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US20080118692A1 - Polyethylene useful for producing film and molded articles in a process which uses solid state stretching - Google Patents

Polyethylene useful for producing film and molded articles in a process which uses solid state stretching Download PDF

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Publication number
US20080118692A1
US20080118692A1 US11/941,295 US94129507A US2008118692A1 US 20080118692 A1 US20080118692 A1 US 20080118692A1 US 94129507 A US94129507 A US 94129507A US 2008118692 A1 US2008118692 A1 US 2008118692A1
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US
United States
Prior art keywords
article
polyethylene
oriented
stretching
biaxially
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.)
Abandoned
Application number
US11/941,295
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English (en)
Inventor
Michael McLeod
Gerhard Guenther
Shannon B. Hoesing
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fina Technology Inc
Original Assignee
Fina Technology Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fina Technology Inc filed Critical Fina Technology Inc
Priority to CA002663929A priority Critical patent/CA2663929A1/en
Priority to US11/941,295 priority patent/US20080118692A1/en
Priority to EP07854677A priority patent/EP2083990A4/en
Priority to JP2009537385A priority patent/JP2010510094A/ja
Priority to MX2009005315A priority patent/MX2009005315A/es
Priority to KR1020097009718A priority patent/KR20090091705A/ko
Priority to PCT/US2007/084942 priority patent/WO2008064112A1/en
Assigned to FINA TECHNOLOGY, INC. reassignment FINA TECHNOLOGY, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HOESING, SHANNON B., GUENTHER, GERHARD, MCLEOD, MICHAEL
Publication of US20080118692A1 publication Critical patent/US20080118692A1/en
Priority to US14/081,393 priority patent/US10040261B2/en
Abandoned legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D22/00—Producing hollow articles
    • B29D22/003—Containers for packaging, storing or transporting, e.g. bottles, jars, cans, barrels, tanks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D23/00—Producing tubular articles
    • B29D23/001—Pipes; Pipe joints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/08—Biaxial stretching during blow-moulding
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
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    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
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    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
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    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1397—Single layer [continuous layer]

Definitions

  • This invention relates to using certain single site catalyzed polyethylene resins in processes where an article is formed, such as through melt extrusion, injection molding, injection blow molding, or casting, then cooled, and then orienting or stretching the article.
  • the articles have good optical properties, gauge distribution, stretching properties, and toughness.
  • the present invention pertains to tape, film, fibers, packaging and containers made from certain types of polyethylene resins.
  • a variety of applications in which films, sheets, tape and other articles are extruded, molded, blown or cast, cooled, and then later heated and stretched or orientated are known in the art and for example also include a double bubble method for biaxially orienting thermoplastic films such as that disclosed in U.S. Pat. Nos. 3,456,044 and 3,555,604 to Pahlke.
  • This method including the steps of producing a primary tubing by melt extrusion from a die, inflating the tubing by introducing air into the interior thereof, then cooling and collapsing the tubing, reinflating the tubing to form a secondary bubble, then reheating the film to its draw temperature.
  • the tubing In the draw or expansion zone, the tubing is oriented in the transverse direction through radial expansion of the bubble and oriented in the machine direction by drawing down the bubble. When machine and/or transverse stretching occurs, the bubble expansion is accompanied by a reduction of the thickness.
  • polystyrene resin and more preferably a polyethylene (PE) homopolymer or copolymer resin, are more suitable for the oriented processes.
  • the polyethylene resins exhibit excellent elasticity, toughness, stretch and optical properties for such applications.
  • FIG. 1 is the Molecular Weight Distribution Traces for M3410 and D350;
  • FIG. 2 shows the Sheet Optics and Gauge Consistency for D350
  • FIG. 3 shows the Sheet Optics and Gauge Consistency for M3410
  • FIG. 4 shows the Thickness Across the Sheet Width for M3410 and D350;
  • FIG. 5 shows the Crystallization Exotherms for M3410 and D350
  • FIG. 6 shows the Melting Endotherms for M3410 and D350
  • FIG. 7 shows the Stretching Temperature Range for M3410 and D350
  • FIG. 8 shows the Drawing Force Versus Time at Various Temperatures for M3410
  • FIG. 9 shows the Drawing Force Versus Time at Various Temperatures for D350
  • FIG. 10 shows the Maximum Stretching Stress Versus Lower Temperature Stretching for M3410 and D350;
  • FIG. 11 shows the Apparent Toughness Versus Lower Temperature Stretching for M3410 and D350;
  • FIG. 13 shows D350 Film Under Crossed Polarizers
  • FIG. 15 shows the Gloss Versus Stretching Temperature for M3410 and D350.
  • such suitable polyethylene resins have a Melt Flow Index (MFI), (g/10 min.) of from 0.3 g/10 min. to 5.0 g/10 min., a density of from 0.912 g/cm 3 to 0.965 g/cm 3 , in another embodiment 0.912 g/cm 3 to 0.950 g/cm 3 , and yet in another embodiment 0.915 g/cm 3 to 0.940 g/cm 3 . Density was measured under ASTM D 792 guidelines. The Melt Flow Index was measured under ASTM D 1238 guidelines.
  • MFI Melt Flow Index
  • suitable polyethylene resins have a melting point of from 110° C. to 140° C. (248° F. to 284° F.), and in yet another embodiment a melting point of from 125° C. to 135° C. (257° F. to 275° F.).
  • the suitable polyethylene resins have a haze (%) of 10% or less, and in another embodiment of 5% or less, clarity of at least 90, and in alternative embodiment at least 95, and in a further embodiment a clarity of at least 98 or greater, and a gloss of at least 60%, or alternatively a gloss of 75% or greater.
  • Haze testing was performed under ASTM D 1003 guidelines. Clarity testing was performed under ASTM D 1746 guidelines, and 450 gloss was tested under ASTM D 2457 guidelines.
  • the films and sheets of the present invention can be used for: food packaging, fragrance and fragrance-impregnated products packaging (e.g. detergents), photographic film packaging, medical applications, geomembranes, agricultural products (e.g., fertilizers, insecticides), converting operations where printing solvents and other surface treatments must not migrate through the film, and packaging where sorption of flavor, aroma, or colorant compounds must be minimized.
  • the films may be used in monolayer and multilayer applications.
  • the films of the present invention can also be used for other applications, where good barrier properties are an advantage, as well as any other uses known to those of ordinary skill in the art for polyethylene films.
  • the thickness of the film, tape, injection blow molded, injection stretch blow molded, and thermoformed articles that can be produced with this type of polyethylene is from 0.1 mil to 100 mils.
  • films and tapes may have a thickness of 0.1 mils to 5 mils
  • injection stretch blow molded articles may have a thickness of 5 mils to 50 mils
  • thermoformed articles may have a thickness of 5 mils to 100 mils.
  • the packaging also includes monolayer and multilayer packaging such as stretch wrap applications and methods (e.g., pulling a film over a container, tray, backing, or other item or packaging, with or without heat sealing), shrink wrap (shrink in both the machine and transverse directions), skin wraps, vacuum wraps, and molded/shaped packaging, for example.
  • stretch wrap applications and methods e.g., pulling a film over a container, tray, backing, or other item or packaging, with or without heat sealing
  • shrink wrap shrink in both the machine and transverse directions
  • skin wraps e.g., skin wrap, vacuum wraps, and molded/shaped packaging, for example.
  • the fibers may also be used in a broad spectrum of products and components used, for example, in artificial turf and woven tape used for carpet.
  • PE polyethylene
  • grade M3410 produced by a metal locene catalyst, commercially available from Total Petrochemicals, USA, Inc.
  • PE resins like M3410 have improved gauge distribution in cast sheeting used in tape production, thermoforming, and uniaxially and biaxially oriented polyethylene films. Through its higher shear response and melt strength, it improves gauge distribution in double bubble and machine direction orientation blown film processes to produce end articles with a more uniform gauge. Providing more consistent gauge in the forming step is critical for the subsequent orienting step or steps.
  • the resin properties of an embodiment of Total M3410 polyethylene resin are set forth in Table IA.
  • the recommended processing extrusion melt temperature for M3410 is from 380° F. to 410° F. (193° C. to 210° C.).
  • the resin properties of an embodiment of Total M2710 polyethylene resin are set forth in Table 1B.
  • the resin and mechanical properties of the CPC D350 polyethylene resin are set forth in Table 2.
  • a polyethylene copolymer known as M3410 was prepared by polymerizing ethylene and hexene in a slurry reactor in the presence of a metallocene catalyst. The resin was cast molded into a sheet and cooled. The sheet was then heated to between 115° C. to 119° C. (239° F. to 246° F.) and bilaterally oriented/transversely stretched using a BrucknerTM Karo IV stretching frame. This polymer was compared against a commercial resin D350 sold by Conoco-Philips Corporation.
  • Table 3 is a comparison of the rheology of the D350 PE resin and the M3410 resin.
  • M3410 also has a broader crystallization range and melting range than D350. See FIG. 5 and FIG. 6 . This increased breadth, particularly in melting behavior, provides a broader temperature range for heating the formed article and stretching it into its final oriented shape. All solid-state stretching processes benefit, including for example, oriented tape, monofilament, fully oriented yarn, fibers, injection stretch blow molding, thermoforming, melt extrusion, injection molding, and machine direction or uniaxially and biaxially oriented films.
  • M3410 has a slightly lower melting temperature than D350. See Table 6.
  • M3410 can first be successfully drawn at 115° C. versus 118° C. for D350. See FIG. 7 , showing stretching temperature range.
  • M3410 can be drawn with 100% success over a 5° C. range, versus only a range of 4° C. for the D350 resin, M3410 has a broader temperature range for solid-state stretching.
  • the maximum stretching stress at the lower stretching temperatures are shown in FIG. 10 .
  • the slope of stress versus temperature is ⁇ 0.535 for M3410, versus ⁇ 0.770 for D350. This shallower slope is a processing advantage. It illustrates that M3410 is less sensitive to changes in temperature than D350.
  • apparent toughness is the area under the stress-strain curve.
  • the slope of apparent toughness versus temperature is ⁇ 1.018 for M3410, versus ⁇ 1.518 for D350. See FIG. 11 .
  • the significance of this test is that the smaller the slope, the broader the temperature range, and the easier it is to process. This result reinforces that M3410 is less sensitive to changes in temperature than D350.
  • M3410 film produces a symmetric, uniform pattern. See FIG. 12 .
  • the M3410 film center has a uniform halo without it being bisected by thicker, less drawn lanes of material.
  • the film made from D350 consistently produced an asymmetric pattern with thicker lanes extending in the direction of stretching, here the machine direction. See FIG. 13 .
  • These thicker lanes are due to propagation of sheet gauge variation, which produces unequal stretching during the stretching step. At 122° C., this variation was sufficient to produce holes in the film adjacent to thick lanes of lightly drawn D350. See FIG. 14 .
  • M3410 consistently produced films with a higher gloss, greater clarity, and a lower haze at its lowest stretching temperature relative to D350 at its lowest stretching temperature See FIG. 15 (gloss vs. stretching temperature) and Table 7.
  • Table 7 shows the optical properties of the two film types, using the ASTM D1003 and D 2457 tests.
  • M3410 stretched at 117° C. has a gloss of 75.1 versus 22.9 for D350 stretched at 119° C.
  • M3410's optical properties are due to its molecular architecture and how it improves casting and stretching behavior.

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  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
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  • Medicinal Chemistry (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Bag Frames (AREA)
  • Wrappers (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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EP07854677A EP2083990A4 (en) 2006-11-21 2007-11-16 USEFUL POLYETHYLENE FOR THE PRODUCTION OF FILM AND SHAPED ITEMS USED IN A SOLID PARTICULAR TRACK
JP2009537385A JP2010510094A (ja) 2006-11-21 2007-11-16 固体状態の引き伸ばしを用いる方法でフィルムおよび成形品を製造する時に有用なポリエチレン
MX2009005315A MX2009005315A (es) 2006-11-21 2007-11-16 Polietileno util para producir pelicula y articulos moldeados en un proceso que usa estiramiento en estado solido.
KR1020097009718A KR20090091705A (ko) 2006-11-21 2007-11-16 고체 상태 스트레칭을 이용하는 공정에서 필름 및 성형된 물품을 생산하는데 유용한 폴리에틸렌
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EP2083990A4 (en) 2010-01-20
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Owner name: FINA TECHNOLOGY, INC., TEXAS

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STCB Information on status: application discontinuation

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