CA2297827A1 - Polyethylenes with enhanced heat seal properties - Google Patents

Polyethylenes with enhanced heat seal properties Download PDF

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Publication number
CA2297827A1
CA2297827A1 CA002297827A CA2297827A CA2297827A1 CA 2297827 A1 CA2297827 A1 CA 2297827A1 CA 002297827 A CA002297827 A CA 002297827A CA 2297827 A CA2297827 A CA 2297827A CA 2297827 A1 CA2297827 A1 CA 2297827A1
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Prior art keywords
component
extrusion
low density
polyethylene
density polyethylene
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Abandoned
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CA002297827A
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French (fr)
Inventor
Ray Edwards
Diane Hines Farnham
Bruce Alexander Gillespie
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Eastman Chemical Co
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Individual
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Priority claimed from US09/088,904 external-priority patent/US6174612B1/en
Application filed by Individual filed Critical Individual
Publication of CA2297827A1 publication Critical patent/CA2297827A1/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/06Polyethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/06Properties of polyethylene
    • C08L2207/066LDPE (radical process)
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C08L2666/06Homopolymers or copolymers of unsaturated hydrocarbons; Derivatives thereof

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

An improved extrusion coating is described comprising at least two polyethylene homopolymers, one component being a low melt index medium density polyethylene homopolymer, and another component being a high melt index low density polyethylene homopolymer. Superior heat seal strengths are achieved with this blend.

Description

POLYETHYLENES WITH ENHANCED HEAT SEAL PROPERTIES
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit under 35 U.S.C. ~ 119(e) of United States Provisional Application Serial No. 60/055,770, filed August 14, 1997, and incorporated herein.
The present invention relates to a composition of matter obtained by the blending of two polyethylenes to provide strong heat seals for extrusion coated structures.
BACKGROUND OF THE INVENTION
Prior art blends of polyethylenes are discussed, for instance, in U.S.
Patent No. 4,339,507. One component of this blend is a linear low density copolymer of ethylene and octene and a second component is a low density polyethylene homopolymer. An example of such a linear low density polyethylene blend is Dow Chemical Company's Linear Low Density Polyethylene 3010. Such blends are typically useful as extrusion coatings onto various structures, such as flexible polymeric film/paper packages far foods, and metallized polymeric film balloons. The coatings serve as heat seal media and as barriers to protect the contents of a package from outside contamination, or to retain the contents, such as a gas such as helium, within a coated and sealed balloon. The ethylene-octene copolymer component of the prior art two-component blends is used to provide strong heat seal strengths required in certain extrusion coated structures.
*rB
However, these prior art blends create many problems in an extrusion coating operation. In particular, the blends require excessively high extruder amps to extrude; some extruders are not rated for these high amps. The high amps requirement is the reason that low density polyethylenes are combined with the copolymers, usually at about 20 weight percent of the low density polyethylene, to enhance processability.
Also, because these prior art blends exhibit high viscosities at the high shear rates associated with extrusion coating, they tend to generate excessive melt temperatures in the feed sections of extruder screws.
These high melt temperatures in the feed section cause extruder output variations, or surging, along with fnelt fracture and gel formation, all of which introduce quality defects. The prior art blends also exhibit high neck-in of the molten polymer web with its associated edge instability. The edge instability of the molten web requires that the edge be trimmed, which results in costly polymer waste. These facts are discussed in a technical article published in rting Magazine, March 1997, entitled "Benefits, Processing Ease, Keep LDPE in the Mix".
The above technical article also reports that "performance capabilities of LDPE (low density polyethylene) are broadened by the addition of comonomers. Vinyl acetate and methyl acrylate are two primary examples." Ethylene vinyl acetate (EVA) copolymers permit lower heat seal initiation temperatures in those heat sealing operations requiring such low sealing temperatures. Ethylene methyl acrylate (EMA) copolymers display strong heat-seal characteristics for both film and extrusion coating applications."
Copolymers of ethylene and methyl acrylate, containing about 2 weight percent to about 5 weight percent methyl acrylate, are thermally stable. However, the prior art blends containing linear low density copolymers of ethylene and octane (or any other a-olefin), and the low density copolymers of ethylene and vinyl acetate, containing about 2 weight percent to about 18 weight percent vinyl acetate, are thermally unstable.
Either copolymer will degrade if it remains for tao long in a heated extruder barrel, such as during a temporary operational shutdown. Such degradation, or molecular breakdown, generates massive detects in subsequent extrusion coatings. In most cases, the extrusion operator must clean his equipment before he can continue with production. Because of the copolymers' being prone to thermal degradation, these copolymers must be purged from the extruder before extruder screw rotation is stopped.
The purge material is usually an inert polymer such as a low density polyethylene homopolymer. Such an inert polyethylene homopolymer can remain in an extruder until that extruder's next operational startup, and it can remain in an extruder through the heat-up cycle necessary to reach the extruder temperatures required to extrusion coat a copolymer. This need for purging the thermally unstable copolymers from extruders is materially costly, with the purge material having to be purchased and inventoried at the site of the extrusion coating operation.
Considering the problems associated with extrusion coating the above two copolymers, there is need for a more ideal homopolymer based on ethylene. Such a polymer would be an inert homopolymer of ethylene, extrusion coatings of which would be capable of equaling or exceeding the heat seal strengths of linear iow density copolymers of ethylene and octene (ar any other a-olefin), or the low density copolymer of ethylene and vinyl acetate. Such an ideal homopolymer would exhibit none of those problems of a linear low density polyethylene blend; that is, the ideal homopolymer would not require high extruder drive amps. Nor would it exhibit high viscosities due to high shear rates, which, in turn, generate excessive melt temperatures, melt fracture, and gels. Nor would such an ideal homopolymer generate high web neck-in, such high neck-in manifesting itself in unstable web edges, which must be trimmed away with loss of material. Finally, such an ideal homopolymer would not require purging each time an extrusion operation is interrupted, and it could remain in the extruder indefinitely between production start-ups.
The present inventors have unexpectedly discovered an improved extrusion coating ethylene homopolymer composition of matter comprising a two-component blend of polyethylene homopolymers. The first component is a low melt index medium density polyethylene to provide strong heat seals. The second component is a high melt index low density polyethylene to provide a good wetting of substrates, such good wetting being essential to good coating-to-substrate adhesion, with a good adhesion being essential to strong heat seals.
The present invention unexpectedly permits heat seal strengths exceeding those of linear low density polyethylene compositions. In addition, the present invention presents none of the aforementioned extrusion coating problems, such as thermal instability, associated with linear low density copolymers of ethylene and octene (or any other a-olefin) or low density copolymers of ethylene and vinyl acetate.
U.S. Patents 5,268,230 and 5,350,476, copending Application Serial No. 09/023,900, filed February 13, 1998 (based on Provisional Application Serial No. 60/036,297, filed February 19, 1997; Eastman Chemical Company Docket No. 70537), and copending Application Serial No.
09/037,558, filed March 9, 1998 (bassed on Provisional Application Serial No. 60/043,222, filed April 9, 1997; Eastman Chemical Company Docket No. 70632) describe processes to produce high gloss extrusion coatings and smooth paper laminates. Similarly, copending Application Serial No.
09/048,455, filed March 26, 1998 (based on Provisional Application Serial No. 60/043,935, filed April 21, 1997; Eastman Chemical Company Docket No. 70638; and on Provisional Application Serial No. 60/055,768, filed August 14, 1997; Eastman Chemical Company Docket No. 70732 ) discloses improved 3-component blends of a linear low density polyethylene and two polyethylene homopolymers. Each of these patents and applications are hereby incorporated by reference. One polyethylene involved in each of the above five documents is a medium density polyethylene of narrow molecular weight distribution having a melt index of 0.5-dg/min to 4-dglmin at 190°C, a swell ratio of 1.2 to 1.35, an annealed density of about 0.926-glee, and a polydispersity index at or below 9. This same medium density polyethylene is the first component of the two component polyethylene blend according to the present invention.
The blend according to the present invention also contains a second component, a low density polyethylene of broad molecular weight distribution having a melt index range of 18-dglmin to 22-dg/min, measured at 190°C, a swell ratio greater than 1.60, an annealed density of about 0.91-glee to about 0.92-glee, and a polydispersity above 9.
The blends are prepared by mixing at least the above two components by methods known in the art. Additional polyethylene components may also be added, as well as other known additives such as fillers, pigments, etc. It is preferred that the first component above be present in a major amount, i.e., greater than 50 weight percent. An even more preferred blend is one wherein the first component above is present in the amount of about 80 weight percent and the second component above is present in the amount of about 20 weight percent.
Various extrusion coating methods are known in the art, such as extruding against glossy chill rolls or matte chill rolls. The composition according to the present invention can be used in any known extrusion process.
EXPERIMENTAL
In the forthcoming examples, the properties are determined as follows:
Melt index was determined in accordance with ASTM D1238-62T at 374°F (190°C).
Swell ratio is defined as the ratio of the diameter of the extrudate over that of the orifice diameter of the extrusion plastometer in ASTM D1238-62T. The diameter of the specimen is measured in the area between 0.159-cm and 0.952-cm of the initial portion of the specimen as it emerges from the extrusion plastometer.
Measurements were made by standard methods according to ASTM D374.
Annealed density was determined in accordance with ASTM D1505.
Polydispersity index is the ratio of the weight-average molecular weight, MW, to number-average molecular weight, M~.. MW and M~ were obtained by size-exclusion chromotography on a Waters 150C gel permeation chromatograph equipped with the standard refractometer detector and a Viscotek 1508 differential viscometer system. The 3-column set consisted of Waters' 103, 10°, and linear-mixed bed (103, 104, and 1050 Micro-Styragel HT columns. The samples were run as 0.125% (weight/volume) solutions in ortho-dichlorobenzene at 140°C.
The data were interpreted using Viscotek Unical software (V4.02), by universal calibration using NBS 1475 (linear polyethylene) and NBS 1476 (branched polyethylene) for any polyethylene sample.
Heat seal strength is determined by thermally welding opposing polymer coating specimens, each 1.00-inch (2.54-cm) wide, using a Sentinel Bar Sealer, Model 12AF. The top sealing bar only is heated to 400°F (205°C), with the non-heated bottom sealing bar protected with a teflon tape. The opposing coatings are clamped between the sealing bars at a force of 40-psi (2.82-Kglcm2) for 2.0-seconds. Sealed specimens are then tested for seal strength in a Thwing-Albert Tensile Tester, Model 1450-24-8, equipped with a 9.8-1b (4.4-Kg) load cell, pulled at a separation rate of 5.0-in/min (12.6-cm/min). Seal strength, in grams, is noted.
EXAMPLES
Fxa~mnle 1 A 2-component polymeric blend according to the present invention was made by blending the following components as previously described in the Description of the Preferred Embodiments, above:
1) 20 weight percent of a 18-22-dglmin melt index, broad molecular weight polyethylene homopolymer.
2) 80 weight percent of a 0.5-4.0-dg/min melt index, narrow molecular weight polyethylene homopolymer.
The resultant melt index of this blend was 2.8-dglmin.
This formulation was extrusion coated to a foillpolyethylenel paperboard structure having aluminum foil as an outer surface; namely, 0.000285-inch (0.00725-mm) foiIILow Density Polyethylene/Bleached Machine-Glazed paper. The foil surface had first been primed with MICA
Corporation's MICA A-291-C, a water based polymeric chromium complex compound, designed for aluminum foil. The polymer was applied to the primed foil at a melt temperature of 580°F (305°C) at a sufficient extrusion rate to achieve a coating thickness of 0.002-inch (0.0508-mm) at 132-fpm (14-m/min).
During extrusion, the extruder feed zones, Zones 1, 2, and 3, equilibrated to 290°F (143°C), 250°F (121°C), and 548°F (287°C), respectively.
Heat seal strength was 9.0-lblinch (1.65 kglcm).
Example 2 - comparative Dow Chemical Company's linear low density polyethylene formula 3010 is a blend of about 20% by weight of a low density homopolymer polyethylene and about 80% by weight of a copolymer of ethylene and octene, containing about 7% to 10% by weight of octene. This formulation was extrusion coated to a foillpolyethylenel paperboard structure having _$_ aluminum foil as an outer surface; namely, 0.000285 foiIILow Density Polyethylene/Bleached Machine-Glazed paper. The foil surface had first been primed with MICA Corporation's MICA A-291-C, a water based polymeric chromium complex compound, designed for aluminum foil. The polymer was applied to the primed foil at a melt temperature of 597°F
(314°C) at a sufficient extrusion rate to achieve a coating thickness of 0.002-inch (0.0508-mm) at 132-fpm (14-m/min).
During extrusion, the extruder feed zones, Zones 1, 2, and 3, equilibrated to 397°F (202°C), 497°F (258°C), and 568°F (298°C), respectively.
Heat seal strength was 6.6-Iblinch (1.84 kglcm).
DSM's linear low density polyethylene formula STAMYLEX 1066F is a blend of about 20% by weight of a low density homopoiymer polyethylene and about 80% by weight of a copolymer of ethylene and octene, containing about 7% to 10% by weight of octene. This formulation was extrusion coated to a foil/polyethylenel paperboard structure having aluminum foil as an outer surface; namely, 0.000285 foiI/Low Density PolyethylenelBleached Machine-Glazed paper. The foil surface had first been primed with MICA
Corporation's MICA A-291-C, a water based polymeric chromium complex compound, designed for aluminum foil. The polymer was applied to the primed foil at a melt temperature of 600°F (316°C} at a sufficient extrusion rate to achieve a coating thickness of 0.002-inch (0.0508-mm) at 132-fpm (14-mlmin).
During extrusion, the extruder feed zones, Zones 1, 2, and 3, equilibrated to 398°F (204°C), 498°F (258°C), and 571°F (300°C), respectively.
Heat seal strength was 5.9-Ib/inch (1.06 kg/cm).

_g_ Example 4 - comparative Rexene's linear tow density polyethylene formula 2503-10 is a blend of about 20% by weight of a low density homopolymer polyethylene and about 80% by weight of a copolymer of ethylene and octene, containing about 7% to 10% by weight of octene. This formulation was extrusion coated to a foiUpolyethylene/ paperboard structure having aluminum foil as an outer surface; namely, 0.000285 foiIILow Density PolyethyleneBleached Machine-Glazed paper. The foil surface had first been primed with MICA
Corporation's MICA A-291-C, a water based polymeric chromium complex compound, designed for aluminum foil. The polymer was applied to the primed foil at a melt temperature of 597°F (314°C) at a sufficient extrusion rate to achieve a coating thickness of 0.002-inch (0.0508-mm) at 132-fpm (14-mlmin).
During extrusion, the extruder feed zones, Zones 1, 2, and 3, equilibrated to 399°F (204°C), 498°F (258°C), and 569°F (298°C), respectively.
Heat seal strength was 7.0-Iblinch (1.34 kglcm).
~nle, 5comparative Millennium's formula GA615050 is a an octene-ethylene copolymer containing 7 weight percent to 10 weight percent octene. Rexene's tow density polyethylene formula 5050 is a polyethylene homopolymer. The two polymers were tumble blended at a ratio of 80 weight percent of the Millennium GA615050 copolymer to 20 weight percent of the Rexene low density formula 5050. Such dilution of the Millennium copolymer was necessary to permit its being extrusion coatable. This tumbled blend was extrusion coated to a foil/polyethylenel paperboard structure having aluminum foil as an outer surface; namely, 0.000285 foiI/Low Density Polyethylene/Bleached Machine-Glazed paper. The foil surface had first been primed with MICA Corporation's MICA A-291-C, a water based polymeric chromium complex compound, designed for aluminum foil. The polymer was applied to the primed foil at a melt temperature of 601°F
(316°C) at a sufficient extrusion rate to achieve a coating thickness of 0.002-inch (0.0508-mm) at 132-fpm (14-mlmin).
During extrusion, the extruder feed zones, Zones 1, 2, and 3, equilibrated to 401°F (205°C), 498°F (258°C), and 563°F (295°C), respectively.
Heat seal strength was 5.1-Ib/inch (0.90 kg/cm).
The above examples show unexpectedly that the present invention (Example 1 ) provides stronger heat seals than the linear low density polyethylene formulations (Examples 2 through 5), even as a pure homopolymer of ethylene, without the presence of an a-olefin-ethylene copolymer. The absence of a copolymer in the present invention means that it is thermally stable, unlike those examples containing copolymers, and requires no purging of an extruder following an operational shutdown.
These examples further show that the present invention, unlike the linear low density polyethylenes, does not build up excessive heat in the feed sections of the extruder. Thus, the present invention solves the problems of surging, melt fracture, and gel formation.
Numerous modifications and variations are possible, and it is to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein within the spirit and scope of the invention. Moreover, all patents, patent applications, provisional patent applications, and literature references cited above are incorporated herein by reference for any disclosure pertinent to the practice of this invention.

Claims (6)

-11-
1. A composition including two polyethylene homopolymers, said composition comprising:
a first component comprising a medium density potyethylene of narrow molecular weight distribution having a melt index of 0.5-dg/min to 4-dg/min at 190°C, a swell ratio of 1.2 to 1.35, an annealed density of about 0.926-g/cc, and a polydispersity index at or below 9; and a second component comprising a low density polyethylene of broad molecular weight distribution having a melt index range of 18-dg/min to 22-dg/min, measured at 190°C, a swell ratio greater than 1.60, an annealed density of about 0.91-g/cc to about 0.92-g/cc, and a polydispersity above 9.
2. A composition according to Claim 1, wherein said first component is present in the amount of greater than 50 weight percent, based on the weight of the composition.
3. A composition according to Claim 1, wherein said first component is present in the amount of about 80 weight percent and said second component is present in the amount of about 20 weight percent.
4. An article comprising a substrate and an extrusion coating, wherein said extrusion coating is a composition according to any of Claims 1, 2, or 3.
5. An article according to Claim 4, including at least one layer between said substrate and said extrusion coating.
6. An article according to Claim 4, including a primer layer between said substrate and said extrusion coating.
CA002297827A 1997-08-14 1998-08-03 Polyethylenes with enhanced heat seal properties Abandoned CA2297827A1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US5577097P 1997-08-14 1997-08-14
US60/055,770 1997-08-14
US09/088,904 US6174612B1 (en) 1998-06-02 1998-06-02 Polyethylenes with enhanced heat seal properties
US09/088,904 1998-06-02
PCT/US1998/016122 WO1999009097A1 (en) 1997-08-14 1998-08-03 Polyethylenes with enhanced heat seal properties

Publications (1)

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CA2297827A1 true CA2297827A1 (en) 1999-02-25

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CA002297827A Abandoned CA2297827A1 (en) 1997-08-14 1998-08-03 Polyethylenes with enhanced heat seal properties

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EP (1) EP1003813A1 (en)
JP (1) JP2001515115A (en)
KR (1) KR20010022793A (en)
CA (1) CA2297827A1 (en)
WO (1) WO1999009097A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000063309A1 (en) * 1999-04-16 2000-10-26 E.I. Du Pont De Nemours And Company Coating composition containing a low mfi ethylene acrylic acid copolymer
WO2019018023A1 (en) 2017-07-21 2019-01-24 Exxonmobil Chemical Patents Inc. Laminate material and process of making the same

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1983000490A1 (en) * 1981-07-28 1983-02-17 Eastman Kodak Co Two-component polyethylene extrusion coating blends
CA1218181A (en) * 1983-04-21 1987-02-17 Asahi Kasei Kogyo Kabushiki Kaisha Polyethylene composition
WO1994006857A1 (en) * 1992-09-16 1994-03-31 Exxon Chemical Patents Inc. Soft films having enhanced physical properties
US5536542A (en) * 1995-07-20 1996-07-16 Eastman Chemical Company Process for low temperature heat sealing of polyethylene

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WO1999009097A1 (en) 1999-02-25
JP2001515115A (en) 2001-09-18
KR20010022793A (en) 2001-03-26
EP1003813A1 (en) 2000-05-31

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