film structure of the present invention is the film's broad heat sealing range, especially in view of the substantially linear ethylene polymer's narrow melting point range (measured using differential scanning calorimetry (DSC)).
Generally, the heat sealing range of the film structure can be from 50°C
3o to 160°C and preferably from 75°C to 130°C. It has been found that the seal layer of the present invention has a broader heat seal range than prior art polyethylene film made from heterogeneously branched ethylene polymers, even at the approximately the same density. A broad heat sealing range is important to allow for more flexibility in the heat 35 sealing process used for making pouches from the film structure.
Generally, the melting point range of the substantially linear ethylene polymer used to make the film structure having the heat seal ranges specified above can be from 50°C to 130°C and preferably from 55°C to 115°C.
Another unexpected feature of the pouch's film structure of the present invention is the film's heat seal strength at low temperatures. Generally, the film structure of the present invention achieves a hot tack strength of at least about 1 Nlinch (39.4 N/m) at a seal bar temperature of about 110°C and at less than about 0.3 seconds using the DTC Hot Tack Strength Method defined hereinbelow or achieves a io heat seal strength of at least 1 lbf/inch (175 N/m) at a seal bar temperature of about 110°C and at less than 0.4 seconds using the DTC
Heat Seal Strength Method defined hereinbelow. The film structure of the present invention also has a hot tack or heat seal initiation temperature of less than about 110°C at a force of at least about 1 N/inch (39.4 N/m).
is It has been found that a seal made with the seal layer of the present invention has a higher strength at lower sealing temperatures than seals with a prior art polyethylene having higher densities. A high heat seal strength at low temperatures is important to allow conventional packaging equipment such as a vertical form, fill and seal machine to run at faster 2o rates and t:o produce pouches with fewer leakers.
It is believed that the use of at least one substantially linear ethylene polymer in a seal layer of a film structure for pouches of the present invention (1) provides a pouch that can be fabricated at a fast rate through a form, fill and seal machine and (2) provides a pouch 25 package having few leakers, particularly when the pouch of the present invention is compared to pouches made with linear low density polyethylene, ultra linear low density polyethylene, high pressure low density polyethylene, or a combination thereof.
In one embodiment of the present invention, a pouch is made 3o from a film structure in tubular form and having transversely heat sealed ends. The film structure has at least one film layer comprising:
(I) from 10 to 100 percent by weight of at least one layer comprising at least one homogeneously branched substantially linear ethylene/a--olefin interpolymer characterized as having:
WO 95/00587 ~21 ~ 5 3 4 0 PCT/US94/06730 {a) a melt flow ratio, I10/I2, >_ 5.63, and (b) a molecular weight distribution, Mw/Mn, defined by the equation: Mw/Mn <_ tIlO/I2) - 4.63; and (II) from 0 to 90 percent by weight of at least one polymer selected from the group consisting of a heterogeneously branched Linear ethylene/C3-Clg Oc-olefin copolymer, a high-pressure low density polyethylene, and an ethylene-vinyl acetate copolymer.
The heterogeneously branched linear ethylene/C3-Clg oc-olefin copolymer of (II) is generally a linear low density polyethylene (such as io that made using Ziegler catalysis). The linear low density polyethylene is often further divided into subsets labeled as very low density polyethylene (VLDPE) or ultra low density polyethylene tULDPE). VLDPE and ULDPE are interchangeable terms herein and are generally used in this manner by those skilled in the art. Generally, the density of the linear i5 low density polyethylene of (II) ranges from 0.87 g/cm3 to 0.94 g/cm3, preferably from 0.87 g/cm3 to 0.915 g/cm3. Preferably, the heterogeneously branched linear low density ethylene/C3-Clg a-olefin copolymer of (II) has a melt index from 0.1 to 10 g/10 minutes.
Preferably, the high-pressure low density polyethylene of (II) 2o has a density from 0.916 to 0.93 g/cm3 and a melt index from 0.1 to 10 g/10 minutes.
Preferably, the ethylene-vinyl acetate copolymer of (II) has a weight ratio of ethylene to vinyl acetate from 2.2:1 to 24:1 and a melt index from 0.2 to 10 8110 minutes.
25 Another embodiment of the present invention includes a pouch made from a blend of:
(a) from 10 to 100 percent by weight of at least one homogeneously branched substantially linear ethylene copolymer interpolymerized from ethylene and at least one alpha-olefin in the range 30 of C3-C2p and having a density of less than 0.915 g/cm3 and a melt index of less than 10.0 g/10 minutes, and (b) from 0 to 90 percent by weight of at least one polymer selected from the group consisting of a heterogeneously branched linear ethylene/C3-Clg oc-olefin copolymer, a high-pressure low-density , .
35 polyethylene and an ethylene-vinyl acetate (EVA) copolymer.
The heterogeneously branched linear ethylene/C3-C1g a-olefin copolymer of (IT) generally is a linear low density polyethylene (such as that made using Ziegler catalysis). The linear low desnity polyethylene includes very low density polyethylene (VLDPE) and ultra low density polyethylene (ULDPE), as described previously. Generally, the density of ~ the linear low density polyethylene of (II) ranges from 0.87 g/cm3 to 0.94 g/cm3, preferably from 0.87 g/cm3 to 0.915 g/cm3. Preferably, the heterogeneously branched linear low density ethylene/C3-C1g oc-olefin copolymer of (II) has a melt index from 0.1 to 10 g/10 minutes.
io Preferably, the high-pressure low density polyethylene of (b) has a density from 0.916 to 0.93 g/cm3 and a melt index from 0.1 to 10 g/10 minutes.
Preferably, the ethylene-vinyl acetate copolymer of (b) has a weight ratio of ethylene to vinyl acetate from 2.2:1 to 24:1 and a melt i5 index from 0.2 to 10 g/10 minutes.
With reference to Figures 3 to 5, the film structure of the pouch of the present invention also includes a multilayer or composite film structure 30, preferably containing the above-described polymeric seal layer being the inner layer of the pouch.
2o As will be understood by those skilled in the art, the multilayer film structure for the pouch of the present invention may contain various combination of film layers as long as the seal layer forms part of the ultimate film structure. The multilayer film structure for the pouch of the present invention may be a coextruded film, a coated film 25 or a laminated film. The film structure also includes the seal layer in combination with a barrier film such as polyester, nylon, ethylene-vinyl alcohol copolymer (EVOH), polyvinylidene dichloride (PVDC) such as Saran"' (Trademark of The Dow Chemical Company) and metallized films. The end use for the pouch tends to dictate, in a large degree, the selection of the 30 other material or materials used in combination with the seal layer film.
The pouches described herein will refer to seal layers used at least on the inside of the pouch.
One embodiment of the film structure 30 for the pouch of the present invention, shown in Figure 3, comprises a homogeneously branched 35 substantially linear ethylene polymer seal layer 31 and at least one polymeric outer layer 32. The polymeric outer layer 32 is preferably a polyethylene film layer, more preferably a heterogeneously branched linear polyethylene referred to hereinafter as "linear low density polyethylene"
("LLDPE") and/or "ultra linear low density polyethylene" .("ULDPE") and/or "very low density polyethylene ("VLDPE"). An example of a commercially , available LLDPE is DOWLEX~ 2045 {Trademark of and commercially available from The Dow Chemical Company). An example of a commercially available ULDPE is ATTANE~ 4201 (Trademark of and commercially available from The Dow Chemical Company).
The LLDPE (including both the VLDPE and ULDPE) useful herein io are heterogeneously branched linear copolymers of ethylene and a minor amount of an alpha-olefin having from 3 to 18 carbon atoms, preferably from 4 to 10 carbon atoms (for example, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, and 1-decene) and most preferably 8 carbon atoms (for example, 1-octene). Generally, the heterogeneously branched LLDPE are i5 made using Ziegler catalysis {for example, using the method described in U.S. Patent No. 4,076,698 (Anderson et al.)).
The LLDPE for the outer layer 32 generally has a density greater than 0.87 g/cm3, more preferably from 0.9 to 0.93 g/cm3; generally has a melt index (I2) from 0.1 to 10 g/10 min, preferably from 0.5 to 2 2o g/10 min; and generally has an Ilp/I2 ratio from 5 to 20, preferably from 7 to 20.
For the heterogeneously branched LLDPE (including both VLDPE
and UDLPE), the Il0/I2 ratio tends to increase as the molecular weight (Mw/Mn) of the LLDPE increases, in surprising contradistinction to the 25 novel homogeneously branched substantially linear ethylene/a.-olefin interpolymers and copolymers discussed herein.
The thickness of the outer layer 32 may be any thickness so long as the seal layer 31 has a minimum thickness of 0.1 mil (2.5 microns).
3o Another embodiment of the film structure 30 for the pouch of the present invention, shown in Figure 4, comprises the polymeric layer 32 sandwiched between two polymeric seal layers 31.
Still another embodiment of the film structure 30 for the pouch of the present invention, shown in Figure 5, comprises at least one 35 polymeric core layer 33 between at least one polymeric outer layer 32 and at least one polymeric seal layer 31. The polymeric layer 33 may be the WO 95/00587 ~ ~ PCT/US94/06730 same LLDPE film layer as the outer layer 32 or preferably a different LLDPE, and more preferably an LLDPE that has a higher density than the outer layer 32. The thickness of the core layer 33 may be any thickness so long as the seal layer 31 has a minimum thickness of 0.1 mil (2.5 microns).
Yet another embodiment (not shown) of the film structure for the pouch of the present invention can be a structure including a seal layer 31 and another polyethylene film layer referred to hereinafter as "high pressure low-density polyethylene" ("LDPE"). The LDPE layer 1o generally has a density from 0.916 to 0.930 g/cm3 and has a melt index from 0.1 to 10 g/10 min. The thickness of the LDPE layer may be any thickness so long as the seal layer 31 has a minimum thickness of 0.1 mil (2.5 microns).
Still another embodiment (not shown) of the film structure for is the pouch of the present invention can be a structure including a seal layer 31 and a layer of EVA copolymer having a weight ratio of ethylene to vinyl acetate from 2.2:1 to 24:1 and a melt index of from 0.2 to 20 g/10 min. The thickness of the EVA layer may be any thickness so long as'the seal layer 31 has a minimum thickness of 0.1 mil (2.5 microns).
2o The thickness of the film structure used for making the pouch of the present invention is from 0.5 mil (12.7 microns) to 10 mils (254 microns), preferably from 1 mil (25.4 microns) to 5 mils (127 microns).
As can be seen from the different embodiments of the present invention shown in Figures 3-5, the film structure for the pouches of the 25 present invention has design flexibility. Different LLDPEs (for example, VLDPE and tJLDPE) can be used in the outer and core layers to optimize specific film properties such as film stiffness. Thus, the film can be optimized for specific applications such as for a vertical form, film and seal machine.
3o The polyethylene film structure used to make a pouch of the present invention is made by either the blown tube extrusion method or the cast extrusion method, methods well known in the art. The blown tube extrusion method is described, for example, in Modern Plastics Mid-October 1989 Encyclopedia Issue, Volume 66, Number 11, pages 264 to 266. The cast 35 extrusion method is described, for example, in Modern Plastics Mid-October 1989 Encyclopedia Issue, Volume 66, Number 11, pages 256 to 257.
Embodiments of the pouches of the present invention, shown in Figures 1 and 2, are hermetically sealed containers filled with "flowable materials". By "flowable materials" it is meant materials which are , flowable under gravity or which may be pumped, but the term "flowable materials" does not include gaseous materials. The flowable materials , include noncarbonated liquids (for example, milk, water, fruit juice, wine) and carbonated liquids {for example, soda, beer, water); emulsions (for example, ice cream mix, soft margerine); pastes (for example, meat io pastes, peanut butter); preserves (for example, jams, pie fillings, marmalade); jellies; doughs; ground meat (for example, sausage meat);
powders {for example, gelatin powders, detergents); granular solids (for example, nuts, sugar, cerial); and like materials. The pouch of the present invention is particularly useful for packaging liquids (for i5 example, milk). The flowable material may also include oleaginous liquids (for example, cooking oil or motor oil).
Once the film structure for the pouch of the present invention is made, the film structure is cut to the desired width for use in conventional pouch-forming machines. The embodiments of the pouch of the 2o present invention shown in Figures 1 and 2 are made in so-called form, fill and seal machines well known in the art. With regard to Figure 1, there is shown a pouch 10 being a tubular member 11 having a longitudinal lap seal 12 and transverse seals 13 such that, a "pillow-shaped" pouch is formed when the pouch is filled with flowable material.
25 With regard to Figure 2, there is shown a pouch 20 being a tubular member 21 having a peripheral fin seal 22 along three sides of the tubular member 11, that is, the top seal 22a and the longitudinal side seals 22b and 22c, and having a bottom substantially concave or "bowl-shaped" member 23 sealed to the bottom portion of the tubular seal 30 21 such that when viewed in cross-section, longitudually, substantially a semi-circular or "bowed-shaped" bottom portion is formed when the pouch is filled with flowable material. The pouch shown in Figure 2 is the so-called "Enviro-Pak" pouch known in the art.
The pouch manufactured according to the present invention is 35 preferably the pouch shown in Figure 1 made on so-called vertical form, fill and seal (VFFS) machines well known in the art. Examples of commercially available VFFS machines include those manufactured by Hayssen or Prepac. A VFFS machine is described in the following reference: F. C.
Lewis, "Form-Fill-Seal," Packaging Encyclopedia, page 180, 1980.
In a VFFS packaging process, a sheet of the plastic film structure described herein is fed into a VFFS machine where the sheet is formed into a continuous tube in a tube-forming section. The tubular member is formed by sealing the longitudinal edges of the film together --either by lapping the plastic film and sealing the film using an inside/outside seal or by fin sealing the plastic film using an 1o inside/inside seal. Next, a sealing bar seals the tube transversely at one end being the bottom of the "pouch", and then the fill material, for example milk, is added to the "pouch." The sealing bar then seals the top end of the pouch and either burns through the plastic film or cuts the film, thus, separating the formed completed pouch from the tube. The i5 process of making a pouch with a VFFS machine is generally described in U.S. Patent Nos. 4,503,102 and 4,521,437.
The capacity of the pouches of the present invention may vary.
Generally, the pouches may contain from 5 milliliters to 10 liters, preferably from 10 milliliters to 8 liters, and more preferably from 1 20 liter to 5 liters of flowable material.
The use of the homogeneously branched substantially linear ethylene/Ot~-olefin interpolymer seal layer of the present invention in a two or three-layer coextruded film product will provide a film structure that can be used for making pouches at a faster rate in the VFFS and such 25 pouches produced will contain fewer leakers.
The pouches of the present invention can also be printed by using techniques known in the art, for example, use of corona treatment before printing.
The pouches of the present invention have excellent 3o performance results when tested by the 5 Foot (1.52 m) Drop Test--a test which is defined herein. Under the 5 Foot (1.52 m) Drop Test, the pouches preferably have a percent failure of less than 40 percent and more preferably less than 20 percent, and especially less than 10 percent.
Use of the pouch for packaging consumer liquids such as milk 35 has its advantages over containers used in the past: the glass bottle, paper carton, and high density polyethylene jug. The previously used containers consumed large amounts of natural resources in their manufacture, required a significant amount of space in landfill, used a large amount of storage space and used more energy in temperature control of the product (due to the heat transfer properties of the container). , The pouches of the present invention made of thin film, used for liquid packaging, offers many advantages over the containers used in the past. The pouches: (1) consume less natural resources, (2) require less space in a landfill, (3) can be recycled, (4) can be processed easily, (5) require less storage space, (6) use less energy for storage io (heat transfer properties of package), (7) can be safely incinerated and (8) can be reused (for example, the empty pouches can be used for other applications such as freezer bags, sandwich bags, and general purpose storage bags).
is Coextruded blown film samples having an A/B/A structure were made using layer ratios of: A=15 percent (by weight of the total structure) and B= 70 percent (by weight of the total structure). Layer B
was an ethylene/1-octane LLDPE having a melt index (I2) of about 1 g/10 2o minute and a density of about 0.92 g/cm3 and did not contain additives.
In the examples, resins 1-3 were all heterogeneously branched ethylene/1-octene copolymers and resins 4-7 were all homogeneously branched substantially linear ethylene/1-octane copolymers. Table 1 summarizes physical properties of the resins used to make A/B/A coextruded blown film 25 samples described in the examples and comparative examples:
Table 1 Resin Resin Melt IndexDensity Mw/Mn I10/I2 type (I2) (g/cm3) -/10 min) 1 * LLDPE 1 0.92 3.73 8 2* ULDPE 1 0.912 4.03 8.2 3 * ULDPE 1 0.905 4.2 8.7 4 SLEP 1.03 0.8713 2.11 7.81 5 SLED 1 0.902 2.02 9.3 6 SLEP 0.97 0.9104 2.2 10.()5 7 SLEP 1.01 0.91fi 2.27 9.48 8 * S1v43 N A N A Iv A N A
Film made by DuPont *Comparative example NA = Not applicable Resins 1, 2, 5, 6, and 7 were dry blended to contain 4,000 ppm Si02 and 1,200 ppm Erucamide. Resin 3 was dry blended to contair 6,000 ppm Si02 and 1,200 ppm Erucamide. Resin 4 was dry blended to contain 14,000 ppm Si02 and 1,200 ppm Erucamide. Resin 8 was a monolayer milk pouch film designated "SM3" made by and available from DuPont Canada and was believed to be a blend of about 8 percent (by weight) of a low density io polyethylene having a density of about 0.92 g/cm3 and about 92 percent (by weight) of a heterogeneously branched linear low denisty polyethylene.
The SM3 film had a final film density reported by DuPont as 0.918 g/cm3.
Film samples were produced on an Egan three layer extruder system. Extruder A had a 2.5 inch (6.35 cm) diameter (Barr2 type) screw is equipped with a Maddox mixer, L/D of 24.1, 60 HP drive. Extruder B had a 2.5 inch (6.35 cm) diameter (DSB II type) screw equipped with a Maddox mixer, L/D of 24:1, 75 HP drive. Extruder C had a 2 inch (5.08 cm) diameter (Modified MHD (Johnson) type) screw equipped with a Maddox mixer, L/D of 24:1, 20 HP drive. The blown film line was. also equipped with an E?
zo inch (20.32 cm) 3-layer co~.~~ctruding die body, a Gloucester Tower, a Sano~' collapsing frame, a Sano bubble sizing cage, and a Sano bubble enclosure.
Each-of the film samples was made at 3 mil target thickness using a blow-up ratio (BUR) of 2.5:1.
*Trade-mark Each film was tested according to the following test anethods:
Puncture- Puncture was measured by using an I,nstrorl Tensile Tester with an integrator, a specimen holder, and a puncturing device.
The Instron was set to obtain a crosshead speed of 10 inches/minute (25.4 em/minute) and a chart speed (if used) of llr inches/minute (25.4 cm/minute). Load range of SO percent of the load cell capacity (100 1b.
(45.36 kg) load for these tests) was used. The puncturing device was installed to the Instron such that the clamping unit was attached to the to lower mount and the ball was attached to the upper mount on the cros_~hc.ad.
Five film specimens were used (each 6 inches (15_24 cm) square). The specimen was clamped in the film holder and the fiirn holder way: secured to the mounting bracket_ The crosshead travel was ~aec and continued until the specimen breaks. Puncture resistance was defined as th,e energy to t5 puncture divided by the volume of the film under test. Puncture resistance (PR.) was calculated as follows:
PR = E/((12)(T)(A)) where PR = puncture resistance (ft-lbs/in3), 2o E = energy (inch-lbs) = area under the load displacement curve, 12 = inches/foot, T = film thickness (inchesi, and A = area of the film sample in the clamp = 12.56 in2 (81 cm2);
i5 part Impact: ASTM D1709, method A;
1;1_mendorf Tear: ASTM D1922;
Tensile Properties: ASTM D882 using an Instron tensile tester 30 (cross-head speed of 500 mm/min, full scale load of S kg, threshold of I
percent of full scale load, break criterion of 80 percent, 2 inch (5.08 cm) gauge length and 1 inch (2.54 cm? sample width); , Coefficient of Friction: ASTM D1894_ Coefficient of friction 35 range is important in order for the film..;to properly move over the forming collars in a vertical-form-fill and ~~c:.a~ machine (for example, a Hayssen *Trade-mark _;p_ form-fill-seal machine): if the coefficient of friction is too low, the film may be too slippery for the pull belts to grip the film and if the coefficient of friction is too high, the film may be too,tacky for the machine to pull the film over the forming collar; typical targets for the Hayssen form-fill-seal machine are:
(i) inside/outside coefficient of friction from 0.10 - 0.30 and (ii) outside/outside coefficient of friction from 0.10 - 040;
Percent and 2 Percent Secant Modulus: ASTM D882. Film io stiffness is important, especially for "free-standing" pouches like that shown in Figure 2. The 1 percent and 2 percent secant modulus tests provide an indication of the stiffness of the film;
Heat Seal Strength: This test measures the force required to separate a seal after the seal has been allowed to cool. Seals were made using the DTC Hot Tack Tester but only the heat seal portion of the unit was used. Conditions used were:
Specimen width: 24.4 mm Sealing time: 0.5 seconds 2o Sealing pressure: 0.27 N/mm/mm No. samples/time: 5 Temperature increments: 5°C.
Seal strength was determined using an Instron Tensile Tester Model No. 1122. The film samples were exposed to relative humidity of 50 percent and a temperature of 23°C for 24-48 hours prior to testing.
Instron test conditions were as follows:
Direction of pull: 90° to seal Crosshead speed: 500 mm/minute Full scale load (FSL): 5 kg 3o Threshold: 1 percent of FSL
Break Criterion: 80 percent Gauge length: 2.0 inches (5.08 cm) and Sample width: 1.0 inch (2.54 cm);
uPar Seal Strenath Versus Sealina Time~ Films were sealed using a DTC Hot Tack Tester model no. 52D. Conditions used were as follows:
Specimen width: 24.4 mm Sealing time: varied Sealing pressure: 0.27 N/mm/mm No. samples/time: 5 Sealing temperature range: 0.1 seconds - 1.0 seconds Temperature: 105°C.
io The seal strength was determined using an Instron Tensile Tester Model No. 1122 using the conditions described in the Heat seal Strength test.
Hot Tack Performance: The hot tack test measures the force i5 required to separate a heat seal before the seal has had a chance to cool.
This test simulates filling a pouch with material just after the seal was made. The hot tack strength is typically the limiting factor in increasing line speeds of a pouch manufacturing and filling operation.
In this test, the films were tested using a DTC Hot Tack 20 Tester Model No. 52D. Conditions used were:
Specimen width: 24.4 mm Sealing Time: 0.5 seconds Sealing Pressure: 0.27 N/mm/mm Delay Time: 0.5 seconds z5 Peel Speed: 150 mm/sec Number of samples/temperature: 5 Temperature Increments: 5°C
Temperature Range: 70°C - 130°C
Hot tack failure of the seals generally occurs in three 3o stages: no seal; seals which pull apart (peeling); and film failure (where the molten film pulls apart with no apparent effect on the seal). Film failure region begins where the hot tack strength reaches a maximum level.
In each case, film failure occurs just in front of the seal. A force of 1 N/inch (0.4 N/cm) was arbitrarily selected to determine the seal 35 initiation temperature.
Water Filled Pouch Perfromance: Pouches were manufactured using a Hayssen Ultimo VFFS unit and contained 2L of water. The following conditions were used on the Hayssen:
Model No.: RCMH@-PRA
M.A. No. U19644 Mass of water = 2,00U grams Bag size = 7 inches (17_8 cm) by 12.5 inches (31.8 cm) Film width = 15.25 inches (38.7 cm) Registration Rolls: on from 5° to 135°
Pull Belts: on from 10° to 140°
Knife. on from 146° to 265°
Jaw close: from 136° to 275°
Platen: on from 136° to 265°
Stager: off is Auxiliary: on from 137° to 355°
Quali-seal: on from 140° to 265°
Start Delay: SO ms Bag eject: on End air seal: 200 ms 2o Empty bags/minute: 60 Filled bags/minute: 15 Seal bar pressure: 150 psi (1034 kPa) Type of side seal: lap, and Seam seal temperature: 260°F (127°C).
25 A Pro/Fill 3000 liquid filler was attached to the VFFS. The settings on the Pro/Fill 3000 were: P.S. = 35, volume = 0903, and C_O.A. _ 70;
(i) Fnd Heat Seal Strength: Water filled pouches were made using sealing bar temperatures starting at 280°F
(138°C). Five 3o pouches were made at this temperature, then the sealing bar temperature was reduced in 5°F (2.8°C) increments until the pouches no longer held water. Five pouches were obtained from each temperature, the water drained, and the empty pouch tested for seal strength using an Instron Tensile Tester Model No. 1122 using the conditions described in the Heat 35 seal Strength test.
*Trade-mark ~ 16 5 3 4 0 PCT~S94/06730 At the seal bar temperature where the pouch no longer holds water, the force of the water being pumped into the pouch was believed to be too great for the hot, semi-molten seal. As a result,, the seal separated and it appeared that the pouch experienced hot tack failure at s this temperature;
(ii) 5 Foot (1 52 m? Drop Test' The seal bar , temperature was set to 250°F (121°C)and 100 pouches were made from each film structure. The pouches were dropped from a height of 5 feet (1.52 m) such that the pouch landed on the platen seal.
io Tables 2, 2A and 3-9 summarize physical property data for the A/B/A film structures made using the resins described in Table 1. In the Tables, "MD" means machine direction and "CD" means cross/transverse direction.
W~ 95/00587 ~ ~ PCT/LTS94/06730 Table 2 Resin i** 2** 3** 4 5 6 7 8**
Av . au a (mils)3.09 3.03 3.04 2.29 3.18 3.08 3.10 3.17 .
1 percent secant31,92828,50427,87321,15425,29128,42229,251NM*
modulus, psi (220)(197)(192)(146)(174)(196)(202) (MD) (MPa) 1 percent secant39,63830,33431,27424,78128,02230,69635,169NM*
modulus, psi (273)(209)(216)(171)(193)(212)(242) (CD) (MPa) 2 percent secant28,50924,21823,95117,62221,84524,73826,09422,800 modu:lus,psi(MD)(197)(167)(165)(122)(151)(171)(180)(157) (MPa) 2 percent secant33,73026,08726,78319,32224,00926,75430,13025,449 modulus, psi (233)(180)(185)(133)(166)(184)(208)(175) (CD) (MPa) Elmendorf tear,534 530 524 283 480 586' 510 239 g/mil (k /mm)(MD) (21) (20.8)(20.6)(11.1)(18.9)(23) (20) (9.4) Elmendorf tear,654 644 638 527 685 640 632 394 g/mil (k /mm) (CD) (25.7)(25.4)(25.1)(20.7)(27) (25.2)(24.9)(15.5) Dart Im act 596 751 889 >1000897 841 681 465 ( ) Punchire, ft-lbs/in326.0 25.8 26.5 52.0 27.8 27.7 24.2 13.8 Q/cm3) (2.15)(2.13)(2.19)(4.3)(2.3)(2.29)(2) (1.14) Tensile yield, 1580 1334 1308 1145 1278 1368 1500 1558 psi (MPa) (10.9)(9.2)(9) (7.9)(8.8)(9.4)(10.3)(10.7) (MD) Tensile yield, 1732 1417 1395 1050 1342 1452 1614 15t psi (MPa) (11.9)(9.8)(9.6)(7.2)(9.3)(10) (11.1)(10.5) (CD) *NM = Not measured **Comparative Example Only WO 95/00587 ~ ~ ~ 5 3 4 0 PCT/US94/06730 Table 2A
Resin 1** 2** 3** 4 5 6 7 8**
Ultimate tensile,5511 5338 5369 5086 6386 5653.5794 5639 psi (MPa) (38) (36.8)(37) (35.1)(44) (39) (39.9)(38.9) (MD) Ultimate tensile,5768 4873 5145 4293 6065 5310 5697 6173 psi (MPa) (39.8)(33.6)(35.4)(29.6)(41.8)(36.6)(39.3)(42.6) (CD) Elongation (percent)685 668 667 593 702 662 687 761 {MD) Elongation (percent)748 701 719 719 716 688 729 682 (CD) Toughness, ft-lbs/in31364 1224 1228 1017 1448 1304 1439 1562 (J/cm3) (113)(101)(102)(84) (120)(108)(119)(129) (MD) Toughness, ft-lbs/in31549 1222 1293 1043 1399 1298 1507 1569 Q/~) {128)(101)(107)(86) (116)(107)(125)(130) (CD) *NM = Not measured **Comparative Example Only The data in Tables 2 and 2A show that films made using both the heterogeneously branched ethylene/a-olefin copolymers and those made using the novel homogeneously branched substantially linear ethylene/oc-olefin interpolymer had higher puncture resistance than the commercially available SM3 film.
Similarly, the data also show that films made using both the i0 heterogeneously branched ethylene/oc-olefin copolymers and those made using the novel homogeneously branched substantially linear ethylene/oc-olefin interpolymer had higher dart impact strength than the commercially available SM3 film. Furthermore, films made using the homogeneously branched substantially linear ethylene/a-olefin interpolymer had higher is dart impact strength than either the SM3 film or film made using heterogeneously branched ethylene/oc-olefin copolymers.
Elmendorf tear also was higher for films made from both the heterogeneously branched ethylene/oc-olefin copolymers and those made using the novel :homogeneously branched substantially linear ethylene/a-olefin interpolymer, as compared with the commercially available SM3 film.
s Table 3 Resin 1** 2** 3** 4 5 6 7 8**
Coefficient of friction Inside/inside Static 0.20 0.25 0.18 1.53 0.24 0.18 0.20 0.14 Kinetic 0.18 0.23 0.16 1.35 0.20 0.16 0.18 O.la Coefficient of friction Outside/outside Static 0.20 0.25 0.23 0.90 0.26 0.14 0.18 0.12 Kinetic 0.17 0.24 0.22 1.03 0.23 0.13 0.16 0.10 **Comparative Example Only The data in Table 3 shows that all of the films tested, except for that made using Resin 4, had a COF between 0.1 and 0.3.
WO 95/00587 21 b 5 3 4 0 PCT/US94/06730 Table 4 Hot Tack Strength, N/inch (N/cm) TemperatureResinResinResinResinResinResinResinResin C (F) 1** 2** 3** 4 5 6 ~7 8**
55 (131) NA NA NA 0.16 NA NA NA NA
(0.06) 65 (149) NA 0.10 NA 0.66 NA NA NA NA
(0.04) (0.26) 70 (158) NA 0.10 0.10 2.83 0.10 NA NA NA
(0.04)(0.04)(1.11)(0.04) 75 (167) NA 0.10 0.90 5.11 0.48 NA NA NA
(0.04)(0.4)(2.01)(0.19) 80 (176) NA 0.30 1.30 5.04 1.21 0.10 NA NA
(0.1)(0.51)(1.98)(0.48)(0.04) 85 (185) NA 0.49 2.10 3.14 2.46 0.20 NA NA
(0.19)(0.83)(1.24)(0.97)(0.08) 90 (194) NA 1.46 2.60 3.80 4.29 0.70 0.10 NA
(0.57)(1.02)(1.5)(1.69)(0.28)(0.04) 95 (203) 0 2.19 2.60 3.40 6.41 1.90 0.40 0 (0.86)(1.02)(1.34)(2.52)(0.75)(0.16) 100 (212) 0.40 2.78 3.10 3.21 6.95 4.30 0.90 0.30 (0.16)(1.09)(1.22)(1.26)(2.74)(1.69)(0.35)(0.12) 105 (221) 1.40 3.13 3.10 2.58 6.30 5.40 2.60 1.10 (0.55)(1.23)(1.22)(1.02)(2.48)(2.13)(1.02)(0.43) 110 (230) 2.90 3.06 3.00 2.39 5.80 5.70 4.20 2.10 (1.14)(1.20)(1.18)(0.94)(2.28)(2.24)(1.65)(0.83) 115 (239) 3.20 2.62 2.90 2.21 5.00 5.00 4.20 3.40 (1.26)(1.03)(1.14)(0.87)(1.97)(1.97)(1.65)(1.34) 120 (248) 3.30 2.41 3.00 1.64 4.20 4.20 4.00 3.60 (1.3)(0.95)(1.18)(0.65)(1.65)(1.65)(1.57)(1.42) 125 (257) 3.00 2.22 2.60 1.73 3.60 3.60 3.30 3.60 (1.18)(0.87)(1.02)(0.68)(1.42)(1.42)(1.3)(1.42) 130 (266) NM 2.10 NM 1.36 2.90 NM NM 3.50 (0.83) (0.54)(1.14) (1.38) **Comparative Example Only NA = Not Applicable; NM = Not Measured WO 95/00587 216 5 3 4 0 PCT~S94/06730 The data in Table 4 shows that films made using the novel homogeneously branched substantially linear ethylene/oc-olefin interpolymer had higher hot tack strength than film made from heterogeneously branched ethylene/ot olefin copolymers and higher hot tack strength than s commercially available SM3 film.
Figure 6 is a graphical illustration of film hot tack strength versus temperature for resin 7 and comparative resin 1.
Figure 7 graphically illustrates film hot tack strength versus temperature for resin 6 and comparative resin 2.
i0 Figure 8 is a graphical illustration of film hot tack strength versus temperature for resin 5 and comparative resin 3.
Figure 9 is a graphical illustration of film hot tack strength versus sealing time for resins 5-7 and comparative resins 1-3 and comparative film 8.
i5 Firgure 17 is a graphical illustration of maximum film hot tack strength versus resin density for resins 5-7 and comparative resins 1-3.
Table 5 Heat Seal Strength, lbs/inch (g/cm) TemperatureResinResin~ ResinResinResinResinResin Resin C (F) 1** 2** 3** 4 5 6 '7 8**
55 (131) NA NA NA 0 NA NA NA NA
60 (140) NA NA NA 1.20 NA NA NA NA
(214) 65 (149) NA NA NA 2.35 NA NA NA NA
(419) 70 (158) NA NA NA 1.87 NA NA NA NA
(334) 75 (167) NA NA 0 1.68 0 NA NA NA
(300) 80 (176) NA 0.09 0.06 2.51 0.54 NA NA NA
(16) (11) (448)(96) 85 (185) NA 0.21 0.14 2.67 2.38 NA NA NA
(38) (25) (477)(425) 90 (194) NA 0.10 1.30 2.86 3.90 0 NA NA
(18) (232)(510)(697) 95 (203) NA 0.61 3.01 2.49 4.18 1.66 NA NA
(109)(538)(445)(747)(296) 100 (212) NA 1.02 3.87 2.78 5.34 4.60 0 0 (182)(691)(497)(954)(822) 105 (221) 0.04 4.05 3.90 3.02 5.80 5.03 2.98 0.20 (7) (723)(697)(539)(1036)(898)(532)(36) 110 (230) 4.26 4.11 3.97 3.41 6.00 6.16 4.97 2.20 (761)(734)(709)(609)(1072)(1100)(888)(393) 115 (239) 4.95 4.34 4.27 3.61 5.50 6.06 5.86 5.10 (884)(775)(763)(645)(982)(1082)(1047)(911) 120 (248) 5.16 4.72 4.65 3.60 5.55 6.24 5.80 7.60 (922)(843)(830)(643)(991)(1114)(1036)(1357) 125 (257) 6.48 5.00 4.80 3.78 5.76 5.50 6.43 8.80 (1157)(893)(857)(675)(1029)(982)(1148)(1572) 130 (266) 6.61 4.20 4.19 3.84 6.10 5.50 5.90 7.50 (1181)(750)(748)(686)(1089)(982)(1054)(1340) **Comparative Example Only NA = Not Applicable W~ 95/00587 216 5 3 4 0 PcT/US94/06730 The data in Table 5 shows that films made using the novel homogeneously branched substantially linear ethylene/oc-olefin interpolymer had higher heat seal strength than film made from heterogeneously branched ethylene/oc-olefin copolymers and lower heat seal initiation temperatures than both the commercially available SM3 film and film made using heterogeneously branched ethylene/a-olefin copolymers.
Figure 10 is a graphical illustration of film heat seal strength versus temperature for resin 7 and comparative resin 1.
Figure 11 is a graphical illustration of film heat seal io strength versus temperature for resin 6 and comparative resin 2.
Figure 12 is a graphical illustration of film heat seal strength versus temperature for resin 5 and comparative resin 3.
Figure 13 is a graphical illustration of film heat seal strength versus sealing time for resins 5-7 and comparative resins 1-3 and i5 comparative film 8.
Table 6 Hot Tack* Strength, N/inch (N/cm) v. Sealing Time, sec Seal Resin Resin Resin Resin Resin Resin Resin 1** 2** 3** 5 6 7 8**
Time, Hot Hot Hot Hot Hot Hot Hot sec tack, tack, tack, tack, tack, tack, tack, N/in N/in N/in N/in N/in N/in N/in (N/cm) (N/cm) (N/cm) (N/cm)(N/cm) (N/cm) (N/cm) 0.1 0 2.10 2.30 5.82 2.50 0.32 0 (0.83) (0.91) (2.29)(0.98) (0.13) 0.2 0.27 2.72 2.98 6.01 4.10 1.44 0.30 (0.11) (1.07) (1.17) (2.37)(1.61) (0.57) (0.12) 0.3 0.47 2.91 3.05 6.13 5.06 1.80 0.75 (0.19) (1.15) (1.20) (2.41)(1.99) (0.71) (0.3) 0.5 1.40 3.13 3.10 6.30 5.40 2.60 1.50 (0.55) (1.23) (1.22) (2.48)(2.13) (1.02) (0.59) 0.7 1.31 3.10 3.11 6.40 5.76 2.87 1.65 (0.52) (1.22) (1.22) (2.52)(2.27) (1.13) (0.65) 1.0 1.40 3.25 3.24 6.16 5.59 3.24 1.80 (0.55) I (1.28)I (1.28)I (2.43)(2.20) (1.28) (0.71) I I ~
*Seal bar temperatures at 105°C
**Comparative Example Only The data in Table 6 shows that films made using the novel homogeneously branched substantially linear ethylene/oc-olefin interpolymer had higher hot tack strength at low hot tack sealing times than film made from heterogeneously branched ethylene/oc-olefin copolymers and commercially available SM3 film.
i0 WO 95/00587 2 ~ 6 5 3 4 0 PCT~S94/06730 Table 7 Heat Seal* Strength, lbs/inch (~/cm) v. Sealing time, sec Seal Resin Resin Resin Resin Resin Resin Resin 1** 2** 3** 5 6 7 8**
Time Heat Heat Heat Heat Heat Heat Heat (sec) seal, seal, seal, seal, seal, seal, seal, lbs/in lbs/in lbs/in lbs/in lbs/in lbs/in lbs/in /cm) ( /csn)( /cm) /cm) ( /cm) ( /cm) /cm) 0.1 0 3.70 3.90 4.66 4.08 0.05 0 (661) (697) (832) (729) (9) 0.2 0.17 4.43 4.09 5.13 4.40 0.21 0.10 (30) (791) (730) (916) (786) (38) (18) 0.3 0.18 4.28 4.20 5.52 4.46 3.80 0.20 (32) (764) (750) (986) (797) (679) (36) 0.5 0.40 4.12 4.10 5.70 5.10 4.20 0.35 (71) (736) (732) (1018) (911) (750) (63) 0.7 0.31 4.27 4.18 5.60 5.20 4.49 0.40 (55) (763) (747) (1000) (929) (802) (71) 1.0 0.40 4.34 4.25 5.73 5.25 4.30 0.42 (71) (775) (759) (1023) (938) (768) (75) *Seal bar temperatures at 105°C
**Comparative Example Only The data in Table 7 shows that films made using~the novel homogeneously branched substantially linear ethylene/a-olefin interpolymer had higher heat seal strength at low heat sealing times than film made from heterogeneously branched ethylene/oc-olefin copolymers and commercially available SM3 film.
i0 Table 8 Hayssen eal ngth 2 L Waterled Pouches,lbf/inch ) Heat S Stre of Fil (N/m Seal Temp ResinResinResin Resin ResinResin F (C) 1 2 3 * 5 6 7 * *
200 (93) NA NA NA 0 NA NA
205 (96) NA NA NA 3.74 NA NA
(656) 210 (99) NA NA 0 4.6 (806)NA NA
215 (102) NA NA 4.2 (736)5.21 0 NA
(913) 220 (104) NA 0 4.25 5.17 5.54 NA
(745) (906) (971) 225 (107) NA 4.65 4.2 4.94 4.98 NA
(815)(736) (866) (961) 230 (110) NA 4.88 4.3 4.98 5.48 NA
(855)(754) (873) (961) 235 (113) N 4.75 4.25 5.25 4.82 N
A A
(833)(745) (920) (845) 240 (116) 0 4.86 4.3 5.42 5.43 0 (852)(754) (950) (952) 245 (118) 5.55 4.95 4.38 5.55 5.28 5.55 (973)(868)(768) (973) (926)(973) 250 (121) 5.65 5.2 4.07 5.6 4.99 5.65 (990)(912)(713) (982) (875)(983) 255 (124) 5.73 5.32 4.32 5.73 5.22 5.73 (1004)(932)(757) (1004) (915)(1004) 260 (127) 5.6 5.4 4.28 5.69 5.45 5.6 (982)(947)(750) (997) (955)(982) 265 (129) 5.8 5.11 4.5 5.72 5.15 5.8 (1017)(896)(789) (1003) (903)(1017) 270 (132) 5.59 5.15 4.45 5.58 5.02 5.59 (980)(903)(780) (978) (880)(980) *Comparative Example Only The data in Table 8 shows that films made using the novel homogeneously branched substantially linear ethylene/a-olefin interpolymer had broader sealing ranges and higher Hayssen heat seal strengths than WO 95/00587 ~ ~ 4 ~ PCT/US94/06730 film made from heterogeneously branched ethylene/oc-olefin copolymers having similar densities.
Figure 14 is a graphical illustration of vertical form-fill-seal film heat seal strength versus temperature for resin 7 and s comparative resin 1.
- Figure 15 is a graphical illustration of vertical form-fill-seal film heat seal strength versus temperature for resin 6 and comparative resin 2.
Figure 16 is a graphical illustration of vertical form-fill-io seal film heat seal strength versus temperature for resin 5 and -comparative resin 3.
Table 9 summarizes data for the five foot drop test Table 9 is Five Foot Drop Test Resin No. of Failed PouchesPercent Failure 1* 100 100 2* 8 8 3* 3 3 38 ~ 38 *Compararive Example Only Although resin 7 and comparative resin 1 have similar density, pouches made from resin 7 had a much lower percent failure than pouches made from comparative resin 1.
2o Similarly, resin 6 and comparative resin 2 have similar density, but pouches made from resin 6 had a lower percent failure than pouches made from comparative resin 2. Pouches made using resin 5 also had lower percent failure than do pouches made using comparative resin 3, even though the resins have similar density.
It is further desired to provide a pouch made from the aforementioned film structures such that the pouch has a reduced failure rate.
We have now discovered that new homogeneously branched substantially linear ethylene/a-olefin interpolym<>rs offer significant io advantages in film structures of pouches. The novel homogeneously branched substantially linear ethylene/a-olefin interpolymers, when used as a seal layer, have good heat sealability at temperatures lower than those necessary for heterogeneously branched linear ethylene/a-olefin interpolymers and are also easily processed on conventional film and heat is seal equipment. Pouches made from film structure_=; comprising the homogeneously branched substantially linear ethyle ne/a-olefin interpolymers, when used as a seal layer or as a core layer, also have surprisingly good bursting performance.
One aspect of the present invention is directed to a pouch 2o made from a film structure in tubular form and having transversely heat sealed ends, the film structure having at least one film layer comprising:
(I) from 10 to 100 percent by weight of at least one homogeneously branched substantially linear ethylene/a-olefin interpolymer characCerized as having:
25 (a) a melt flow ratio, I10/I2, _> 5.63, and (b) a molecular weight distribution, Mw/Mn, defined by the equation. Mw/Mn S (I10/I2) - 9.63; and (II) from 0 to 90 percent by weight of at least one polymer selected from the group consisting of a heterogeneously 3o branched linear ethylene/C3-Clg a-olefin copolymer., a high-pressure low density polyethylene, and an ethylene-vinyl acetate copolymer.
One embodiment of the present invention is a pouch made from a two-layer (that is, A/B) coextruded film containing an outer layer of a heterogeneously branched linear low density polyethylene and an inner seal 35 layer of the aforementioned homogeneously branched substantially linear ethylene interpolymer.
Another embodiment of the present invent:ion is a pouch made from a three-layer (that is, A/B/A or A/B/C) coextruded film containing an outer layer and a core layer comprising heterogeneously branched linear low density polyethylene (either the same or different heterogeneously branched linear low density polyethylenes~) or a high pressure iow density polyethylene and an inner seal layer comprising the aforementioned homogeneou~;ly branched substantially linear ethylene interpolymer.
In these embodiments the outer layer may comprise at least one polymer selected from the group consisting of a heterogeneously branched linear ethylene/C3-C18 a-alefin copolymer, a high-pressure low density polyethylene, and an ethylene/vinyl acetate polymer.
Another aspect of the present invention is a process for preparing the aforementioned pouch.
In one embodiment of this aspect there i.s provided a process of preparing a pouch in a vertical form containing a flowable material comprising the steps of forming a film structure; forming the film structure into a tubular member;
heat-sealing longitudinal edges and first transverse end of the tubular member to form the pouch; filling the pouch with the flowable material; and sealing a second transverse end of the tubular member, the film structure having at least one layer comprising: (a) from 10 to 100 percent by weight of at least one homogeneously branched substantially linear ethylene/a-olefin interpolymer, and (b) from 0 to 90 percent by weight of at least one polymer selected from th.e group consisting of a heterogeneously branched linear ethylene/C3-C18 ~-olefin copolymer, a high-pressure low density polyethylene and an ethylene/vinyl acetate copolymer.
In another embodiment there is provided a process of preparing a pouch in a vertical form containing a flowable material comprising the steps of forming a film structure; forming the film structure into a tubular member;
heat-sealing longitudinal edges and first transverse end of the tubular member to form the pouch; filling the pouch with the flowable material; and sealing a second transverse end of the tubular member, the film structure having at least one layer comprising: (I) (a) from 10 to 100 percent by weight of at least one homogeneously branched substantially linear ethylene/a-olefin interpolymer, and (b) from 0 to 90 percent by weight of at least one polymer selected from the group consisting of a heterogeneously branched linear ethylene/C3-C18 a-olefin copolymer, a high-pressure low density polyethylene and an ethylene/vinyl acetate copolymer; and at least one layer comprising: (II) a heterogeneously branched linear ethylene/C3-C1$ a-olefin copolymer having a density greater than 0.87 g/cm3 and a melt index .from 0.1 to 10 g/10 minutes.
According to another embodiment of the process described above, the film structure includes at least one other layer comprising: a high-pressure low density polyethylene having a density from 0.916 to 0.93 g/cm3 and a melt index from 0.1 to 10 g/10 minutes.
Film structures for the pouches of the present invention have a better seal at lower sealing temperatures and shorter dwell times than currently obtainable with commercially available film. Use of the films for making pouches of the present invention in form, fill and seal machines leads to machine speeds higher than currently obtainable with the use of commercially available film.
-4a-Figure 1 shows a perspective view of a pouch package of the present invention.
Figure 2 shows a perspective view of another pouch package of the present invention.
Figure 3 shows a partial, enlarged cross-sectional view of the film structure of a pouch of the present invention.
Figure 4 shows another partial, enlarged cross-sectional view of another~embodiment of the film structure of a pouch of the present invention.
Figure 5 shows yet another partial, enlarged cross-sectional view of another embodiment of the film structure of a pouch of the present invention.
Figure 6 is a graphical illustration of film hot tack strength versus temperature for resin 7 and comparative resin 1.
-4b-WO 95/00587 216 5 3 4 0 PCT~S94/06730 Figure 7 is a graphical illustration of film hot tack strength versus temperature for resin 6 and comparative resin 2.
Figure 8 is a graphical illustration of film hot tack strength versus temperature for resin 5 and comparative resin 3.
Figure 9 is a graphical illustration of film hot tack strength versus sealing time for resins 5-7 and comparative resins 1-3 and comparative film 8.
io Figure 10 is a graphical illustration of film heat seal strength versus temperature for resin 7 and comparative resin 1.
Figure 11 is a graphical illustration of film heat seal strength versus temperature for resin 6 and comparative resin 2.
Figure 12 is a graphical illustration of film heat seal strength versus temperature for resin 5 and comparative resin 3.
2o Figure 13 is a graphical illustration of film heat seal strength versus sealing time for resins 5-7 and comparative resins 1-3 and comparative film 8.
Figure 14 is a graphical illustration of vertical form-fill-seal film heat seal strength versus temperature for resin 7 and comparative resin 1.
Figure 15 is a graphical illustration of vertical form-fill-seal film heat seal strength versus temperature for resin 6 and 3o comparative resin 2.
Figure 16 is a graphical illustration of vertical form-fill-seal film heat seal strength versus temperature for resin 5 and comparative resin 3.
Firgure 17 is a graphical illustration of maximum Ellen hot tack strength versus resin density for resins 5-7 and comparative resins 1-3.
s The pouch of the present invention, for example as shown in Figures 1 and 2, for packaging tlowable materials i~ manufactured Cror» a monolayer film structure of a polymeric seal layer which is a homogeneously branched substantially linear ethylene/a-olefin interpolymer (referred to hereinafter as "SLEP"l.
lo The SLEP of the present invention is generally an interpolymer of ethylene with at least one a-olefin having from 3 to 2U carbon atoms.
The term "interpolymer" is used herein to indicate a copolymer, or a terpolymer, or the like. That is, at least one other comonomer is polymerized with ethylene to make the interpolymer. For example, a SLEP
~5 terpolymer comprising ethylene!1-octene/1-hexane may be employed in the film structure as the polymeric seal layer.
Copolymers of ethylene and a C3-C20 tx-olefin are especially preferred, for example, the SLEP may be selected from.ethylene/propene, ethylene/1-butane, ethylene/1-pentane, ethylene/~L-methyl-1-pentane, 2o ethylene/1-hexane, ethylenell-heptene, ethylene/7~-octane and ethylene/1-decene copolymers, preferably ethylene/1-octane copolymer.
The term "substantially linear" means that the interpolymer backbone is substituted with 0.01 long chain branches/1000 carbons to 3 long chain branches/1000 carbons, more preferably from 0.01 long chain 25 branches/1000 carbons to 1 long chain branches/1000 carbons,. and especially from 0.05 long chain branches/1000 carbons to Z Tang chain branches/1000 carbons_ Long chain branching is defined herein as a chain length of at least about 6 carbons, above which the length cannot be distinguished 3o using 13C nuclear magnetic resonance spectroscopy. The length of the long chain branch can vary, but can be about as long as the length of the polymer back-bone itself.
Long chain branching is determined by using 1~C nuclear magnetic ,resonance (NMR) spectroscopy and is quantified using the method s5 of Randall ( ev. Macromol. Chem. PhDs-, C29 (2&3), p. 285-297j.
_t-The substantially linear ethylene/a-olefin copolymers and interpolymers of the present invention are herein defined as in USP
5,278,236 and in USP 5,278,272. The substantially linear.
ethylene/a-olefin copolymers and interpolymers useful for forming the s compositions described herein are homogeneously branched (th.st is, the comonomer is randomly distributed within a given interpclymer molecule and wherein substantially all of the interpolymer molecules have the same ethylene/comonomer ratio within that interpolymer).
The SCHDI (Short Chain Branch Distribution Index) or CDBI
~o (Composition Distribution Branch Index) is defined as the weight percent of the polymer molecules having a comonomer content within SO percent of the median total molar comonomer content. The CDBI of a polymer i:~ readily calculated from data obtained from techniques known in the art, such as, for example, temperature rising elution fractionation (abbr.eviated herein is as 'TREF') as described, for example, in Wild et al, Journal of .Polymer Science, ,~oy_r~. ghys. ~, Vol. 20, p. 441 (1982), or in U.S. Patent 4,798,081.
The SCBDI or CDBI for the substantially linear ethylene/oc-olefin interpolymers and copolymers used in the present invention i.s preferably 2o greater than 30 percent, especially greater than 50 percent. The substantially linear ethylene/cx-olefin interpolymers and copolymers used in this invention essentially lack a measurable "high density" fraction as measured by the TREF technique. The "high density" fraction includes linear homopolymer polyethylene. The "high density" polymer fraction can 25 be described as a polymer fraction with a degree of branching less than or equal to 2 methyls~1000 carbons. The terms 'essentially lacks a measurable high density fraction" means that the substantially linear interpolymers and copolymers do not contain a polymer fraction with a degree of branching less than or equal to 2 methyls/1000 carbons.
3a The novel homogeneously branched SLED are easily distinguished from homogeneously branched linear ethylene/oc-olefin interpolymers. The term "linear ethylene/OC-olefin interpolymer" means that the interpolymer does not have long chain branching. That is, the linear ethylene/oc-olefin interpolymer has an absence of long chain branching, as for example the 35 homogeneously branched linear low density polyethylene polymers made using uniform branching distribution polymerization processes (for example, as _;._.
WO 95/00587 216 5 3 4 0 PCT~S94/06730 described in USP 3,645,992 (Elston)). For both the linear and substantially linear interpolymers, however, the term "homogeneously branched" means that the comonomer is randomly distributed within a given interpolymer molecule and wherein substantially alI of the interpolymer , molecules have the same ethylene/comonomer ratio within that interpolymer.
The term "linear ethylene/oc-olefin interpolymer" does not refer to high pressure branched (free-radical polymerized) polyethylene which is known to those skilled in the art to have numerous long chain branches.
The homogeneously branched substantially linear io ethylene/oc-olefin copolymers and interpolymers also have a single melting point, as opposed to traditional Ziegler polymerized (heterogeneously branched) polymers having two or more melting points, as determined using differential scanning calorimetry (DSC) over a temperature range of from -20°C to 150°C. In addition, the novel homogeneously branched i5 substantially linear ethyleneloc-olefin copolymers and interpolymers have melting points which correlate with the density of the copolymer or interpolymer, that is, as the density decreases, the peak melting point of the polymer decreases in a directly linear fashion. Heterogeneously branched ethylene polymers have peak melting points which do not vary 2o substantially with the density of the polymer, primarily due to the presence of a high density polymer fraction which melts at about 122°C
(the melting point of homopolymer linear polyethylene).
The density of the homogeneously branched substantially linear ethylene/oc olefin interpolymers or copolymers (as measured in accordance 25 with ASTM D-792) for use in the present invention is generally less than 0.94 g/cm3 and preferably from 0.85 g/cm3 to 0.94 g/cm3.
Generally, the homogeneously branched substantially linear ethylene/oc-olefin polymer is used alone in the seal layer of the film or film structure. However, the homogeneously branched substantially linear 3o ethylene/oc-olefin polymer can be blended with other polymers for use as the heat seal layer. Generally, the amount of the homogeneously branched substantially linear ethylene/oc-olefin polymer is from 10 percent to 100 percent, by weight of the film structure.
The molecular weight of the homogeneously branched 35 substantially linear ethylene/oc-olefin interpolymers and copolymers for use in the present invention is conveniently indicated using a melt index _g_ measurement according to ASTM D-1238, Condition 190'C/2.16 kg (formerly known as "Condition (E)" and also known as I2). Melt index is inversely proportional to the molecular weight of the polymer. Thus, the higher the molecular weight, the lower the melt index, although the relationship is not linear. The melt index for the homogeneously branched substantially linear ethylene/o:-olefin interpolymers and copolymers useful herein is generally 10 grams/10 minutes (g/10 min) or less, preferably from 0.01 g/10 min to 10 g/10 min.
Another measurement useful in characterizing the molecular to weight of th~= homogeneously branched substantially linear ethylene/0~-olefin interpolymers and copolymers is conveniently indicated using a melt index measurement according to ASTM t:)-1238, Condition 190'C/10 kg (formerly known as "Condition (N)" and also known as I10)-The ratio of these two melt index terms is the melt flow ratio and is is designated as I10/I2. For the homogeneously branched substantially linear ethylene/OC-olefin interpolymers and copolymers used in this invention, the I10/I2 ratio indicates the degree of long chain branching, that is, the higher the I10/I2 ratio, the more long chain branching in the polymer.
Generally, the I10/I2 ratio of the homogeneously branched substantially 20 linear ethylene/CC-olefin interpolymers and copolymers is at least 5.63, preferably at least 7, especially at least 8 or above. Generally, the I10/I2 ratio can be as high as 30, preferably no higher than 20.
The molecular weight distribution (Mw/Mn) of the homogeneously 25 branched substantially linear ethylene/oc-olefin interpolymers and copolymers is analyzed by gel permeation chromatography (GPC) on a Waters 150C high temperature chromatographic unit equipped with three mixed porosity columns (Polymer Laboratories 103, 104, 105, and 106), operating' at a system temperature of 140°C. The solvent is 1,2,4-trichlorobenzene, so from which 0.3 percent by weight solutions of the samples axe prepared for injection. The flow rate is 1.0 milliliters/minute and the injection size is 200 microliters.
The molecular weight determination is deduced by using narrow molecular weight distribution polystyrene standards (from Polymer 35 Laboratories) in conjunction with their elution ~rolumes. The equivalent polyethylene molecular weig'r~ts are determined by using appropriate Mark-*Trade-mark s Houwink coefficients for polyethylene and polystyrene (as described by Williams and Word in journal of Polvme~ Science, Polymer Letters, Vol. 6, (621) 1968.) to derive the following~equation: -Mpolyethylene = a~'' (Mpolystyrene)b- ~ ' ~, -In this equation, a = 0.4316 and b = 1Ø Height average molecular weight, MW. is calculated in the usual manner according to the following ~o formula:'M,~ = E wi° Mi. Where wi-and M~ ire the weight fraction and ' ~ .
molecular'Weight, respectively, o'f the ith Erection eluting from the GPC
column. -For the homogeneously branched substantially linear ethylene/ac-olefin interpolymers and copolymers, the Mw/Mn is preferably a from 1_5 to 2_5, especially 2.
Additives, known to those skilled in the art, such as antioxidants (for example,. hindered phenolics (for. example, Irganox~ 1010 or Irganox~ 1076 made by Ciba Geigy Corp.), phosphites (for exaople, 2o Irgafos~ 168 made by Ciba Geigy Corp.)), cling additives (for example;
polyisobutylene (Pr8)), Standostab P~PQT"' supplied by Sandoz, anti-block additives, slip additives, U~,l stabilizers, pigments, processing aids, can also be added to the polymers from which the pouches of the present invention are made.
The 'theological processing index' (PI) is the apparent viscosity (in kpoise) of a polymer measured by a gas extrusion rheometer (G~R). The gas extrusion rheometer is described by M.vShida, R.N. Shroff and L.V. Cancio in.poly~r_ g.naineerina Science, Vol. 17, no_ 11, p. 770 (1977), and in °Rheometers for Molten Plastics' by John Dealy, published by Van Nostrand Reinhold Co. (1982) on page 97-99. All GER experiments .are perfortaed at a temperature~of 190°C, at nitrogen pressures between .
5250 to S00 psig (36.3 to 3.55 MPA) using a 0_0296 inch (0.752 ~) diameter, 20:1 L/D die with an entrance angle of 180°. For the as homogeneously branched ethylene polymers described herein, the PI is the apparent viscosity (in kpoise) of a material measured by G~R at an -1(1-WO 95/00587 216 5 3 4 0 PCT~S94/06730 apparent shear stress of 2.15 x 106 dyne/cm2. The novel substantially linear ethylene/ot-olefin interpolymers and copolymers described herein preferably have a PI in the range of 0.01 )cpoise to 50 kpoise, more preferably about 15 kpoise or less. The novel substantially linear ethylene/oc--olefin polymers described herein for use in the pouches have a PI less than or equal to about 70 percent of the PI of a linear ethylene/ot-olefin polymer at about the same or substantially the same I2 and Mw/Mn and the same comonomer(s).
An apparent shear stress vs. apparent shear rate plot is used io to identify the melt fracture phenomena. According to Ramamurthy in Journal of Rheo1_oav, 30(2), 337-357, 1986, above a certain critical flow rate, the abserved extrudate irregularities may be broadly classified into two main types: surface melt fracture and gross melt fracture. Surface melt fracture occurs under apparently steady flow conditions and ranges in i5 detail from loss of specular gloss to the more severe form of "sharkskin".
Gross melt fracture occurs at unsteady flow conditions and ranges in detail from regular (alternating rough and smooth, helical, etc.} to random distortions.
Ramamurthy {Journal of Rheoloav) and Moynihan, Baird and zo Ramanathan in Journal of Non-Newtonian Flu,'_d Mechan,'_cs, 36, 255-263 (1990), both disclose that the onset of sharkskin (that is, melt fracture) for linear low density polyethylene {LLDPE) occurs at an apparent shear stress of 1-1.4 x 106 dyne/cm2, which was observed to be coincident with the change in slope of the flow curve. Ramamurthy also discloses that the 25 onset of surface melt fracture or of gross melt fracture for high pressure low density polyethylene (HP-LDPE) occurs at an apparent shear stress of about 0.13 MPa (1.3 x 106 dynes/cm2).
Kalika and Denn in Journal of Rheoloav, 31, 815-834 (1987) confirmed the surface defects or sharkskin phenomena for LLDPE, but the 3o results of their work determined a critical shear stress of 2.3 x 106 dyne/cm2, significantly higher than that found by Ramamurthy and Moynihan et al.
In this disclosure, the onset of surface melt fracture {OSMF) is characterized at the beginning of losing extrudate gloss at 35 which the surface roughness of extrudate can only be detected by 40X
magnification. Surprisingly, the critical shear rate at onset of surface melt fracture for the substantially linear ethylene/a-olefin interpolymers and copolymers is at least 50 percent greater than the critical shear rate at the onset of surface melt fracture of a linear ethyleng/oc-olefin interpolymer or copolymer (either a heterogeneously branched polymer (for , s example, LLDPE) or a homogeneously branched polymer (for example, that described in USP 3,645,992 (Elston)) having about the same or y substantially the same I2 and Mw/Mn and the same comonomer(s).
The critical shear rate and critical shear stress at onset of surface melt fracture (OSMF) and onset of gross melt fracture (OGMF) will 1o be used herein based on the changes of surface roughness and configurations of the extrudates extruded by a GER. In contrast to both LLDPE and high pressure LDPE, the critical shear stress at onset of gross melt fracture for the substantially linear ethylene/oc-olefin interpolymers and copolymers, especially those having a density greater than about 0.9 is g/cm3, is greater than about 4 x 106 dynes/cm2.
The films and film structures disclosed herein can be monolayer or multilayer film structures, with the proviso that the homogeneously branched substantially linear ethylene/oc-olefin copolymers 2o and interpolymers be used as at least one layer, preferably the seal layer. The thickness of the seal layer may be from at least about 0.1 mil (2.5 microns) and greater, preferably from 0.2 mil (5 microns) to 10 mil (254 microns) and more preferably from 0.4 mil (10 microns) to 5 mil (127 microns).
25 A surprising feature of the pouch's film structure of the present invention is the film's broad heat sealing range, especially in view of the substantially linear ethylene polymer's narrow melting point range (measured using differential scanning calorimetry (DSC)).
Generally, the heat sealing range of the film structure can be from 50°C
3o to 160°C and preferably from 75°C to 130°C. It has been found that the seal layer of the present invention has a broader heat seal range than prior art polyethylene film made from heterogeneously branched ethylene polymers, even at the approximately the same density. A broad heat sealing range is important to allow for more flexibility in the heat 35 sealing process used for making pouches from the film structure.
Generally, the melting point range of the substantially linear ethylene polymer used to make the film structure having the heat seal ranges specified above can be from 50°C to 130°C and preferably from 55°C to 115°C.
Another unexpected feature of the pouch's film structure of the present invention is the film's heat seal strength at low temperatures. Generally, the film structure of the present invention achieves a hot tack strength of at least about 1 Nlinch (39.4 N/m) at a seal bar temperature of about 110°C and at less than about 0.3 seconds using the DTC Hot Tack Strength Method defined hereinbelow or achieves a io heat seal strength of at least 1 lbf/inch (175 N/m) at a seal bar temperature of about 110°C and at less than 0.4 seconds using the DTC
Heat Seal Strength Method defined hereinbelow. The film structure of the present invention also has a hot tack or heat seal initiation temperature of less than about 110°C at a force of at least about 1 N/inch (39.4 N/m).
is It has been found that a seal made with the seal layer of the present invention has a higher strength at lower sealing temperatures than seals with a prior art polyethylene having higher densities. A high heat seal strength at low temperatures is important to allow conventional packaging equipment such as a vertical form, fill and seal machine to run at faster 2o rates and t:o produce pouches with fewer leakers.
It is believed that the use of at least one substantially linear ethylene polymer in a seal layer of a film structure for pouches of the present invention (1) provides a pouch that can be fabricated at a fast rate through a form, fill and seal machine and (2) provides a pouch 25 package having few leakers, particularly when the pouch of the present invention is compared to pouches made with linear low density polyethylene, ultra linear low density polyethylene, high pressure low density polyethylene, or a combination thereof.
In one embodiment of the present invention, a pouch is made 3o from a film structure in tubular form and having transversely heat sealed ends. The film structure has at least one film layer comprising:
(I) from 10 to 100 percent by weight of at least one layer comprising at least one homogeneously branched substantially linear ethylene/a--olefin interpolymer characterized as having:
WO 95/00587 ~21 ~ 5 3 4 0 PCT/US94/06730 {a) a melt flow ratio, I10/I2, >_ 5.63, and (b) a molecular weight distribution, Mw/Mn, defined by the equation: Mw/Mn <_ tIlO/I2) - 4.63; and (II) from 0 to 90 percent by weight of at least one polymer selected from the group consisting of a heterogeneously branched Linear ethylene/C3-Clg Oc-olefin copolymer, a high-pressure low density polyethylene, and an ethylene-vinyl acetate copolymer.
The heterogeneously branched linear ethylene/C3-Clg oc-olefin copolymer of (II) is generally a linear low density polyethylene (such as io that made using Ziegler catalysis). The linear low density polyethylene is often further divided into subsets labeled as very low density polyethylene (VLDPE) or ultra low density polyethylene tULDPE). VLDPE and ULDPE are interchangeable terms herein and are generally used in this manner by those skilled in the art. Generally, the density of the linear i5 low density polyethylene of (II) ranges from 0.87 g/cm3 to 0.94 g/cm3, preferably from 0.87 g/cm3 to 0.915 g/cm3. Preferably, the heterogeneously branched linear low density ethylene/C3-Clg a-olefin copolymer of (II) has a melt index from 0.1 to 10 g/10 minutes.
Preferably, the high-pressure low density polyethylene of (II) 2o has a density from 0.916 to 0.93 g/cm3 and a melt index from 0.1 to 10 g/10 minutes.
Preferably, the ethylene-vinyl acetate copolymer of (II) has a weight ratio of ethylene to vinyl acetate from 2.2:1 to 24:1 and a melt index from 0.2 to 10 8110 minutes.
25 Another embodiment of the present invention includes a pouch made from a blend of:
(a) from 10 to 100 percent by weight of at least one homogeneously branched substantially linear ethylene copolymer interpolymerized from ethylene and at least one alpha-olefin in the range 30 of C3-C2p and having a density of less than 0.915 g/cm3 and a melt index of less than 10.0 g/10 minutes, and (b) from 0 to 90 percent by weight of at least one polymer selected from the group consisting of a heterogeneously branched linear ethylene/C3-Clg oc-olefin copolymer, a high-pressure low-density , .
35 polyethylene and an ethylene-vinyl acetate (EVA) copolymer.
The heterogeneously branched linear ethylene/C3-C1g a-olefin copolymer of (IT) generally is a linear low density polyethylene (such as that made using Ziegler catalysis). The linear low desnity polyethylene includes very low density polyethylene (VLDPE) and ultra low density polyethylene (ULDPE), as described previously. Generally, the density of ~ the linear low density polyethylene of (II) ranges from 0.87 g/cm3 to 0.94 g/cm3, preferably from 0.87 g/cm3 to 0.915 g/cm3. Preferably, the heterogeneously branched linear low density ethylene/C3-C1g oc-olefin copolymer of (II) has a melt index from 0.1 to 10 g/10 minutes.
io Preferably, the high-pressure low density polyethylene of (b) has a density from 0.916 to 0.93 g/cm3 and a melt index from 0.1 to 10 g/10 minutes.
Preferably, the ethylene-vinyl acetate copolymer of (b) has a weight ratio of ethylene to vinyl acetate from 2.2:1 to 24:1 and a melt i5 index from 0.2 to 10 g/10 minutes.
With reference to Figures 3 to 5, the film structure of the pouch of the present invention also includes a multilayer or composite film structure 30, preferably containing the above-described polymeric seal layer being the inner layer of the pouch.
2o As will be understood by those skilled in the art, the multilayer film structure for the pouch of the present invention may contain various combination of film layers as long as the seal layer forms part of the ultimate film structure. The multilayer film structure for the pouch of the present invention may be a coextruded film, a coated film 25 or a laminated film. The film structure also includes the seal layer in combination with a barrier film such as polyester, nylon, ethylene-vinyl alcohol copolymer (EVOH), polyvinylidene dichloride (PVDC) such as Saran"' (Trademark of The Dow Chemical Company) and metallized films. The end use for the pouch tends to dictate, in a large degree, the selection of the 30 other material or materials used in combination with the seal layer film.
The pouches described herein will refer to seal layers used at least on the inside of the pouch.
One embodiment of the film structure 30 for the pouch of the present invention, shown in Figure 3, comprises a homogeneously branched 35 substantially linear ethylene polymer seal layer 31 and at least one polymeric outer layer 32. The polymeric outer layer 32 is preferably a polyethylene film layer, more preferably a heterogeneously branched linear polyethylene referred to hereinafter as "linear low density polyethylene"
("LLDPE") and/or "ultra linear low density polyethylene" .("ULDPE") and/or "very low density polyethylene ("VLDPE"). An example of a commercially , available LLDPE is DOWLEX~ 2045 {Trademark of and commercially available from The Dow Chemical Company). An example of a commercially available ULDPE is ATTANE~ 4201 (Trademark of and commercially available from The Dow Chemical Company).
The LLDPE (including both the VLDPE and ULDPE) useful herein io are heterogeneously branched linear copolymers of ethylene and a minor amount of an alpha-olefin having from 3 to 18 carbon atoms, preferably from 4 to 10 carbon atoms (for example, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, and 1-decene) and most preferably 8 carbon atoms (for example, 1-octene). Generally, the heterogeneously branched LLDPE are i5 made using Ziegler catalysis {for example, using the method described in U.S. Patent No. 4,076,698 (Anderson et al.)).
The LLDPE for the outer layer 32 generally has a density greater than 0.87 g/cm3, more preferably from 0.9 to 0.93 g/cm3; generally has a melt index (I2) from 0.1 to 10 g/10 min, preferably from 0.5 to 2 2o g/10 min; and generally has an Ilp/I2 ratio from 5 to 20, preferably from 7 to 20.
For the heterogeneously branched LLDPE (including both VLDPE
and UDLPE), the Il0/I2 ratio tends to increase as the molecular weight (Mw/Mn) of the LLDPE increases, in surprising contradistinction to the 25 novel homogeneously branched substantially linear ethylene/a.-olefin interpolymers and copolymers discussed herein.
The thickness of the outer layer 32 may be any thickness so long as the seal layer 31 has a minimum thickness of 0.1 mil (2.5 microns).
3o Another embodiment of the film structure 30 for the pouch of the present invention, shown in Figure 4, comprises the polymeric layer 32 sandwiched between two polymeric seal layers 31.
Still another embodiment of the film structure 30 for the pouch of the present invention, shown in Figure 5, comprises at least one 35 polymeric core layer 33 between at least one polymeric outer layer 32 and at least one polymeric seal layer 31. The polymeric layer 33 may be the WO 95/00587 ~ ~ PCT/US94/06730 same LLDPE film layer as the outer layer 32 or preferably a different LLDPE, and more preferably an LLDPE that has a higher density than the outer layer 32. The thickness of the core layer 33 may be any thickness so long as the seal layer 31 has a minimum thickness of 0.1 mil (2.5 microns).
Yet another embodiment (not shown) of the film structure for the pouch of the present invention can be a structure including a seal layer 31 and another polyethylene film layer referred to hereinafter as "high pressure low-density polyethylene" ("LDPE"). The LDPE layer 1o generally has a density from 0.916 to 0.930 g/cm3 and has a melt index from 0.1 to 10 g/10 min. The thickness of the LDPE layer may be any thickness so long as the seal layer 31 has a minimum thickness of 0.1 mil (2.5 microns).
Still another embodiment (not shown) of the film structure for is the pouch of the present invention can be a structure including a seal layer 31 and a layer of EVA copolymer having a weight ratio of ethylene to vinyl acetate from 2.2:1 to 24:1 and a melt index of from 0.2 to 20 g/10 min. The thickness of the EVA layer may be any thickness so long as'the seal layer 31 has a minimum thickness of 0.1 mil (2.5 microns).
2o The thickness of the film structure used for making the pouch of the present invention is from 0.5 mil (12.7 microns) to 10 mils (254 microns), preferably from 1 mil (25.4 microns) to 5 mils (127 microns).
As can be seen from the different embodiments of the present invention shown in Figures 3-5, the film structure for the pouches of the 25 present invention has design flexibility. Different LLDPEs (for example, VLDPE and tJLDPE) can be used in the outer and core layers to optimize specific film properties such as film stiffness. Thus, the film can be optimized for specific applications such as for a vertical form, film and seal machine.
3o The polyethylene film structure used to make a pouch of the present invention is made by either the blown tube extrusion method or the cast extrusion method, methods well known in the art. The blown tube extrusion method is described, for example, in Modern Plastics Mid-October 1989 Encyclopedia Issue, Volume 66, Number 11, pages 264 to 266. The cast 35 extrusion method is described, for example, in Modern Plastics Mid-October 1989 Encyclopedia Issue, Volume 66, Number 11, pages 256 to 257.
Embodiments of the pouches of the present invention, shown in Figures 1 and 2, are hermetically sealed containers filled with "flowable materials". By "flowable materials" it is meant materials which are , flowable under gravity or which may be pumped, but the term "flowable materials" does not include gaseous materials. The flowable materials , include noncarbonated liquids (for example, milk, water, fruit juice, wine) and carbonated liquids {for example, soda, beer, water); emulsions (for example, ice cream mix, soft margerine); pastes (for example, meat io pastes, peanut butter); preserves (for example, jams, pie fillings, marmalade); jellies; doughs; ground meat (for example, sausage meat);
powders {for example, gelatin powders, detergents); granular solids (for example, nuts, sugar, cerial); and like materials. The pouch of the present invention is particularly useful for packaging liquids (for i5 example, milk). The flowable material may also include oleaginous liquids (for example, cooking oil or motor oil).
Once the film structure for the pouch of the present invention is made, the film structure is cut to the desired width for use in conventional pouch-forming machines. The embodiments of the pouch of the 2o present invention shown in Figures 1 and 2 are made in so-called form, fill and seal machines well known in the art. With regard to Figure 1, there is shown a pouch 10 being a tubular member 11 having a longitudinal lap seal 12 and transverse seals 13 such that, a "pillow-shaped" pouch is formed when the pouch is filled with flowable material.
25 With regard to Figure 2, there is shown a pouch 20 being a tubular member 21 having a peripheral fin seal 22 along three sides of the tubular member 11, that is, the top seal 22a and the longitudinal side seals 22b and 22c, and having a bottom substantially concave or "bowl-shaped" member 23 sealed to the bottom portion of the tubular seal 30 21 such that when viewed in cross-section, longitudually, substantially a semi-circular or "bowed-shaped" bottom portion is formed when the pouch is filled with flowable material. The pouch shown in Figure 2 is the so-called "Enviro-Pak" pouch known in the art.
The pouch manufactured according to the present invention is 35 preferably the pouch shown in Figure 1 made on so-called vertical form, fill and seal (VFFS) machines well known in the art. Examples of commercially available VFFS machines include those manufactured by Hayssen or Prepac. A VFFS machine is described in the following reference: F. C.
Lewis, "Form-Fill-Seal," Packaging Encyclopedia, page 180, 1980.
In a VFFS packaging process, a sheet of the plastic film structure described herein is fed into a VFFS machine where the sheet is formed into a continuous tube in a tube-forming section. The tubular member is formed by sealing the longitudinal edges of the film together --either by lapping the plastic film and sealing the film using an inside/outside seal or by fin sealing the plastic film using an 1o inside/inside seal. Next, a sealing bar seals the tube transversely at one end being the bottom of the "pouch", and then the fill material, for example milk, is added to the "pouch." The sealing bar then seals the top end of the pouch and either burns through the plastic film or cuts the film, thus, separating the formed completed pouch from the tube. The i5 process of making a pouch with a VFFS machine is generally described in U.S. Patent Nos. 4,503,102 and 4,521,437.
The capacity of the pouches of the present invention may vary.
Generally, the pouches may contain from 5 milliliters to 10 liters, preferably from 10 milliliters to 8 liters, and more preferably from 1 20 liter to 5 liters of flowable material.
The use of the homogeneously branched substantially linear ethylene/Ot~-olefin interpolymer seal layer of the present invention in a two or three-layer coextruded film product will provide a film structure that can be used for making pouches at a faster rate in the VFFS and such 25 pouches produced will contain fewer leakers.
The pouches of the present invention can also be printed by using techniques known in the art, for example, use of corona treatment before printing.
The pouches of the present invention have excellent 3o performance results when tested by the 5 Foot (1.52 m) Drop Test--a test which is defined herein. Under the 5 Foot (1.52 m) Drop Test, the pouches preferably have a percent failure of less than 40 percent and more preferably less than 20 percent, and especially less than 10 percent.
Use of the pouch for packaging consumer liquids such as milk 35 has its advantages over containers used in the past: the glass bottle, paper carton, and high density polyethylene jug. The previously used containers consumed large amounts of natural resources in their manufacture, required a significant amount of space in landfill, used a large amount of storage space and used more energy in temperature control of the product (due to the heat transfer properties of the container). , The pouches of the present invention made of thin film, used for liquid packaging, offers many advantages over the containers used in the past. The pouches: (1) consume less natural resources, (2) require less space in a landfill, (3) can be recycled, (4) can be processed easily, (5) require less storage space, (6) use less energy for storage io (heat transfer properties of package), (7) can be safely incinerated and (8) can be reused (for example, the empty pouches can be used for other applications such as freezer bags, sandwich bags, and general purpose storage bags).
is Coextruded blown film samples having an A/B/A structure were made using layer ratios of: A=15 percent (by weight of the total structure) and B= 70 percent (by weight of the total structure). Layer B
was an ethylene/1-octane LLDPE having a melt index (I2) of about 1 g/10 2o minute and a density of about 0.92 g/cm3 and did not contain additives.
In the examples, resins 1-3 were all heterogeneously branched ethylene/1-octene copolymers and resins 4-7 were all homogeneously branched substantially linear ethylene/1-octane copolymers. Table 1 summarizes physical properties of the resins used to make A/B/A coextruded blown film 25 samples described in the examples and comparative examples:
Table 1 Resin Resin Melt IndexDensity Mw/Mn I10/I2 type (I2) (g/cm3) -/10 min) 1 * LLDPE 1 0.92 3.73 8 2* ULDPE 1 0.912 4.03 8.2 3 * ULDPE 1 0.905 4.2 8.7 4 SLEP 1.03 0.8713 2.11 7.81 5 SLED 1 0.902 2.02 9.3 6 SLEP 0.97 0.9104 2.2 10.()5 7 SLEP 1.01 0.91fi 2.27 9.48 8 * S1v43 N A N A Iv A N A
Film made by DuPont *Comparative example NA = Not applicable Resins 1, 2, 5, 6, and 7 were dry blended to contain 4,000 ppm Si02 and 1,200 ppm Erucamide. Resin 3 was dry blended to contair 6,000 ppm Si02 and 1,200 ppm Erucamide. Resin 4 was dry blended to contain 14,000 ppm Si02 and 1,200 ppm Erucamide. Resin 8 was a monolayer milk pouch film designated "SM3" made by and available from DuPont Canada and was believed to be a blend of about 8 percent (by weight) of a low density io polyethylene having a density of about 0.92 g/cm3 and about 92 percent (by weight) of a heterogeneously branched linear low denisty polyethylene.
The SM3 film had a final film density reported by DuPont as 0.918 g/cm3.
Film samples were produced on an Egan three layer extruder system. Extruder A had a 2.5 inch (6.35 cm) diameter (Barr2 type) screw is equipped with a Maddox mixer, L/D of 24.1, 60 HP drive. Extruder B had a 2.5 inch (6.35 cm) diameter (DSB II type) screw equipped with a Maddox mixer, L/D of 24:1, 75 HP drive. Extruder C had a 2 inch (5.08 cm) diameter (Modified MHD (Johnson) type) screw equipped with a Maddox mixer, L/D of 24:1, 20 HP drive. The blown film line was. also equipped with an E?
zo inch (20.32 cm) 3-layer co~.~~ctruding die body, a Gloucester Tower, a Sano~' collapsing frame, a Sano bubble sizing cage, and a Sano bubble enclosure.
Each-of the film samples was made at 3 mil target thickness using a blow-up ratio (BUR) of 2.5:1.
*Trade-mark Each film was tested according to the following test anethods:
Puncture- Puncture was measured by using an I,nstrorl Tensile Tester with an integrator, a specimen holder, and a puncturing device.
The Instron was set to obtain a crosshead speed of 10 inches/minute (25.4 em/minute) and a chart speed (if used) of llr inches/minute (25.4 cm/minute). Load range of SO percent of the load cell capacity (100 1b.
(45.36 kg) load for these tests) was used. The puncturing device was installed to the Instron such that the clamping unit was attached to the to lower mount and the ball was attached to the upper mount on the cros_~hc.ad.
Five film specimens were used (each 6 inches (15_24 cm) square). The specimen was clamped in the film holder and the fiirn holder way: secured to the mounting bracket_ The crosshead travel was ~aec and continued until the specimen breaks. Puncture resistance was defined as th,e energy to t5 puncture divided by the volume of the film under test. Puncture resistance (PR.) was calculated as follows:
PR = E/((12)(T)(A)) where PR = puncture resistance (ft-lbs/in3), 2o E = energy (inch-lbs) = area under the load displacement curve, 12 = inches/foot, T = film thickness (inchesi, and A = area of the film sample in the clamp = 12.56 in2 (81 cm2);
i5 part Impact: ASTM D1709, method A;
1;1_mendorf Tear: ASTM D1922;
Tensile Properties: ASTM D882 using an Instron tensile tester 30 (cross-head speed of 500 mm/min, full scale load of S kg, threshold of I
percent of full scale load, break criterion of 80 percent, 2 inch (5.08 cm) gauge length and 1 inch (2.54 cm? sample width); , Coefficient of Friction: ASTM D1894_ Coefficient of friction 35 range is important in order for the film..;to properly move over the forming collars in a vertical-form-fill and ~~c:.a~ machine (for example, a Hayssen *Trade-mark _;p_ form-fill-seal machine): if the coefficient of friction is too low, the film may be too slippery for the pull belts to grip the film and if the coefficient of friction is too high, the film may be too,tacky for the machine to pull the film over the forming collar; typical targets for the Hayssen form-fill-seal machine are:
(i) inside/outside coefficient of friction from 0.10 - 0.30 and (ii) outside/outside coefficient of friction from 0.10 - 040;
Percent and 2 Percent Secant Modulus: ASTM D882. Film io stiffness is important, especially for "free-standing" pouches like that shown in Figure 2. The 1 percent and 2 percent secant modulus tests provide an indication of the stiffness of the film;
Heat Seal Strength: This test measures the force required to separate a seal after the seal has been allowed to cool. Seals were made using the DTC Hot Tack Tester but only the heat seal portion of the unit was used. Conditions used were:
Specimen width: 24.4 mm Sealing time: 0.5 seconds 2o Sealing pressure: 0.27 N/mm/mm No. samples/time: 5 Temperature increments: 5°C.
Seal strength was determined using an Instron Tensile Tester Model No. 1122. The film samples were exposed to relative humidity of 50 percent and a temperature of 23°C for 24-48 hours prior to testing.
Instron test conditions were as follows:
Direction of pull: 90° to seal Crosshead speed: 500 mm/minute Full scale load (FSL): 5 kg 3o Threshold: 1 percent of FSL
Break Criterion: 80 percent Gauge length: 2.0 inches (5.08 cm) and Sample width: 1.0 inch (2.54 cm);
uPar Seal Strenath Versus Sealina Time~ Films were sealed using a DTC Hot Tack Tester model no. 52D. Conditions used were as follows:
Specimen width: 24.4 mm Sealing time: varied Sealing pressure: 0.27 N/mm/mm No. samples/time: 5 Sealing temperature range: 0.1 seconds - 1.0 seconds Temperature: 105°C.
io The seal strength was determined using an Instron Tensile Tester Model No. 1122 using the conditions described in the Heat seal Strength test.
Hot Tack Performance: The hot tack test measures the force i5 required to separate a heat seal before the seal has had a chance to cool.
This test simulates filling a pouch with material just after the seal was made. The hot tack strength is typically the limiting factor in increasing line speeds of a pouch manufacturing and filling operation.
In this test, the films were tested using a DTC Hot Tack 20 Tester Model No. 52D. Conditions used were:
Specimen width: 24.4 mm Sealing Time: 0.5 seconds Sealing Pressure: 0.27 N/mm/mm Delay Time: 0.5 seconds z5 Peel Speed: 150 mm/sec Number of samples/temperature: 5 Temperature Increments: 5°C
Temperature Range: 70°C - 130°C
Hot tack failure of the seals generally occurs in three 3o stages: no seal; seals which pull apart (peeling); and film failure (where the molten film pulls apart with no apparent effect on the seal). Film failure region begins where the hot tack strength reaches a maximum level.
In each case, film failure occurs just in front of the seal. A force of 1 N/inch (0.4 N/cm) was arbitrarily selected to determine the seal 35 initiation temperature.
Water Filled Pouch Perfromance: Pouches were manufactured using a Hayssen Ultimo VFFS unit and contained 2L of water. The following conditions were used on the Hayssen:
Model No.: RCMH@-PRA
M.A. No. U19644 Mass of water = 2,00U grams Bag size = 7 inches (17_8 cm) by 12.5 inches (31.8 cm) Film width = 15.25 inches (38.7 cm) Registration Rolls: on from 5° to 135°
Pull Belts: on from 10° to 140°
Knife. on from 146° to 265°
Jaw close: from 136° to 275°
Platen: on from 136° to 265°
Stager: off is Auxiliary: on from 137° to 355°
Quali-seal: on from 140° to 265°
Start Delay: SO ms Bag eject: on End air seal: 200 ms 2o Empty bags/minute: 60 Filled bags/minute: 15 Seal bar pressure: 150 psi (1034 kPa) Type of side seal: lap, and Seam seal temperature: 260°F (127°C).
25 A Pro/Fill 3000 liquid filler was attached to the VFFS. The settings on the Pro/Fill 3000 were: P.S. = 35, volume = 0903, and C_O.A. _ 70;
(i) Fnd Heat Seal Strength: Water filled pouches were made using sealing bar temperatures starting at 280°F
(138°C). Five 3o pouches were made at this temperature, then the sealing bar temperature was reduced in 5°F (2.8°C) increments until the pouches no longer held water. Five pouches were obtained from each temperature, the water drained, and the empty pouch tested for seal strength using an Instron Tensile Tester Model No. 1122 using the conditions described in the Heat 35 seal Strength test.
*Trade-mark ~ 16 5 3 4 0 PCT~S94/06730 At the seal bar temperature where the pouch no longer holds water, the force of the water being pumped into the pouch was believed to be too great for the hot, semi-molten seal. As a result,, the seal separated and it appeared that the pouch experienced hot tack failure at s this temperature;
(ii) 5 Foot (1 52 m? Drop Test' The seal bar , temperature was set to 250°F (121°C)and 100 pouches were made from each film structure. The pouches were dropped from a height of 5 feet (1.52 m) such that the pouch landed on the platen seal.
io Tables 2, 2A and 3-9 summarize physical property data for the A/B/A film structures made using the resins described in Table 1. In the Tables, "MD" means machine direction and "CD" means cross/transverse direction.
W~ 95/00587 ~ ~ PCT/LTS94/06730 Table 2 Resin i** 2** 3** 4 5 6 7 8**
Av . au a (mils)3.09 3.03 3.04 2.29 3.18 3.08 3.10 3.17 .
1 percent secant31,92828,50427,87321,15425,29128,42229,251NM*
modulus, psi (220)(197)(192)(146)(174)(196)(202) (MD) (MPa) 1 percent secant39,63830,33431,27424,78128,02230,69635,169NM*
modulus, psi (273)(209)(216)(171)(193)(212)(242) (CD) (MPa) 2 percent secant28,50924,21823,95117,62221,84524,73826,09422,800 modu:lus,psi(MD)(197)(167)(165)(122)(151)(171)(180)(157) (MPa) 2 percent secant33,73026,08726,78319,32224,00926,75430,13025,449 modulus, psi (233)(180)(185)(133)(166)(184)(208)(175) (CD) (MPa) Elmendorf tear,534 530 524 283 480 586' 510 239 g/mil (k /mm)(MD) (21) (20.8)(20.6)(11.1)(18.9)(23) (20) (9.4) Elmendorf tear,654 644 638 527 685 640 632 394 g/mil (k /mm) (CD) (25.7)(25.4)(25.1)(20.7)(27) (25.2)(24.9)(15.5) Dart Im act 596 751 889 >1000897 841 681 465 ( ) Punchire, ft-lbs/in326.0 25.8 26.5 52.0 27.8 27.7 24.2 13.8 Q/cm3) (2.15)(2.13)(2.19)(4.3)(2.3)(2.29)(2) (1.14) Tensile yield, 1580 1334 1308 1145 1278 1368 1500 1558 psi (MPa) (10.9)(9.2)(9) (7.9)(8.8)(9.4)(10.3)(10.7) (MD) Tensile yield, 1732 1417 1395 1050 1342 1452 1614 15t psi (MPa) (11.9)(9.8)(9.6)(7.2)(9.3)(10) (11.1)(10.5) (CD) *NM = Not measured **Comparative Example Only WO 95/00587 ~ ~ ~ 5 3 4 0 PCT/US94/06730 Table 2A
Resin 1** 2** 3** 4 5 6 7 8**
Ultimate tensile,5511 5338 5369 5086 6386 5653.5794 5639 psi (MPa) (38) (36.8)(37) (35.1)(44) (39) (39.9)(38.9) (MD) Ultimate tensile,5768 4873 5145 4293 6065 5310 5697 6173 psi (MPa) (39.8)(33.6)(35.4)(29.6)(41.8)(36.6)(39.3)(42.6) (CD) Elongation (percent)685 668 667 593 702 662 687 761 {MD) Elongation (percent)748 701 719 719 716 688 729 682 (CD) Toughness, ft-lbs/in31364 1224 1228 1017 1448 1304 1439 1562 (J/cm3) (113)(101)(102)(84) (120)(108)(119)(129) (MD) Toughness, ft-lbs/in31549 1222 1293 1043 1399 1298 1507 1569 Q/~) {128)(101)(107)(86) (116)(107)(125)(130) (CD) *NM = Not measured **Comparative Example Only The data in Tables 2 and 2A show that films made using both the heterogeneously branched ethylene/a-olefin copolymers and those made using the novel homogeneously branched substantially linear ethylene/oc-olefin interpolymer had higher puncture resistance than the commercially available SM3 film.
Similarly, the data also show that films made using both the i0 heterogeneously branched ethylene/oc-olefin copolymers and those made using the novel homogeneously branched substantially linear ethylene/oc-olefin interpolymer had higher dart impact strength than the commercially available SM3 film. Furthermore, films made using the homogeneously branched substantially linear ethylene/a-olefin interpolymer had higher is dart impact strength than either the SM3 film or film made using heterogeneously branched ethylene/oc-olefin copolymers.
Elmendorf tear also was higher for films made from both the heterogeneously branched ethylene/oc-olefin copolymers and those made using the novel :homogeneously branched substantially linear ethylene/a-olefin interpolymer, as compared with the commercially available SM3 film.
s Table 3 Resin 1** 2** 3** 4 5 6 7 8**
Coefficient of friction Inside/inside Static 0.20 0.25 0.18 1.53 0.24 0.18 0.20 0.14 Kinetic 0.18 0.23 0.16 1.35 0.20 0.16 0.18 O.la Coefficient of friction Outside/outside Static 0.20 0.25 0.23 0.90 0.26 0.14 0.18 0.12 Kinetic 0.17 0.24 0.22 1.03 0.23 0.13 0.16 0.10 **Comparative Example Only The data in Table 3 shows that all of the films tested, except for that made using Resin 4, had a COF between 0.1 and 0.3.
WO 95/00587 21 b 5 3 4 0 PCT/US94/06730 Table 4 Hot Tack Strength, N/inch (N/cm) TemperatureResinResinResinResinResinResinResinResin C (F) 1** 2** 3** 4 5 6 ~7 8**
55 (131) NA NA NA 0.16 NA NA NA NA
(0.06) 65 (149) NA 0.10 NA 0.66 NA NA NA NA
(0.04) (0.26) 70 (158) NA 0.10 0.10 2.83 0.10 NA NA NA
(0.04)(0.04)(1.11)(0.04) 75 (167) NA 0.10 0.90 5.11 0.48 NA NA NA
(0.04)(0.4)(2.01)(0.19) 80 (176) NA 0.30 1.30 5.04 1.21 0.10 NA NA
(0.1)(0.51)(1.98)(0.48)(0.04) 85 (185) NA 0.49 2.10 3.14 2.46 0.20 NA NA
(0.19)(0.83)(1.24)(0.97)(0.08) 90 (194) NA 1.46 2.60 3.80 4.29 0.70 0.10 NA
(0.57)(1.02)(1.5)(1.69)(0.28)(0.04) 95 (203) 0 2.19 2.60 3.40 6.41 1.90 0.40 0 (0.86)(1.02)(1.34)(2.52)(0.75)(0.16) 100 (212) 0.40 2.78 3.10 3.21 6.95 4.30 0.90 0.30 (0.16)(1.09)(1.22)(1.26)(2.74)(1.69)(0.35)(0.12) 105 (221) 1.40 3.13 3.10 2.58 6.30 5.40 2.60 1.10 (0.55)(1.23)(1.22)(1.02)(2.48)(2.13)(1.02)(0.43) 110 (230) 2.90 3.06 3.00 2.39 5.80 5.70 4.20 2.10 (1.14)(1.20)(1.18)(0.94)(2.28)(2.24)(1.65)(0.83) 115 (239) 3.20 2.62 2.90 2.21 5.00 5.00 4.20 3.40 (1.26)(1.03)(1.14)(0.87)(1.97)(1.97)(1.65)(1.34) 120 (248) 3.30 2.41 3.00 1.64 4.20 4.20 4.00 3.60 (1.3)(0.95)(1.18)(0.65)(1.65)(1.65)(1.57)(1.42) 125 (257) 3.00 2.22 2.60 1.73 3.60 3.60 3.30 3.60 (1.18)(0.87)(1.02)(0.68)(1.42)(1.42)(1.3)(1.42) 130 (266) NM 2.10 NM 1.36 2.90 NM NM 3.50 (0.83) (0.54)(1.14) (1.38) **Comparative Example Only NA = Not Applicable; NM = Not Measured WO 95/00587 216 5 3 4 0 PCT~S94/06730 The data in Table 4 shows that films made using the novel homogeneously branched substantially linear ethylene/oc-olefin interpolymer had higher hot tack strength than film made from heterogeneously branched ethylene/ot olefin copolymers and higher hot tack strength than s commercially available SM3 film.
Figure 6 is a graphical illustration of film hot tack strength versus temperature for resin 7 and comparative resin 1.
Figure 7 graphically illustrates film hot tack strength versus temperature for resin 6 and comparative resin 2.
i0 Figure 8 is a graphical illustration of film hot tack strength versus temperature for resin 5 and comparative resin 3.
Figure 9 is a graphical illustration of film hot tack strength versus sealing time for resins 5-7 and comparative resins 1-3 and comparative film 8.
i5 Firgure 17 is a graphical illustration of maximum film hot tack strength versus resin density for resins 5-7 and comparative resins 1-3.
Table 5 Heat Seal Strength, lbs/inch (g/cm) TemperatureResinResin~ ResinResinResinResinResin Resin C (F) 1** 2** 3** 4 5 6 '7 8**
55 (131) NA NA NA 0 NA NA NA NA
60 (140) NA NA NA 1.20 NA NA NA NA
(214) 65 (149) NA NA NA 2.35 NA NA NA NA
(419) 70 (158) NA NA NA 1.87 NA NA NA NA
(334) 75 (167) NA NA 0 1.68 0 NA NA NA
(300) 80 (176) NA 0.09 0.06 2.51 0.54 NA NA NA
(16) (11) (448)(96) 85 (185) NA 0.21 0.14 2.67 2.38 NA NA NA
(38) (25) (477)(425) 90 (194) NA 0.10 1.30 2.86 3.90 0 NA NA
(18) (232)(510)(697) 95 (203) NA 0.61 3.01 2.49 4.18 1.66 NA NA
(109)(538)(445)(747)(296) 100 (212) NA 1.02 3.87 2.78 5.34 4.60 0 0 (182)(691)(497)(954)(822) 105 (221) 0.04 4.05 3.90 3.02 5.80 5.03 2.98 0.20 (7) (723)(697)(539)(1036)(898)(532)(36) 110 (230) 4.26 4.11 3.97 3.41 6.00 6.16 4.97 2.20 (761)(734)(709)(609)(1072)(1100)(888)(393) 115 (239) 4.95 4.34 4.27 3.61 5.50 6.06 5.86 5.10 (884)(775)(763)(645)(982)(1082)(1047)(911) 120 (248) 5.16 4.72 4.65 3.60 5.55 6.24 5.80 7.60 (922)(843)(830)(643)(991)(1114)(1036)(1357) 125 (257) 6.48 5.00 4.80 3.78 5.76 5.50 6.43 8.80 (1157)(893)(857)(675)(1029)(982)(1148)(1572) 130 (266) 6.61 4.20 4.19 3.84 6.10 5.50 5.90 7.50 (1181)(750)(748)(686)(1089)(982)(1054)(1340) **Comparative Example Only NA = Not Applicable W~ 95/00587 216 5 3 4 0 PcT/US94/06730 The data in Table 5 shows that films made using the novel homogeneously branched substantially linear ethylene/oc-olefin interpolymer had higher heat seal strength than film made from heterogeneously branched ethylene/oc-olefin copolymers and lower heat seal initiation temperatures than both the commercially available SM3 film and film made using heterogeneously branched ethylene/a-olefin copolymers.
Figure 10 is a graphical illustration of film heat seal strength versus temperature for resin 7 and comparative resin 1.
Figure 11 is a graphical illustration of film heat seal io strength versus temperature for resin 6 and comparative resin 2.
Figure 12 is a graphical illustration of film heat seal strength versus temperature for resin 5 and comparative resin 3.
Figure 13 is a graphical illustration of film heat seal strength versus sealing time for resins 5-7 and comparative resins 1-3 and i5 comparative film 8.
Table 6 Hot Tack* Strength, N/inch (N/cm) v. Sealing Time, sec Seal Resin Resin Resin Resin Resin Resin Resin 1** 2** 3** 5 6 7 8**
Time, Hot Hot Hot Hot Hot Hot Hot sec tack, tack, tack, tack, tack, tack, tack, N/in N/in N/in N/in N/in N/in N/in (N/cm) (N/cm) (N/cm) (N/cm)(N/cm) (N/cm) (N/cm) 0.1 0 2.10 2.30 5.82 2.50 0.32 0 (0.83) (0.91) (2.29)(0.98) (0.13) 0.2 0.27 2.72 2.98 6.01 4.10 1.44 0.30 (0.11) (1.07) (1.17) (2.37)(1.61) (0.57) (0.12) 0.3 0.47 2.91 3.05 6.13 5.06 1.80 0.75 (0.19) (1.15) (1.20) (2.41)(1.99) (0.71) (0.3) 0.5 1.40 3.13 3.10 6.30 5.40 2.60 1.50 (0.55) (1.23) (1.22) (2.48)(2.13) (1.02) (0.59) 0.7 1.31 3.10 3.11 6.40 5.76 2.87 1.65 (0.52) (1.22) (1.22) (2.52)(2.27) (1.13) (0.65) 1.0 1.40 3.25 3.24 6.16 5.59 3.24 1.80 (0.55) I (1.28)I (1.28)I (2.43)(2.20) (1.28) (0.71) I I ~
*Seal bar temperatures at 105°C
**Comparative Example Only The data in Table 6 shows that films made using the novel homogeneously branched substantially linear ethylene/oc-olefin interpolymer had higher hot tack strength at low hot tack sealing times than film made from heterogeneously branched ethylene/oc-olefin copolymers and commercially available SM3 film.
i0 WO 95/00587 2 ~ 6 5 3 4 0 PCT~S94/06730 Table 7 Heat Seal* Strength, lbs/inch (~/cm) v. Sealing time, sec Seal Resin Resin Resin Resin Resin Resin Resin 1** 2** 3** 5 6 7 8**
Time Heat Heat Heat Heat Heat Heat Heat (sec) seal, seal, seal, seal, seal, seal, seal, lbs/in lbs/in lbs/in lbs/in lbs/in lbs/in lbs/in /cm) ( /csn)( /cm) /cm) ( /cm) ( /cm) /cm) 0.1 0 3.70 3.90 4.66 4.08 0.05 0 (661) (697) (832) (729) (9) 0.2 0.17 4.43 4.09 5.13 4.40 0.21 0.10 (30) (791) (730) (916) (786) (38) (18) 0.3 0.18 4.28 4.20 5.52 4.46 3.80 0.20 (32) (764) (750) (986) (797) (679) (36) 0.5 0.40 4.12 4.10 5.70 5.10 4.20 0.35 (71) (736) (732) (1018) (911) (750) (63) 0.7 0.31 4.27 4.18 5.60 5.20 4.49 0.40 (55) (763) (747) (1000) (929) (802) (71) 1.0 0.40 4.34 4.25 5.73 5.25 4.30 0.42 (71) (775) (759) (1023) (938) (768) (75) *Seal bar temperatures at 105°C
**Comparative Example Only The data in Table 7 shows that films made using~the novel homogeneously branched substantially linear ethylene/a-olefin interpolymer had higher heat seal strength at low heat sealing times than film made from heterogeneously branched ethylene/oc-olefin copolymers and commercially available SM3 film.
i0 Table 8 Hayssen eal ngth 2 L Waterled Pouches,lbf/inch ) Heat S Stre of Fil (N/m Seal Temp ResinResinResin Resin ResinResin F (C) 1 2 3 * 5 6 7 * *
200 (93) NA NA NA 0 NA NA
205 (96) NA NA NA 3.74 NA NA
(656) 210 (99) NA NA 0 4.6 (806)NA NA
215 (102) NA NA 4.2 (736)5.21 0 NA
(913) 220 (104) NA 0 4.25 5.17 5.54 NA
(745) (906) (971) 225 (107) NA 4.65 4.2 4.94 4.98 NA
(815)(736) (866) (961) 230 (110) NA 4.88 4.3 4.98 5.48 NA
(855)(754) (873) (961) 235 (113) N 4.75 4.25 5.25 4.82 N
A A
(833)(745) (920) (845) 240 (116) 0 4.86 4.3 5.42 5.43 0 (852)(754) (950) (952) 245 (118) 5.55 4.95 4.38 5.55 5.28 5.55 (973)(868)(768) (973) (926)(973) 250 (121) 5.65 5.2 4.07 5.6 4.99 5.65 (990)(912)(713) (982) (875)(983) 255 (124) 5.73 5.32 4.32 5.73 5.22 5.73 (1004)(932)(757) (1004) (915)(1004) 260 (127) 5.6 5.4 4.28 5.69 5.45 5.6 (982)(947)(750) (997) (955)(982) 265 (129) 5.8 5.11 4.5 5.72 5.15 5.8 (1017)(896)(789) (1003) (903)(1017) 270 (132) 5.59 5.15 4.45 5.58 5.02 5.59 (980)(903)(780) (978) (880)(980) *Comparative Example Only The data in Table 8 shows that films made using the novel homogeneously branched substantially linear ethylene/a-olefin interpolymer had broader sealing ranges and higher Hayssen heat seal strengths than WO 95/00587 ~ ~ 4 ~ PCT/US94/06730 film made from heterogeneously branched ethylene/oc-olefin copolymers having similar densities.
Figure 14 is a graphical illustration of vertical form-fill-seal film heat seal strength versus temperature for resin 7 and s comparative resin 1.
- Figure 15 is a graphical illustration of vertical form-fill-seal film heat seal strength versus temperature for resin 6 and comparative resin 2.
Figure 16 is a graphical illustration of vertical form-fill-io seal film heat seal strength versus temperature for resin 5 and -comparative resin 3.
Table 9 summarizes data for the five foot drop test Table 9 is Five Foot Drop Test Resin No. of Failed PouchesPercent Failure 1* 100 100 2* 8 8 3* 3 3 38 ~ 38 *Compararive Example Only Although resin 7 and comparative resin 1 have similar density, pouches made from resin 7 had a much lower percent failure than pouches made from comparative resin 1.
2o Similarly, resin 6 and comparative resin 2 have similar density, but pouches made from resin 6 had a lower percent failure than pouches made from comparative resin 2. Pouches made using resin 5 also had lower percent failure than do pouches made using comparative resin 3, even though the resins have similar density.
Claims (37)
1. A pouch made from a film structure in tubular form and having transversely heat sealed ends, the film structure having at least one film layer comprising:
(I) from 10 to 100 percent by weight of at least one homogeneously branched substantially linear ethylene/.alpha.-olefin interpolymer characterized as having:
(a) a melt flow ratio, I0/I2, >= 5.63, and (b) a molecular weight distribution, M w/M n, defined by the equation: M w/M n <= (I10/I2) - 4.63; and (II) from 0 to 90 percent by weight of at least one polymer selected from the group consisting of a heterogeneously branched linear ethylene/C3-C,8 .alpha.-olefin copolymer, a high-pressure low density polyethylene, and an ethylene-vinyl acetate copolymer.
(I) from 10 to 100 percent by weight of at least one homogeneously branched substantially linear ethylene/.alpha.-olefin interpolymer characterized as having:
(a) a melt flow ratio, I0/I2, >= 5.63, and (b) a molecular weight distribution, M w/M n, defined by the equation: M w/M n <= (I10/I2) - 4.63; and (II) from 0 to 90 percent by weight of at least one polymer selected from the group consisting of a heterogeneously branched linear ethylene/C3-C,8 .alpha.-olefin copolymer, a high-pressure low density polyethylene, and an ethylene-vinyl acetate copolymer.
2. The pouch of claim 1, wherein component (II) is present in the at least one film layer of the film structure.
3. The pouch of claim 1 or 2, wherein the film layer comprising (I) and (II) is a seal layer.
4. The pouch of claim 3, wherein the film structure has an outer layer comprising at least one polymer selected from the group consisting of a heterogeneously branched linear ethylene/C3-C18 .alpha.-olefin copolymer, a high-pressure low density polyethylene, and an ethylene-vinyl acetate copolymer.
5. The pouch of claim 4, wherein the film structure has a core layer comprising a high-pressure low density polyethylene.
6. The pouch of-. claim 1 or 2, wherein the homogeneously branched substantially linear ethylene/.alpha.-olefin interpolymer is a copolymer of ethylene and a C3-C20 .alpha.-olefin.
7. The pouch of claim 1 or 2, wherein the homogeneously branched substantially linear ethylene/.alpha.-olefin interpolymer is a copolymer of ethylene and 1-octene.
8. The pouch of claim 1 or 2, wherein the homogeneously branched substantially linear ethylene/.alpha.-olefin interpolymer is a terpolymer of ethylene and at least one C3-C20 .alpha.-olefin.
9. The pouch of claim 1 or 2, wherein the molecular weight distribution, M w/M n, of the homogeneously branched substantially, linear ethylene/.alpha.-olefin interpolymer of (I) is from 1.5 to 2.5.
10. The pouch of claim 1 or 2, wherein the melt flow ratio, I10/I2, of the homogeneously branched substantially linear ethylene/.alpha.-olefin interpolymer of (I) is at least 7.
11. The pouch of claim 1 or 2, wherein the homogeneously branched substantially linear ethylene/.alpha.-olefin interpolymer of (I) has a melt index, I2, from 0.01 grams/10 minutes to 10 grams/10 minutes, and a density from 0.85 grams/cm3 to 0.94 grams/cm3, a molecular weight distribution, M w/M n, from 1.5 to 2.5, and a melt flow ratio, I10/I2, of at least 7.
12. The pouch of claim 1 or 2, wherein the heterogeneously branched linear ethylene/C3-C18-.alpha.-olefin copolymer of (II) has a density from 0.87 to 0.94 g/cm3 and a melt index from 0.1 to 10 g/10 minutes.
13. The pouch of claim 1 or 2, wherein the high-pressure low density polyethylene of (II) has a density from 0.916 to 0.93 g/cm3 and a melt index from 0.1 to 10 g/10 minutes.
14. The pouch of claim 1 or 2, wherein the ethylene-vinyl acetate copolymer of (II) has a weight ratio of ethylene to vinyl acetate from 2.2:1 to 24:1 and a melt index from 0.2 to 10 g/10 minutes.
15. The pouch of any one of claims 1 to 14, wherein the pouch holds from 5 mL to 5000 mL.
16. The pouch of any one of claims 1 to 14, for containing flowable material.
17. The pouch of claim 16, for containing milk.
18. The pouch of any one of claims 1 to 17, wherein the homogeneously branched substantially linear ethylene/.alpha.-olefin interpolymer is further characterized as having: (c) a critical shear rate at onset of surface melt fracture of at least 50 percent greater than the critical shear rate at the onset of surface melt fracture of a linear ethylene/.alpha.-olefin interpolymer having about the same I2 and M w/M n.
19. A process of preparing a pouch in a vertical form containing a flowable material comprising the steps of forming a film structure; forming the film structure into a tubular member; heat-sealing longitudinal edges and first transverse end of the tubular member to form the pouch;
filling the pouch with the flowable material; and sealing a second transverse end of the tubular member, the film structure having at least one layer comprising:
(a) from 10 to 100 percent by weight of at least one homogeneously branched substantially linear ethylene/.alpha.-olefin interpolymer, and (b) from 0 to 90 percent by weight of at least one polymer selected from the group consisting of a heterogeneously branched linear ethylene/C3-C18 .alpha.-olefin copolymer, a high-pressure low density polyethylene and an ethylene/vinyl acetate copolymer.
filling the pouch with the flowable material; and sealing a second transverse end of the tubular member, the film structure having at least one layer comprising:
(a) from 10 to 100 percent by weight of at least one homogeneously branched substantially linear ethylene/.alpha.-olefin interpolymer, and (b) from 0 to 90 percent by weight of at least one polymer selected from the group consisting of a heterogeneously branched linear ethylene/C3-C18 .alpha.-olefin copolymer, a high-pressure low density polyethylene and an ethylene/vinyl acetate copolymer.
20. The process of claim 19, wherein component (b) is present in the at least one layer of the film structure.
21. A process of preparing a pouch in a vertical form containing a flowable material comprising the steps of forming a film structure; forming the film structure into a tubular member; heat-sealing longitudinal edges and first transverse end of the tubular member to form the pouch;
filling the pouch with the flowable material; and sealing a second transverse end of the tubular member, the film structure having at least one layer comprising:
(I) (a) from 10 to 100 percent by weight of at least one homogeneously branched substantially linear ethylene/.alpha.-olefin interpolymer, and (b) from 0 to 90 percent by weight of at least one polymer selected from the group consisting of a heterogeneously branched linear ethylene/C3-C18 .alpha.-olefin copolymer, a high-pressure low density polyethylene and an ethylene/vinyl acetate copolymer; and at least one layer comprising:
(II) a heterogeneously branched linear ethylene/C3-C18 .alpha.-olefin copolymer having a density greater than 0.87 g/cm3 and a melt index from 0.1 to 10 g/10 minutes.
filling the pouch with the flowable material; and sealing a second transverse end of the tubular member, the film structure having at least one layer comprising:
(I) (a) from 10 to 100 percent by weight of at least one homogeneously branched substantially linear ethylene/.alpha.-olefin interpolymer, and (b) from 0 to 90 percent by weight of at least one polymer selected from the group consisting of a heterogeneously branched linear ethylene/C3-C18 .alpha.-olefin copolymer, a high-pressure low density polyethylene and an ethylene/vinyl acetate copolymer; and at least one layer comprising:
(II) a heterogeneously branched linear ethylene/C3-C18 .alpha.-olefin copolymer having a density greater than 0.87 g/cm3 and a melt index from 0.1 to 10 g/10 minutes.
22. The process of claim 21, wherein component (I)(b) is present in the at least one layer of the film structure.
23. The process of claim 22, wherein the film structure includes at least one other layer comprising:
(III) a high-pressure low density polyethylene having a density from 0.916 to 0.93 g/cm3 and a melt index from 0.1 to 10 g/10 minutes.
(III) a high-pressure low density polyethylene having a density from 0.916 to 0.93 g/cm3 and a melt index from 0.1 to 10 g/10 minutes.
24. The process of any one of claims 19 to 22, wherein said homogeneously branched substantially linear/ethylene .alpha.-olefin interpolymer is a copolymer of ethylene and a C3-C20 .alpha.-olefin.
25. The process of any one of claims 19 to 22, wherein said homogeneously branched substantially linear ethylene/.alpha.-olefin interpolymer is an ethylene/1-octene copolymer.
26. The process of any one of claims 19 to 22, wherein said homogeneously branched substantially linear ethylene/.alpha.-olefin interpolymer is an ethylene/1-hexene copolymer.
27. The process of any one of claims 19 to 22, wherein said homogeneously branched substantially linear ethylene/.alpha.-olefin interpolymer is an ethylene/1-butene copolymer.
28. The process of any one of claims 19 to 22, wherein said homogeneously branched substantially linear ethylene/.alpha.-olefin interpolymer is an ethylene/propene copolymer.
29. The process of any one of claims 19 to 22, wherein said homogeneously branched substantially linear ethylene/.alpha.-olefin interpolymer has a density from 0.85 g/cm3 to 0.94 g/cm3
30. The process of any one of claims 19 to 22, wherein said homogeneously branched substantially linear ethylene/.alpha.-olefin interpolymer has a melt index from 0.01 g/10 minutes to 10 g/10 minutes.
31. The process of any one of claims 19 to 22, wherein said homogeneously branched substantially linear ethylene/.alpha.-olefin interpolymer has a I10/I2 ratio from 7 to 20.
32. The process of any one of claims 19 to 22, wherein said homogeneously branched substantially linear ethylene/.alpha.-olefin interpolymer has a M w/M n from 1.5 to 2.5.
33. The process of any one of claims 19 to 22, wherein said homogeneously branched substantially linear ethylene/.alpha.-olefin interpolymer has a M w/M n of 2.
34. The process of any one of claims 19 to 22, wherein said film structure has a heat sealing range from 50°C to 160°C.
35. The process of any one of claims 19 to 22, wherein said film structure has a heat sealing range from 75°C to 130°C.
36. The process of any one of claims 19 to 22, wherein said homogeneously branched substantially linear ethylene/.alpha.-olefin interpolymer has a melting point range from 50°C to 130°C.
37. The process of any one of claims 19 to 22, wherein said homogeneously branched substantially linear ethylene/.alpha.-olefin interpolymer has a melting point range from 55°C to 110°C.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/082,136 | 1993-06-24 | ||
US08/082,136 US5360648A (en) | 1993-06-24 | 1993-06-24 | Pouch for packaging flowable materials |
PCT/US1994/006730 WO1995000587A1 (en) | 1993-06-24 | 1994-06-14 | Pouch for packaging flowable materials |
Publications (2)
Publication Number | Publication Date |
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CA2165340A1 CA2165340A1 (en) | 1995-01-05 |
CA2165340C true CA2165340C (en) | 2003-10-14 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002165340A Expired - Lifetime CA2165340C (en) | 1993-06-24 | 1994-06-14 | Pouch for packaging flowable materials |
Country Status (11)
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US (2) | US5360648A (en) |
EP (1) | EP0705302B1 (en) |
JP (1) | JPH08511744A (en) |
AU (1) | AU682526B2 (en) |
CA (1) | CA2165340C (en) |
DE (1) | DE69413228T2 (en) |
ES (1) | ES2123146T3 (en) |
FI (1) | FI111547B (en) |
MX (1) | MX9404784A (en) |
NZ (1) | NZ269022A (en) |
WO (1) | WO1995000587A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10960649B2 (en) | 2017-11-14 | 2021-03-30 | Liqui-Box Corporation | Flex-crack resistant and thermally resistant aseptic bulk bags for flexible packaging |
Families Citing this family (103)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5360648A (en) * | 1993-06-24 | 1994-11-01 | The Dow Chemical Company | Pouch for packaging flowable materials |
US5525659A (en) * | 1993-09-08 | 1996-06-11 | The Dow Chemical Company | Batch inclusion packages |
GB9321254D0 (en) * | 1993-10-14 | 1993-12-01 | Du Pont Canada | Pouches of ethylene copolymer film containing a flowable material |
JPH09510484A (en) * | 1994-03-15 | 1997-10-21 | エクソン・ケミカル・パテンツ・インク | Polymer blends, films and articles thereof |
US5614297A (en) * | 1994-05-19 | 1997-03-25 | Viskase Corporation | Polyolefin stretch film |
US6419966B1 (en) * | 1994-12-22 | 2002-07-16 | Exxonmobil Chemical Patents Inc. | Polyethylene articles with improved resistance to water vapor transmission |
US20030199657A1 (en) * | 1994-12-22 | 2003-10-23 | Davis Donna Sue | Polyethylene articles with improved resistance to water vapor transmission |
EP0756931B2 (en) * | 1995-07-31 | 2011-06-22 | Kureha Corporation | Multilayer film |
US6550966B1 (en) * | 1995-08-28 | 2003-04-22 | S.C. Johnson Home Storage, Inc. | Freezer storage bag |
TW421626B (en) * | 1995-09-12 | 2001-02-11 | Dow Chemical Co | Pouches for packaging flowable materials |
US5879768A (en) * | 1995-10-06 | 1999-03-09 | The Dow Chemical Company | Pouches for packaging flowable materials |
US5965224A (en) * | 1995-11-13 | 1999-10-12 | First Brands Corporation | Closure bag with internal tack surfaces |
US5721025A (en) † | 1995-12-05 | 1998-02-24 | The Dow Chemical Company | Pouches for packaging flowable materials in pouches |
GB9620651D0 (en) * | 1996-10-02 | 1996-11-20 | Norester S A | A laminate |
US6086967A (en) * | 1996-11-06 | 2000-07-11 | The Dow Chemical Company | Modified atmosphere films useful in the packaging of perishable food |
US5843540A (en) * | 1996-11-15 | 1998-12-01 | Tetra Laval Holdings & Finance, S.A. | Multi-layer flexible container for flowable materials |
JP2001507296A (en) * | 1996-12-26 | 2001-06-05 | デュポン カナダ インコーポレイテッド | Film with improved sealing properties |
AU742162B2 (en) * | 1997-02-11 | 2001-12-20 | Dow Chemical Company, The | Pouches for packaging flowable materials |
CH692846A5 (en) | 1997-02-24 | 2002-11-29 | Baxter Biotech Tech Sarl | Multilayered co-extruded films for sterilizable containers fluids. |
US5928740A (en) * | 1997-02-28 | 1999-07-27 | Viskase Corporation | Thermoplastic C2 -α-olefin copolymer blends and films |
AU8605798A (en) * | 1997-08-04 | 1999-02-22 | Dow Chemical Company, The | Pouch for packaging flowable materials |
US6416833B1 (en) | 1997-08-22 | 2002-07-09 | Dupont Canada Inc. | Interpolymer film pouch |
US6316547B1 (en) | 1997-09-11 | 2001-11-13 | The Procter & Gamble Company | Masterbatch composition |
EP0905043A1 (en) | 1997-09-27 | 1999-03-31 | The Procter & Gamble Company | Sachet with increased content quantity and process for producing the same |
WO1999033913A1 (en) * | 1997-12-31 | 1999-07-08 | Shell Oil Company | Easy-open packaging |
DE19806475A1 (en) * | 1998-02-17 | 1999-08-19 | Wolff Walsrode Ag | Multi-layer sealing layer and hermetically sealable packaging material made with it |
WO1999051433A1 (en) * | 1998-04-03 | 1999-10-14 | The Dow Chemical Company | Polymeric adhesive composition for polyvinylidene chloride interpolymers |
GB9818869D0 (en) * | 1998-08-29 | 1998-10-21 | Rexam Med Packaging Ltd | Polymeric films and packages produced therefrom |
US6153238A (en) * | 1999-04-22 | 2000-11-28 | Schreiber Foods, Inc. | Packaged decorator cheese product with cap |
US6237308B1 (en) | 1999-05-14 | 2001-05-29 | Glopak Inc. | High-speed pouch forming, sealing and filling machine, method of operation, and multi-layer film therefore |
US20020009579A1 (en) | 1999-05-17 | 2002-01-24 | Yves Quintin | Multi-layer film structure for use with a high-speed pouch forming, filling and sealing machine |
US6371643B2 (en) | 1999-06-02 | 2002-04-16 | S. C. Johnson Home Storage, Inc. | Multi-Layered freezer storage bag |
US6544382B2 (en) | 1999-11-15 | 2003-04-08 | Pactiv Corporation | Apparatus for high-speed heating and cooling of a polymer |
US6548572B1 (en) | 1999-12-07 | 2003-04-15 | Dupont Canada Inc. | Surface printing inks and coatings for use |
US6497676B1 (en) | 2000-02-10 | 2002-12-24 | Baxter International | Method and apparatus for monitoring and controlling peritoneal dialysis therapy |
US6403717B1 (en) | 2000-07-12 | 2002-06-11 | Univation Technologies, Llc | Ethylene inter-polymer blends |
US6440533B1 (en) | 2000-09-22 | 2002-08-27 | Tredegar Film Products Corporation | PVC replacement film |
JP3841648B2 (en) * | 2001-02-27 | 2006-11-01 | ジョンソン・プロフェッショナル株式会社 | Bag |
EP1458567A1 (en) * | 2001-10-19 | 2004-09-22 | Dupont Canada Inc. | Composite film structure for manufacturing pouches using rotary thermic sealing |
AU2002338996A1 (en) * | 2001-11-22 | 2003-06-30 | Metso Paper, Inc. | Delivery system for consumption and/or spare parts |
US20030125662A1 (en) | 2002-01-03 | 2003-07-03 | Tuan Bui | Method and apparatus for providing medical treatment therapy based on calculated demand |
MXPA05000289A (en) * | 2002-06-27 | 2005-09-20 | Pliant Corp | Lap sealable film with a peel layer. |
US7238164B2 (en) | 2002-07-19 | 2007-07-03 | Baxter International Inc. | Systems, methods and apparatuses for pumping cassette-based therapies |
EP1573261B9 (en) * | 2002-12-20 | 2009-08-12 | Ewald Dörken Ag | Method for producing elements from phase change material |
WO2004072176A2 (en) * | 2003-02-04 | 2004-08-26 | Dow Global Technologies Inc. | Film layers made from polymer blends |
US20040202750A1 (en) * | 2003-04-10 | 2004-10-14 | Versluys Robert Thor | Easy-open chub package with heat-sealed ends |
MXPA05013347A (en) * | 2003-06-10 | 2006-04-05 | Dow Global Technologies Inc | Film layers made from ethylene polymer blends. |
US7041352B2 (en) * | 2003-07-01 | 2006-05-09 | Pechiney Emballage Flexible Europe | Thermoplastic structures for the storing and transporting of organoleptic sensitive products |
GB0318019D0 (en) * | 2003-08-01 | 2003-09-03 | Exxonmobil Chem Patents Inc | Bags made from ethylene copolymer films, and films and uses of such copolymers for making such bags |
US8357749B2 (en) | 2003-08-25 | 2013-01-22 | Dow Global Technologies Llc | Coating composition and articles made therefrom |
US9169406B2 (en) | 2003-08-25 | 2015-10-27 | Dow Global Technologies Llc | Coating compositions |
US8158711B2 (en) | 2003-08-25 | 2012-04-17 | Dow Global Technologies Llc | Aqueous dispersion, its production method, and its use |
US7947776B2 (en) | 2003-08-25 | 2011-05-24 | Dow Global Technologies Llc | Aqueous dispersion, its production method, and its use |
US7803865B2 (en) * | 2003-08-25 | 2010-09-28 | Dow Global Technologies Inc. | Aqueous dispersion, its production method, and its use |
US7763676B2 (en) | 2003-08-25 | 2010-07-27 | Dow Global Technologies Inc. | Aqueous polymer dispersions and products from those dispersions |
US8946329B2 (en) | 2003-08-25 | 2015-02-03 | Dow Global Technologies Llc | Coating compositions |
US8349929B2 (en) | 2003-08-25 | 2013-01-08 | Dow Global Technologies Llc | Coating composition and articles made therefrom |
US8722787B2 (en) | 2003-08-25 | 2014-05-13 | Dow Global Technologies Llc | Coating composition and articles made therefrom |
US8779053B2 (en) | 2003-08-25 | 2014-07-15 | Dow Global Technologies Llc | Coating compositions |
AU2005224261B2 (en) * | 2004-03-19 | 2010-04-01 | Dow Global Technologies, Inc. | Film layers made from polymer formulations |
DE202004016420U1 (en) * | 2004-05-17 | 2005-03-24 | Huhtamaki Ronsberg, Zweigniederlassung Der Huhtamaki Deutschland Gmbh & Co. Kg | Stand-up pouch with optimized tear properties |
US7775716B2 (en) | 2004-05-26 | 2010-08-17 | Kee Plastics Ab | Piping bag, blank for manufacturing a piping bag and method of manufacturing a piping bag |
US20060083875A1 (en) * | 2004-10-15 | 2006-04-20 | Sonoco Development, Inc., A Corporation Of South Carolina | Lap sealable laminate for retort pouch |
CN101132781A (en) * | 2004-12-09 | 2008-02-27 | 茵西斯医疗公司 | Room-temperature stable dronabinol formulations |
US20060251343A1 (en) * | 2005-05-09 | 2006-11-09 | True Charles W | Flexible independent multi-layer container and method for forming |
MY148274A (en) * | 2005-07-08 | 2013-03-29 | Dow Global Technologies Inc | Layered film compositions, packages prepared therefrom, and methods of use |
US20070062823A1 (en) * | 2005-09-16 | 2007-03-22 | The Lazy Joe Paint Wrapper Company | Wrapper for painting devices |
NL1031061C2 (en) * | 2006-02-03 | 2007-08-06 | Reynards Internat Holding B V | Piping bag for applying food to a substrate. |
US20070243331A1 (en) * | 2006-02-17 | 2007-10-18 | Dow Global Technologies Inc. | Heat sealable compositions from aqueous dispersions |
ATE534699T1 (en) | 2006-04-26 | 2011-12-15 | Liqui Box Canada Inc | CRACKET-RESISTANT FILMS MADE OF LOW DENSITY POLYETHYLENE |
EP2046290A4 (en) * | 2006-08-04 | 2011-08-17 | Insys Therapeutics Inc | Aqueous dronabinol formulations |
US8211533B2 (en) * | 2006-09-05 | 2012-07-03 | Liqui-Box Corporation | Resin blend of ethylene alpha olefin interpolymer and heterogeneous interpolymer for liquid packaging films |
US7731689B2 (en) | 2007-02-15 | 2010-06-08 | Baxter International Inc. | Dialysis system having inductive heating |
US8870812B2 (en) | 2007-02-15 | 2014-10-28 | Baxter International Inc. | Dialysis system having video display with ambient light adjustment |
US8361023B2 (en) | 2007-02-15 | 2013-01-29 | Baxter International Inc. | Dialysis system with efficient battery back-up |
US8558964B2 (en) | 2007-02-15 | 2013-10-15 | Baxter International Inc. | Dialysis system having display with electromagnetic compliance (“EMC”) seal |
US7998115B2 (en) * | 2007-02-15 | 2011-08-16 | Baxter International Inc. | Dialysis system having optical flowrate detection |
JP2008208173A (en) * | 2007-02-23 | 2008-09-11 | Nitto Denko Corp | Surface protecting sheet |
JP2010535774A (en) * | 2007-08-06 | 2010-11-25 | インシス セラピューティクス インコーポレイテッド | Oral cannabinoid liquid formulations and methods of treatment |
EP2214903A1 (en) * | 2007-11-27 | 2010-08-11 | Dow Global Technologies Inc. | A multilayer structure for the manufacture of packaging and packaging thereof |
EP2080615A1 (en) | 2008-01-18 | 2009-07-22 | Dow Global Technologies Inc. | Coated substrates and packages prepared therefrom |
US20100172600A1 (en) * | 2009-01-06 | 2010-07-08 | The Coca-Cola Company | Flexible container and method of making the same |
EP2275254A1 (en) * | 2009-07-17 | 2011-01-19 | Dow Global Technologies Inc. | Coated substrates and packages prepared therefrom |
DE202009012547U1 (en) * | 2009-09-17 | 2010-02-11 | Rapp, Günther | Cleaning product, in particular for the windscreen washer system of a motor vehicle |
US20110150368A1 (en) * | 2009-12-21 | 2011-06-23 | Justin Alan Ellsworth | Bag and Article of Manufacture |
US20110236540A1 (en) | 2010-03-24 | 2011-09-29 | Cryovac, Inc. | Ovenable cook-in film with reduced protein adhesion |
BR112012025478A2 (en) | 2010-04-16 | 2019-09-24 | Liqui Box Corp | multilayer film to produce pouches to contain dispersible materials and process to produce pouches filled with a dispersible material |
CA2794597C (en) | 2010-04-16 | 2021-05-04 | Liqui-Box Corporation | Multi-layer, ethylene polymer-based films with novel polypropylene blend-based stiffening layer |
WO2011130489A2 (en) | 2010-04-16 | 2011-10-20 | Liqui-Box Corporation | Multi-layer, ethylene polymer-based films with high-density polyethylene based stiffening layer |
EP2615161B1 (en) * | 2010-09-06 | 2019-12-25 | Toyo Seikan Kaisha, Ltd. | Cell culture container formed by a multilayer film |
US20120213896A1 (en) | 2011-02-23 | 2012-08-23 | Cryovac, Inc. | Ovenable Cook-In Film Providing Decreased Protein Adhesion |
JP5825023B2 (en) * | 2011-09-30 | 2015-12-02 | 東ソー株式会社 | Laminated body |
KR102177644B1 (en) | 2012-12-28 | 2020-11-11 | 다우 글로벌 테크놀로지스 엘엘씨 | A coating composition and articles made therefrom |
EP2922925B1 (en) | 2012-12-28 | 2019-12-04 | Dow Global Technologies LLC | Coating compositions |
KR101391998B1 (en) * | 2013-04-10 | 2014-05-27 | 두희글로벌로지스틱스 (주) | The material supplying method |
JP2017526589A (en) | 2014-08-21 | 2017-09-14 | ダウ グローバル テクノロジーズ エルエルシー | Flexible container and method for making a flexible container |
CN108290335B (en) * | 2015-12-11 | 2021-08-10 | 陶氏环球技术有限责任公司 | Multilayer polyethylene film, and articles made therefrom |
WO2018063694A1 (en) * | 2016-09-29 | 2018-04-05 | Dow Global Technologies Llc | Multilayer stretch films and methods thereof |
US11179516B2 (en) | 2017-06-22 | 2021-11-23 | Baxter International Inc. | Systems and methods for incorporating patient pressure into medical fluid delivery |
ES1189859Y (en) | 2017-07-31 | 2017-11-06 | Liquibox Spain Sl | STERILIZING MACHINE FOR LIQUID CONTAINER BAGS |
US11383910B2 (en) | 2017-09-13 | 2022-07-12 | Liqui-Box Corporation | Process for preventing organoleptic degradation in flexibly-packaged sensitive foods and packaged products thereof |
US11246578B2 (en) | 2019-05-15 | 2022-02-15 | Covidien Lp | Tissue collection bags with inner surface pouches |
JP6994640B2 (en) * | 2020-06-22 | 2022-01-14 | 東洋インキScホールディングス株式会社 | Adhesive resin composition, sheet, lid material, member set and container using the composition |
Family Cites Families (68)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USB632416I5 (en) * | 1956-03-01 | 1976-03-09 | ||
US3250825A (en) * | 1962-11-09 | 1966-05-10 | Phillips Petroleum Co | Blends of crystalline polyethylene or ethylene-butene copolymer with amorphous ethylene-higher alpha-olefin copolymers |
CA849081A (en) * | 1967-03-02 | 1970-08-11 | Du Pont Of Canada Limited | PRODUCTION OF ETHYLENE/.alpha.-OLEFIN COPOLYMERS OF IMPROVED PHYSICAL PROPERTIES |
US3682767A (en) * | 1970-10-02 | 1972-08-08 | Du Pont | Ethylene copolymer blend for liquid packaging film |
US3741253A (en) * | 1971-03-30 | 1973-06-26 | Grace W R & Co | Laminates of ethylene vinyl acetate polymers and polymers of vinylidene chloride |
BE795750A (en) * | 1972-02-22 | 1973-08-21 | Union Carbide Corp | MULTI-LAYER HEAT SHRINKABLE FILM |
US4071674A (en) * | 1972-09-14 | 1978-01-31 | Mitsui Petrochemical Industries Ltd. | Process for polymerization or copolymerization of olefin and catalyst compositions used therefor |
JPS5213580A (en) * | 1975-07-23 | 1977-02-01 | Kureha Chem Ind Co Ltd | Preparation of multiply resin laminate |
US4151318A (en) * | 1976-06-21 | 1979-04-24 | Mobil Oil Corporation | Laminar thermoplastic film constructions |
JPS5952643B2 (en) * | 1977-01-27 | 1984-12-20 | 三井化学株式会社 | ethylene copolymer |
CA1157617A (en) * | 1977-12-14 | 1983-11-29 | Milton L. Weiner | Oriented polypropylene with linear low density polyethylene copolymer coating |
US4505969A (en) * | 1977-12-14 | 1985-03-19 | Mobil Oil Corporation | Oriented polypropylene with linear low density poly-ethylene copolymer coating |
DE2801541A1 (en) * | 1978-01-14 | 1979-07-19 | Hoechst Ag | AETHYLENE COPOLYMERS AND THEIR USE FOR THE PRODUCTION OF FILMS |
US4302566A (en) * | 1978-03-31 | 1981-11-24 | Union Carbide Corporation | Preparation of ethylene copolymers in fluid bed reactor |
US4302565A (en) * | 1978-03-31 | 1981-11-24 | Union Carbide Corporation | Impregnated polymerization catalyst, process for preparing, and use for ethylene copolymerization |
US4243619A (en) * | 1978-03-31 | 1981-01-06 | Union Carbide Corporation | Process for making film from low density ethylene hydrocarbon copolymer |
JPS6036942B2 (en) * | 1978-05-22 | 1985-08-23 | 三井化学株式会社 | Multilayer laminated structure |
JPS5512008A (en) * | 1978-06-29 | 1980-01-28 | Mitsui Petrochemical Ind | Packing laminate sack |
US4303710A (en) * | 1978-08-16 | 1981-12-01 | Mobil Oil Corporation | Coextruded multi-layer polyethylene film and bag construction |
DE2847986A1 (en) * | 1978-11-04 | 1980-05-22 | Huels Chemische Werke Ag | METHOD FOR PRODUCING POWDER-SHAPED, THERMOPLASTIC COPOLYMERS FROM AETHYLENE AND BUTEN- (1) |
JPS603323B2 (en) * | 1978-12-11 | 1985-01-28 | 三井化学株式会社 | Polymerization method of olefins |
US4333299A (en) * | 1979-04-27 | 1982-06-08 | Hamilton Joel A | Form fill and seal package making |
US4357191A (en) * | 1980-03-03 | 1982-11-02 | Mobil Oil Corporation | Laminar thermoplastic film constructions |
US4390573A (en) * | 1980-03-03 | 1983-06-28 | Mobil Oil Corporation | Laminar thermoplastic film constructions |
JPS5734145A (en) * | 1980-08-07 | 1982-02-24 | Mitsui Petrochem Ind Ltd | Ethylene-alpha-olefin copolymer composition |
US4367841A (en) * | 1980-11-18 | 1983-01-11 | Mobil Oil Corporation | Thermoplastic carrying bag with binary polyolefin resin blend |
US4346834A (en) * | 1980-11-18 | 1982-08-31 | Mobil Oil Corporation | Thermoplastic carrying bag with polyolefin resin blend |
US4356221A (en) * | 1981-05-15 | 1982-10-26 | Union Carbide Corporation | Melt-extruded multilayer polyethylene bag film |
JPS57193353A (en) * | 1981-05-25 | 1982-11-27 | Sekisui Chemical Co Ltd | Film for shrinkable packing |
JPS58109547A (en) * | 1981-12-23 | 1983-06-29 | Toyo Soda Mfg Co Ltd | Ethylene polymer composition for extrusion coating |
JPS58120654A (en) * | 1982-01-13 | 1983-07-18 | Mitsui Petrochem Ind Ltd | Ethylene-alpha-olefin copolymer composition |
US4503102A (en) * | 1982-01-20 | 1985-03-05 | Du Pont Of Canada, Inc. | Pouches of ethylene-α-olefin copolymer/ethylene-vinyl acetate copolymer blends |
US4405666A (en) * | 1982-04-02 | 1983-09-20 | Mobil Oil Corporation | Film laminate food wrap and food pouch therefrom |
US4418114A (en) * | 1982-04-29 | 1983-11-29 | Mobil Oil Corporation | Coextruded thermoplastic stretch-wrap |
AU565262B2 (en) * | 1982-06-02 | 1987-09-10 | Du Pont Canada Inc. | Pouches of copolymer film |
US4405667A (en) * | 1982-08-06 | 1983-09-20 | American Can Company | Retortable packaging structure |
JPS5975933A (en) * | 1982-10-25 | 1984-04-28 | Tokuyama Soda Co Ltd | Composition for laminate |
US4547413A (en) * | 1982-12-01 | 1985-10-15 | Union Carbide Corporation | Shrinkable film for poultry bags |
US4447480A (en) * | 1982-12-01 | 1984-05-08 | Union Carbide Corporation | Shrinkable film for poultry bags |
US4525257A (en) * | 1982-12-27 | 1985-06-25 | Union Carbide Corporation | Low level irradiated linear low density ethylene/alpha-olefin copolymers and film extruded therefrom |
US4534154A (en) * | 1983-05-10 | 1985-08-13 | Gaubert R J | Method and machine for filling bags with liquid |
US4565720A (en) * | 1983-07-27 | 1986-01-21 | Idemitsu Petrochemical Co., Ltd. | Packaging bag |
US4565742A (en) * | 1983-10-20 | 1986-01-21 | Du Pont Canada Inc. | Process for forming a sealant WEB-PVDC-base film laminate |
JPS6088016A (en) * | 1983-10-21 | 1985-05-17 | Mitsui Petrochem Ind Ltd | Ethylene copolymer |
US4701359A (en) * | 1985-01-28 | 1987-10-20 | Fuji Photo Film Co., Ltd. | Packaging material for photosensitive materials |
US4640856A (en) * | 1985-04-29 | 1987-02-03 | W. R. Grace & Co., Cryovac Div. | Multi-layer packaging film and receptacles made therefrom |
CA1340037C (en) * | 1985-06-17 | 1998-09-08 | Stanley Lustig | Puncture resistant, heat-shrinkable films containing very low density polyethylene copolymer |
US5059481A (en) * | 1985-06-17 | 1991-10-22 | Viskase Corporation | Biaxially stretched, heat shrinkable VLDPE film |
EP0216509B1 (en) * | 1985-08-23 | 1991-09-18 | Showa Denko Kabushiki Kaisha | Medical bag |
NZ217626A (en) * | 1985-09-30 | 1989-11-28 | W R Grace & Co Conn Formerly W | Packaging film consisting of #a# olefin copolymers |
CA1324749C (en) * | 1987-04-10 | 1993-11-30 | Vincent Wayne Herran | Flexible stretch/shrink film |
US4963419A (en) * | 1987-05-13 | 1990-10-16 | Viskase Corporation | Multilayer film having improved heat sealing characteristics |
US4837084A (en) * | 1987-07-02 | 1989-06-06 | W. R. Grace & Co.-Conn. | Thermoplastic multi-layer packaging film and bags made therefrom |
JPH07103276B2 (en) * | 1987-09-11 | 1995-11-08 | 日本石油化学株式会社 | Ethylene-based thermoplastic resin composition |
US4820557A (en) * | 1987-09-17 | 1989-04-11 | W. R. Grace & Co.-Conn. | Thermoplastic packaging film of low I10 /I2 |
US4869912A (en) * | 1988-02-12 | 1989-09-26 | Abbott Laboratories | Pre-filled nurser pouch |
GB2227448B (en) * | 1988-11-18 | 1992-09-30 | Grace W R & Co | Multi-layer film structure for packaging and bags made therefrom |
US5272236A (en) * | 1991-10-15 | 1993-12-21 | The Dow Chemical Company | Elastic substantially linear olefin polymers |
JP2878431B2 (en) * | 1990-10-16 | 1999-04-05 | エスエムシー株式会社 | Suction transfer device |
AU660043B2 (en) * | 1991-07-18 | 1995-06-08 | Exxon Chemical Patents Inc. | Heat sealed article |
US5288531A (en) * | 1991-08-09 | 1994-02-22 | The Dow Chemical Company | Pouch for packaging flowable materials |
US5278272A (en) * | 1991-10-15 | 1994-01-11 | The Dow Chemical Company | Elastic substantialy linear olefin polymers |
WO1994006859A1 (en) * | 1992-09-15 | 1994-03-31 | The Dow Chemical Company | Impact modification of thermoplastics |
US5360648A (en) * | 1993-06-24 | 1994-11-01 | The Dow Chemical Company | Pouch for packaging flowable materials |
JPH07193353A (en) * | 1993-12-27 | 1995-07-28 | Yokogawa Electric Corp | Socket for component |
JP3568130B2 (en) * | 1994-09-02 | 2004-09-22 | 株式会社協和製作所 | Double pinion switchgear |
JPH08109547A (en) * | 1994-10-06 | 1996-04-30 | Tsudakoma Corp | Device for removing defective yarn |
JPH0975933A (en) * | 1995-09-18 | 1997-03-25 | Noto Isamu | Method for recovering oil on water surface and oil recovering device used for the same |
-
1993
- 1993-06-24 US US08/082,136 patent/US5360648A/en not_active Expired - Lifetime
-
1994
- 1994-06-14 DE DE69413228T patent/DE69413228T2/en not_active Expired - Lifetime
- 1994-06-14 NZ NZ269022A patent/NZ269022A/en unknown
- 1994-06-14 JP JP7502916A patent/JPH08511744A/en active Pending
- 1994-06-14 WO PCT/US1994/006730 patent/WO1995000587A1/en active IP Right Grant
- 1994-06-14 ES ES94921959T patent/ES2123146T3/en not_active Expired - Lifetime
- 1994-06-14 CA CA002165340A patent/CA2165340C/en not_active Expired - Lifetime
- 1994-06-14 EP EP94921959A patent/EP0705302B1/en not_active Expired - Lifetime
- 1994-06-14 AU AU72466/94A patent/AU682526B2/en not_active Ceased
- 1994-06-23 MX MX9404784A patent/MX9404784A/en unknown
- 1994-10-31 US US08/332,201 patent/US5508051A/en not_active Expired - Lifetime
-
1995
- 1995-12-22 FI FI956245A patent/FI111547B/en not_active IP Right Cessation
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10960649B2 (en) | 2017-11-14 | 2021-03-30 | Liqui-Box Corporation | Flex-crack resistant and thermally resistant aseptic bulk bags for flexible packaging |
Also Published As
Publication number | Publication date |
---|---|
EP0705302A1 (en) | 1996-04-10 |
US5508051A (en) | 1996-04-16 |
EP0705302B1 (en) | 1998-09-09 |
AU7246694A (en) | 1995-01-17 |
WO1995000587A1 (en) | 1995-01-05 |
AU682526B2 (en) | 1997-10-09 |
DE69413228D1 (en) | 1998-10-15 |
FI111547B (en) | 2003-08-15 |
JPH08511744A (en) | 1996-12-10 |
NZ269022A (en) | 1997-11-24 |
DE69413228T2 (en) | 1999-01-28 |
FI956245A (en) | 1995-12-22 |
US5360648A (en) | 1994-11-01 |
CA2165340A1 (en) | 1995-01-05 |
ES2123146T3 (en) | 1999-01-01 |
FI956245A0 (en) | 1995-12-22 |
MX9404784A (en) | 1995-01-31 |
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