WO1998037142A1 - Scellement de polyethylene a un substrat - Google Patents

Scellement de polyethylene a un substrat Download PDF

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Publication number
WO1998037142A1
WO1998037142A1 PCT/US1998/003601 US9803601W WO9837142A1 WO 1998037142 A1 WO1998037142 A1 WO 1998037142A1 US 9803601 W US9803601 W US 9803601W WO 9837142 A1 WO9837142 A1 WO 9837142A1
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WO
WIPO (PCT)
Prior art keywords
ethylene
copolymer
film
propylene
weight
Prior art date
Application number
PCT/US1998/003601
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English (en)
Inventor
Fiona Donald
Achiel Josephus Maria Van Loon
Pierre A. De Waegeneer
Original Assignee
Exxon Chemical Patents 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
Priority claimed from US08/806,182 external-priority patent/US6094889A/en
Application filed by Exxon Chemical Patents Inc. filed Critical Exxon Chemical Patents Inc.
Priority to EP98910046A priority Critical patent/EP0963410A1/fr
Priority to BR9807778-3A priority patent/BR9807778A/pt
Priority to JP53698898A priority patent/JP2001512404A/ja
Priority to CA002279900A priority patent/CA2279900A1/fr
Priority to AU64387/98A priority patent/AU6438798A/en
Priority to IL13134598A priority patent/IL131345A0/xx
Publication of WO1998037142A1 publication Critical patent/WO1998037142A1/fr
Priority to NO994048A priority patent/NO994048L/no

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions 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
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2555/00—Characteristics of bituminous mixtures
    • C08L2555/40—Mixtures based upon bitumen or asphalt containing functional additives

Definitions

  • This invention relates to heat sealable films comprising at least a layer of polyethylene, preferably metallocene polyethylene (mPE) sealed to a substrate, preferably polypropylene.
  • mPE metallocene polyethylene
  • Polyethylene has traditionally been used as a sealing layer in polyolefin films and packaging because of its ability to seal quickly and maintain a strong seal strength.
  • PE polyethylene
  • polypropylene PP
  • special glues or tie layers must be ussed to seal the PE to the PP or other substrates. This causes difficulties in construction and packaging particularly with packages involving food.
  • USSN 806 182 addresses films comprising: (I) a first surface layer comprising a homopolymer of ethylene having an Mw/Mn of 3 or less or a copolymer of ethylene and up to 50 weight% of a C3 to C20 olefin having a CDBI of 50 % or more, and (ii) a second surface layer comprising a homopolymer of propylene or copolymer of propylene and up to 50 weight % of a comonomer where the ethylene layer is sealed directly to the propylene layer.
  • WO 95/00333 discloses heat shrinkable films where an outer layer of a multilayer heat shrinkable film is an ethylene or propylene polymer formed by polymerization in the presence of a single site catalyst.
  • EXACT TM resins are disclosed as suitable as the outer layer, but the films are not disclosed as being bonded to polypropylene.
  • EP Patent Application 0 597 502 discloses oriented single and multilayer films of metallocene polyethylenes, however polypropylene is not disclosed as suitable substrate to bond the film to.
  • US patent 5,482,770 discloses irradiated oriented multilayer films having a barrier layer of EVOH and other core or sealayers of metallocene polyethylenes.
  • This invention relates to a film comprising a first surface layer comprising a homopolymer of ethylene having an Mw/Mn of 3 or less or a copolymer of ethylene and up to 50 weight % of a C3 to C20 olefin having an Mw/Mn of 6 or less, wherein the copolymer has a CDBI of 50 % or more, preferably 60% or more wherein the first surface layer is sealed to a polypropylene substrate.
  • This invention has the benefit of producing seals with a good peel character, particularrly when the polyethylene homopolymer or copolymer is blended with 50 % or less of a second polymer that has low or no seal strength to polypropylene.
  • Figure 1 is a graph of the heat seal strength of films 2, 3 and 4.
  • Film 4 is the diamond shape (- ⁇ -).
  • Film 2 is the square shape (- ⁇ -).
  • Film 3 is the triangle shape (-A-). Detailed Description of the Invention.
  • this invention relates to a film comprising a first surface layer comprising a homopolymer of ethylene having a Mw/Mn of 3 or less, or a copolymer of ethylene and up to 50 weight %, preferably 1 to 35 weight %, preferably 1-20 weight % of one or more C3 to C20 olefins, (based upon the weight of the copolymer) having an Mw/Mn of 6 or less, preferably 3 or less, even more preferably between 1 and 2.5, wherein the polymer or copolymer preferably has: a) a density of 0.86 g/cm 3 to 0.96 g/cm 3 , preferably 0.88 to 0.94 g/cm 3 , more preferably between 0.88 g/cm 3 and 0.935 g/ cm 3 , more preferably between 0.88 g/cm 3 and 0.93 g/ cm 3 ' more preferably between 0.910 g/cm 3 and 0.925 g/ cm 3
  • CDBI Composition Distribution Breadth Index
  • the C3 to C20 an d C4 to C20 olefin comonomers for the polyethylene or polypropylene copolymers described above may be any polymerizable olefin monomer and are preferably a linear, branched or cyclic olefin, even more preferably an ⁇ -olefm.
  • Suitable olefins include propylene, butene, isobutylene, pentene, isopentene, cyclopentene, hexene, isohexene, cyclohexene, heptene, isoheptene, cycloheptene, octene, isooctene, cyclooctene, nonene, cyclononene, decene, isodecene, dodecene, isodecene, 4-methyl-pentene-l, 3- methy 1-pentene- 1, 3,5,5 -trimethyl hexene- 1.
  • Suitable comonomers also include dienes, trienes, and styrenic monomers.
  • Preferred examples include styrene, - methyl styrene, para-alkyl styrene (such as para-methyl styrene), hexadiene, norbornene, vinyl norbornene, ethylidene norbornene, butadiene, isoprene, heptadiene, octadiene, dicyclopentadiene, and cyclopentadiene.
  • Preferred comonomers for the copolymer of ethylene are propylene, butene, hexene and/or octene.
  • Preferred comonomers for the copolymer of propylene are ethylene, butene and /or hexene.
  • polyethylene or polypropylene copolymers described above may also contain termonomers and tetramonomers which may be one or more of: ethylene, any of the C3 to C20 olefins described above, any C4 to C30 linear, cyclic or branched dienes or trienes and any styreneic monomers such as styrene, ⁇ -methyl styrene, or para-methyl styrene.
  • Preferred examples include butene, butadiene, pentadiene, cyclopentadiene, hexadiene, cyclohexadiene, heptadiene, octadiene, nonadiene, norbornene, vinyl norbornene, ethylidene norbornene, isoprene and heptadiene.
  • the polyethylene copolymers described above preferably have a composition distribution breadth index (CDBI) of 50 % or more, preferably above 60%, even more preferably above 70%.
  • CDBI composition distribution breadth index
  • the polyethylene copolymer has a CDBI between 60 and 85 %, even more preferably between 65 and 85 %.
  • the ethylene homopolymer or copolymer has a CDBI of 65 to 85 %, a density of 0.89 to 0.96 g/cm 3 , preferably 0.915 to 0.96 g/cm 3 and a Mw/Mn between 1 and 2.5.
  • the ethylene homopolymer or copolymer has a density of 0.86 to 0.925 g/cm 3 and a CDBI of over 80%, preferably between 80 and 99%.
  • the polyethylene homopolymers and copolymers described above are metallocene polyethylenes (mPE's).
  • mPE's metallocene polyethylenes
  • the usage of the term polyethylene herein is defined to include metallocene polyethylenes.
  • the mPE homopolymers or copolymers are typically produced using mono- or bis-cyclopentadienyl transition metal catalysts in combination with an activator of alumoxane and/or a non-coordinating anion in solution, slurry, high pressure or gas phase.
  • the catalyst and activator may be supported or unsupported and the cyclopentadienyl rings by may substituted or unsubstituted.
  • the polypropylene homopolymer or copolymer preferably has an MFR (melt flow rate) of 1 to 20 as measured according to ASTM D 1238 (230 °C, 2.16 kg).
  • MFR melt flow rate
  • the polypropylene homopolymer or copolymer preferably has a CDBI of 50 % or more, preferably above 60%, even more preferably above 70 %.
  • Polypropylenes having a CDBI above 60% are available from Exxon Chemical Company in Baytown, Texas under the tradename ACHIEVETM.
  • polymers can be subsitiuted for the polyproplyene substrate.
  • polymers include styrenic block copolymers (such as SBS or SIS block copolymers), polycarbonate, PMP Poly-4-mentylpentene-l, PVC polyvinylchloride, Polyester, PET polyester, oriented polyester (either mono or biaxially oriented to the same or different extents), PBT Polybutylenetetraphtalate, PS polystyrene, HIPS high impact polystyrene, EPS Expanded polystyrene, ABS Acrylonitrile butadiene styrene copolymers, and PA polyamides. PVDC and/or acrylate coatings can also be applied to these polymers or the polypropylene substrate and then bonded to the mPE.
  • PVDC and/or acrylate coatings can also be applied to these polymers or the polypropylene substrate and then bonded to the mPE.
  • polypropylene homopolymer or copolymer can be blended with another propylene homopolymer or copolymer as described above or may be blended with another homopolymer and/or copolymer, including but not limited to, homopolypropylene, propylene copolymerized with up to 50 weight % of ethylene or a C4 to C20 -olefin, polybutene, ethylene vinyl acetate, low density polyethylene (density 0.915 to less than 0.935 g/cm 3 ) linear low density polyethylene, ultra low density polyethylene (density 0.86 to less than 0.90 g/cm 3 ), very low density polyethylene (density 0.90 to less than 0.915 g/cm 3 ), medium density polyethylene (density 0.935 to less than 0.945 g/cm 3 ), high density polyethylene (density 0.945 to 0.98 g/cm 3 ), ethylene vinyl acetate, EMA, copolymers of
  • the polypropylene is present in the blend at from 10 to 99 weight %, based upon the weight of the polymers in the blend, preferably 20 to 95 weight %.
  • the substrate comprises a random copolymer of propylene and up to 6 weight % ethylene.
  • the substrate comprises tactic polypropylene, preferably isotactic polypropylene, even more preferably polypropylene having a 90 % or more isotactic pentads as measured by 13 C NMR.
  • tactic is meant having tacticity.
  • the substrate is syndiotactic polypropylene, preferably syndiotactic polypropylene produced using mono- or bis- cyclopentadienyl transition metal catalysts in combination with an activator of alumoxane and/or a non-coordinating anion in solution, slurry, high pressure or gas phase.
  • the catalyst and activator may be supported or unsupported and the cyclopentadienyl rings by may substituted or unsubstituted.
  • Such syndiotactic polypropylene produced with such catalyst/activator combinations is commercially available from Fina Oil and Chemicals in Belgium under the tradename FinaproTM.
  • the mPE homopolymers or copolymers described above for use as a surface layer may be used alone, may be blended with other mPE homopolymers or copolymers, or they may be blended with other polyolefin homopolymers and copolymers, including but not limited to, homopolypropylene, propylene copolymerized with up to 50 weight % of ethylene or a C4 to C20 -olefin, polybutene, ethylene vinyl acetate, low density polyethylene (density 0.915 to less than 0.935 g/cm 3 ) linear low density polyethylene, ultra low density polyethylene (density 0.86 to less than 0.90 g/cm 3 ), very low density polyethylene (density 0.90 to less than 0.915 g/cm 3 ), medium density polyethylene (density 0.935 to less than 0.945 g/cm 3 ), high density polyethylene (density 0.945 to 0.98 g/cm 3 ), ethylene
  • selected polymers named above can be used to alter the peelability of the seal.
  • LDPE not produced by metallocenes
  • Other polymers that can be used include HDPE, EVA's havining less than 10 weight % VA, polybutene, elastomers, and the like.
  • the mPE is present in the blend at from 10 to 99 weight %, based upon the weight of the polymers in the blend, preferably the mPE is present at 20 to 95 weight %, even more preferably at least 30 to 90 weight %, even more preferably at least 40 to 90 weight %, even more preferably at least 50 to 90 weight %, even more preferably at least 60 to 90 weight %, even more preferably at least 70 to 90 weight %.
  • the blends described above may be produced by mixing the two or more polymers together, by connecting reactors together in series to make reactor blends or by using more than one catalyst in the same reactor to produce multiple species of polymer.
  • the polymers can be mixed together prior to being put into the extruder or may be mixed in the extruder.
  • the polyethylene homopolymers or copolymers described above and the blends thereof are typically formed into bilayer or multilayer films.
  • These films may be formed by any of the conventional techniques known in the art including extrusion, co-extrusion, extrusion coating, lamination, blowing and casting.
  • the film may be obtained by the flat film or tubular process which may be followed by orientation in an uniaxial direction or in two mutually perpendicular directions in the plane of the film.
  • a copending application to biaxially oriented mPE films in shrink wrap was filed on November 22, 1996 under serial number 08/755,105.
  • mPE is used as the sealing layer.
  • This invention also relates to films as described above where one or more of the layers are oriented in the transverse and/or longitudinal directions to the same or different extents. This orientation may occur before or after the individual layers are brought together.
  • the polyethylene layer can be extrusion coated or laminated onto an oriented polypropylene layer or the polyethylene and polypropylene can be coextruded together into a film then oriented.
  • oriented polypropylene could be laminated to oriented polyethylene or oriented polyethylene could be coated onto polypropylene then optionally the combination could be oriented even further.
  • a preferred embodiment includes a structure where the ethylene homopolymer or copolymer, preferably mPE, described above is coated, preferably extrusion coated or laminated, onto a film of polypropylene, preferably oriented polypropylene then the mPE side is bonded to a substrate.
  • the oriented polypropylene can be oriented in one direction or in both the longitudinal and transverse directions to the same or different degrees.
  • the films are oriented in the Machine Direction (MD) at a ratio of up to 15, preferably between 5 and 7, and in the Transverse Direction (TD) at a ratio of up to 15 preferably 7 to 9.
  • MD Machine Direction
  • TD Transverse Direction
  • the film is oriented to the same extent in both the MD and TD directions.
  • the polyethylene surface layer is combined with one or more other layers.
  • the other layer(s) may be any layer typically included in multilayer film structures.
  • the other layer or layers may be:
  • Preferred polyolefms include homopolymers or copolymers of C2 to C40 olefins, preferably C2 to C20 olefins, preferably a copolymer of an ⁇ -olefin and another olefin or ⁇ -olefin (ethylene is defined to be an ⁇ -olefin for purposes of this invention).
  • ethylene is defined to be an ⁇ -olefin for purposes of this invention.
  • thermoplastic polymers such as ultra low density polyethylene, very low density polyethylene, linear low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymer of propylene and ethylene and/or butene and/or hexene, elastomers such as ethylene propylene rubber, ethylene propylene diene monomer rubber, neoprene, and blends of thermoplastic polymers and elastomers, such as for example, thermoplastic elastomers and rubber toughened plastics.
  • thermoplastic polymers such as ultra low density polyethylene, very low density polyethylene, linear low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copo
  • Preferred polar polymers include homopolymers and copolymers of esters, amides, acetates, anhydrides, copolymers of a C2 to C20 olefin, such as ethylene and/or propylene and/or butene with one or more polar monomers such as acetates, anhydrides, esters, alcohol, and or acrylics.
  • Preferred examples include polyesters, polyamides, ethylene vinyl acetate copolymers, and polyvinyl chloride.
  • Preferred cationic polymers include polymers or copolymers of geminally disubstituted olefins, alpha-heteroatom olefins and/or styrenic monomers.
  • Preferred geminally disubstituted olefins include isobutylene, isopentene, isoheptene, isohexane, isooctene, isodecene, and isododecene.
  • Preferred alpha- heteroatom olefins include vinyl ether and vinyl carbazole
  • preferred styrenic monomers include styrene, alkyl styrene, para-alkyl styrene, alpha-methyl styrene, chloro-styrene, and bromo-para-methyl styrene.
  • Preferred examples of cationic polymers include butyl rubber, isobutylene copolymerized with para methyl styrene, polystyrene, and poly- ⁇ -methyl styrene. 4. Miscellaneous
  • Other preferred layers can be paper, wood, cardboard, metal, metal foils (such as aluminum foil and tin foil), metallized surfaces, glass (including silicon oxide (SiO x )coatings applied by evaporating silicon oxide onto a film surface), fabric, spunbonded fibers, and non-wovens (particularly polypropylene spun bonded fibers or non-wovens), and substrates coated with inks, dyes, pigments, PVDC and the like.
  • the multilayer structures can have more than one layer of the polyethylene homopolymer or copolymers, particularly the mPE homopolymers or copolymers. Further any of the above layers may be oriented before or after being combined with the other layers.
  • a particularly preferred embodiment includes an ABC structure film where the A layer comprises mPE or a blend comprising mPE and the B layer is isotactic polypropylene, highly isotactic polypropylene, one or more barrier layers, EN A, an adhesive layer/glue, or a metal foil, and the C layer is a random copolymer of propylene and up to 20 weight % of ethylene, preferably 3 to 6 weight % ethylene, even more preferably 3.5 to 5.5 weight % ethylene, or a terpolymer of propylene, ethylene and butene wherein the mPE layer is sealed to a polypropylene substrate.
  • structures described herein are characterized by a heat seal strength of 8 ⁇ /15mm or more at a seal bar temperature of 90 to 150 °C. 8N/15mrn is the minimum typically required for packaging integrity.
  • peel strength can be adjusted by either treating the mPE surface, for example with corona treatment, (and the like) or by blending in additional polymers.
  • the films to be sealed to the substrate may vary in total thickness depending on the intended application, however films of a thickness from 5 to 250 ⁇ m are usually suitable. Films intended for packaging are usually from 10 to 150 ⁇ m thick.
  • the thickness of the sealing layer is typically 2 to 50 ⁇ m. There may be a sealing layer on both the inner and outer surfaces of the film or the sealing layer may be present on only the inner or the outer surface.
  • the first surface layer is heat sealed to a polypropylene substrate, particularly a substrate of a thick film (whether mono or coextruded), a blow molded article (whether mono or coextruded), an injection molded article (whether mono or coextruded), and thermoformed article (whether mono or coextruded), a sheet (whether mono or coextruded), a rotational molded article (whether mono or coextruded).
  • a polypropylene substrate particularly a substrate of a thick film (whether mono or coextruded), a blow molded article (whether mono or coextruded), an injection molded article (whether mono or coextruded), and thermoformed article (whether mono or coextruded), a sheet (whether mono or coextruded), a rotational molded article (whether mono or coextruded).
  • the mPE layer is sealed to a formed article such as a packaging container (for example a microwave dinner dish, snack comtainers or a dairy cup).
  • the mPE layer has the benefit of producing breathable lid stock.
  • Additives such one or more of as tackifiers, antistats, antiblock, antioxidants, pigments, fillers, antifog, processing aids, UV stabilizers, neutralizers, lubricants, surfactants and/or nucleating agents may also be present in one or more than one layer in the films or the substrates.
  • Preferred additives include polybutene, antifog, silicon dioxide, titanium dioxide, calcium carbonate, barium sulfate, polydimethylsiloxane, talc, dyes, wax, metal stearate, calcium stearate, carbon black, lactate, low molecular weight resins and glass beads.
  • one or both of surface layers may be modified by corona treatment, electron beam irradiation, gamma irradiation, or microwave. In a preferred embodiment one or both of the surface layers is modified by corona treatment.
  • the films described herein may also comprise from 5 to 60 weight %, based upon the weight of the polymer and the resin, of a hydrocarbon resin.
  • the resin may be combined with the polymer of the seal layer(s) or may be combined with the polymer in the core layer(s).
  • the resin preferably has a softening point above 100 °C, even more preferably from 130 to 180 °C.
  • Preferred hydrocarbon resins include those described in EPA 288 227 and EPA 247 898.
  • films comprising a hydrocarbon resin may be oriented in uniaxial or biaxial directions to the same or different degrees.
  • a preferred combination includes one surface layer of mPE and one surface or core layer of an isotactic polypropylene blended with hydrocarbon resin having a softening point between 130 and 180 °C, preferably between 140 and 180 °C wherein the mPE layer is sealed to a substrate, preferably polypropylene.
  • a substrate preferably a polymer comprising homopolypropylene or a copolymer of propylene and up to 50 weight % of ethylene or a C to C20 olefin,
  • PP4342C2 is a polypropylene homopolymer having an MFR of 2.4 and an isotactic index of 95 as measured by heptane insolubles.
  • ECD 103 is an ethylene hexene copolymer produced in the gas phase having approximately 7.6 weight % hexene, a melt index of about 1 g/lOmin, a Mw/Mn of about 2.3, a CDBI of about 67% and a density of about 0.917 g/cm 3 , sold under the tradename EXCEEDTM by Exxon Chemical Company in Baytown, Texas.
  • EXACT 3132 is an ethylene hexene copolymer produced in a high pressure process having about 15.4 weight % hexene, a melt index of about 1.2 g/ 10 min, a density of about 0.900 g/cm 3 , a CDBI of about 91%, and an Mw/Mn of about 1.9 produced by and available from Exxon Chemical Company in Baton Rouge, Texas.
  • DOW NG 5056 E01 and Dow 5056 E are ethylene octene copolymers having about 11.6 weight % octene, an Mw/Mn of about 3.1, a melt index of about Ig/lOmin, a density of about 0.919 g/cm 3 , and a CDBI of about 45% produced by and available from Dow Chemical Company in Zurich, Switzerland. E differs from E01 in that slip and antiblock additives are included in E01.
  • VITRA BOPP is a 25 ⁇ m thick trilayer film of an ABA structure where the A layer is a random copolymer of propylene with about 4.5 weight % ethylene (RCP), and the B layer is a homopolymer of isotactic polypropylene, available from VITRA located in Wommelgem, Belgium.
  • RCP weight % ethylene
  • One of the A layers was corona treated for a final surface tension of about 38 dynes/cm (38 mN/m).
  • CDBI Composition Distribution Breadth Index
  • MI Melt Index
  • Melt Flow Rate was measured according ASTM D 1238 (at 230 °C and 2.16 kg)
  • Mw and Mn were measured by GPC (Gel Permeation Chromatography) on a Waters 150 gel permeation chromatograph equipped with a differential refractive index (DRI) detector and a Chromatix KMX-6 on line light scattering photometer. The system was used at 135 °C with 1 ,2,4-trichlorobenzene as the mobile phase.
  • Shodex Showa Denko America, Inc
  • polystyrene gel columns 802, 803, 804 and 805 were used. This technique is discussed in "Liquid Chromatography of Polymers and Related Materials III", J. Cazes editor, Marcel Dekker. 1981, p. 207, which is incorporated herein by reference.
  • the structure was folded between TEFLONTM film and inserted between the sealing bars. At various the sealing bars were closed with a pressure of 0.5 MPa for 0.5 seconds. The structure was removed from the Top wave machine and conditioned for a minimum of 12 hours at 23 °C ⁇ 3 °C and 50% humidity ⁇ 5% humidity.
  • Seal Strength was tested according to the following procedure. After conditioning for a minimum of 12 hours at 23 °C ⁇ 3 °C and 50% humidity ⁇ 5% humidity, the seal strength of 15mm wide sample was measured in a Zwick tensile instrument under the following conditions: speed-100 mm/min, load cell- 200N, and clamp distance-50 mm. The structure was placed between the clamps and the clamps were moved apart at a speed of lOO m min. During the rest the force (N) was recorded as a function of elongation (%). Four test specimens were measured and the average seal strength curve was recorded. The seal strength was the force at which the test specimen failed.
  • Three trilayer polyethylene films (50 ⁇ m thick, approximately 17 ⁇ m per layer) were produced on a three layer Barmag blown film line with a die of 250 mm and a gap of 1.6 mm under the conditions listed in Tables 2-4.
  • Table 1 shows the composition of the films labelled films 2-4). Thereafter the films were laminated to the 25 ⁇ m thick VITRA BOPP film which had been corona treated and had a measured surface tension of 38 dynes/cm(38 mN/m). Prior to adhesive lamination the polyethylene films had also been corona treated. The outside layer of the polyethylene film was laminated to the treated side of the VITRA BOPP film.
  • the films were laminated on an RK Print Coat Rotary Koater laminator to the VITRA BOPP using an adhesive comprising ADCOTETM 301 A, ADCOTETM 350A (6:4 ratio by weight) and ethyl acetate as solvent mixed at a 30% solids level.
  • ADCOTE chemicals are availabe from Morton International in Germany. Table 5 contains lamination details. Table 1
  • PPA polymer processing aid, Schulman's Polybatch AMF 702.

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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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Wrappers (AREA)
  • Adhesive Tapes (AREA)

Abstract

La présente invention concerne un film formé d'une première couche de surface comprenant un homopolymère d'éthylène possédant un rapport Mw/Mn inférieur ou égal à 3, ou un copolymère d'éthylène et 50 % en poids ou moins d'une oléfine en C3 à C20 doté d'un indice de largeur de répartition de la composition (CDBI) supérieur ou égal à 50 %; la première couche de surface est scellée à un substrat, comprenant de préférence un homopolymère de propylène ou un copolymère de propylène et 50 % en poids ou plus d'un comonomère.
PCT/US1998/003601 1997-02-25 1998-02-24 Scellement de polyethylene a un substrat WO1998037142A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP98910046A EP0963410A1 (fr) 1997-02-25 1998-02-24 Scellement de polyethylene a un substrat
BR9807778-3A BR9807778A (pt) 1997-02-25 1998-02-24 Selos de polietileno para um substrato
JP53698898A JP2001512404A (ja) 1997-02-25 1998-02-24 支持体へのポリエチレンのシール
CA002279900A CA2279900A1 (fr) 1997-02-25 1998-02-24 Scellement de polyethylene a un substrat
AU64387/98A AU6438798A (en) 1997-02-25 1998-02-24 Seals of polyethylene to a substrate
IL13134598A IL131345A0 (en) 1997-02-25 1998-02-24 Seals of polyethylene to a substrate
NO994048A NO994048L (no) 1997-02-25 1999-08-23 Forseglinger av polyetylen mot et substrat

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US08/806,182 1997-02-25
US08/806,182 US6094889A (en) 1997-02-25 1997-02-25 Method of form and seal packaging
US84773097A 1997-04-28 1997-04-28
US08/847,730 1997-04-28

Publications (1)

Publication Number Publication Date
WO1998037142A1 true WO1998037142A1 (fr) 1998-08-27

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Country Status (11)

Country Link
EP (1) EP0963410A1 (fr)
JP (1) JP2001512404A (fr)
KR (1) KR20000075475A (fr)
AU (1) AU6438798A (fr)
BR (1) BR9807778A (fr)
CA (1) CA2279900A1 (fr)
IL (1) IL131345A0 (fr)
NO (1) NO994048L (fr)
PL (1) PL335377A1 (fr)
TR (1) TR199902046T2 (fr)
WO (1) WO1998037142A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1057863A1 (fr) * 1999-06-04 2000-12-06 Wolff Walsrode AG Film de polyolèfine transparent avec couche d'étanchéité sur du papier pour utilisation comme thermosoudage d'un matériau d'emballage
US6262174B1 (en) 1999-06-17 2001-07-17 The Dow Chemical Company Polymer compositions which exhibit high hot tack
FR2837471A1 (fr) * 2002-03-25 2003-09-26 Flexico France Sarl Film notamment pour sachet d'emballage
US20080299364A1 (en) * 2005-08-30 2008-12-04 Borealis Technology Oy Film
EP2204338A1 (fr) * 2002-12-20 2010-07-07 E. I. du Pont de Nemours and Company Poche et récipient à boisson à plusieurs compartiments comprenant un joint cassable
WO2011054133A1 (fr) * 2009-11-09 2011-05-12 Exxonmobil Chemical Patents Inc. Films polymères et leurs procédés de fabrication
WO2012058789A1 (fr) * 2010-11-05 2012-05-10 Exxonmobil Chemical Patents Inc. Films polymères et procédés pour les fabriquer
WO2019238967A1 (fr) * 2018-06-15 2019-12-19 Total Research & Technology Feluy Structures multicouches de polyéthylène et de polypropylène et leurs utilisations
CN113512218A (zh) * 2021-08-09 2021-10-19 茂名联塑建材有限公司 一种高表面张力的pe薄膜及其制备方法和应用

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010088688A (ko) * 2001-08-21 2001-09-28 이순만 P.v.c 및 스티렌대체용합성수지 및 제조방법
KR20010112189A (ko) * 2001-11-23 2001-12-20 안창근 P.v.c 대체용 합성수지 및 제조방법
KR101467532B1 (ko) * 2013-03-22 2014-12-01 일신화학공업 주식회사 성능이 향상된 자기점착성 보호필름

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995013321A1 (fr) * 1993-11-12 1995-05-18 Exxon Chemical Patents Inc. Films thermosoudables et articles obtenus a partir de ceux-ci
WO1995023697A1 (fr) * 1994-03-02 1995-09-08 Minnesota Mining And Manufacturing Company Films thermosensibles
EP0787581A1 (fr) * 1996-02-02 1997-08-06 Oji-Yuka Synthetic Paper Co., Ltd. Etiquette pour étiquetage dans le moule et récipient décoré avec cell-ci
EP0802046A2 (fr) * 1996-04-19 1997-10-22 W.R. Grace & Co.-Conn. Feuille multicouche ayant une adhésion améliorée entre les couches
WO1997044178A1 (fr) * 1996-05-20 1997-11-27 Union Camp Corporation Film obtenu par coextrusion-soufflage et produits realises a l'aide de ce film

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995013321A1 (fr) * 1993-11-12 1995-05-18 Exxon Chemical Patents Inc. Films thermosoudables et articles obtenus a partir de ceux-ci
WO1995023697A1 (fr) * 1994-03-02 1995-09-08 Minnesota Mining And Manufacturing Company Films thermosensibles
EP0787581A1 (fr) * 1996-02-02 1997-08-06 Oji-Yuka Synthetic Paper Co., Ltd. Etiquette pour étiquetage dans le moule et récipient décoré avec cell-ci
EP0802046A2 (fr) * 1996-04-19 1997-10-22 W.R. Grace & Co.-Conn. Feuille multicouche ayant une adhésion améliorée entre les couches
WO1997044178A1 (fr) * 1996-05-20 1997-11-27 Union Camp Corporation Film obtenu par coextrusion-soufflage et produits realises a l'aide de ce film

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1057863A1 (fr) * 1999-06-04 2000-12-06 Wolff Walsrode AG Film de polyolèfine transparent avec couche d'étanchéité sur du papier pour utilisation comme thermosoudage d'un matériau d'emballage
US6262174B1 (en) 1999-06-17 2001-07-17 The Dow Chemical Company Polymer compositions which exhibit high hot tack
FR2837471A1 (fr) * 2002-03-25 2003-09-26 Flexico France Sarl Film notamment pour sachet d'emballage
EP2204338A1 (fr) * 2002-12-20 2010-07-07 E. I. du Pont de Nemours and Company Poche et récipient à boisson à plusieurs compartiments comprenant un joint cassable
US20080299364A1 (en) * 2005-08-30 2008-12-04 Borealis Technology Oy Film
WO2011054133A1 (fr) * 2009-11-09 2011-05-12 Exxonmobil Chemical Patents Inc. Films polymères et leurs procédés de fabrication
WO2012058789A1 (fr) * 2010-11-05 2012-05-10 Exxonmobil Chemical Patents Inc. Films polymères et procédés pour les fabriquer
WO2019238967A1 (fr) * 2018-06-15 2019-12-19 Total Research & Technology Feluy Structures multicouches de polyéthylène et de polypropylène et leurs utilisations
CN113512218A (zh) * 2021-08-09 2021-10-19 茂名联塑建材有限公司 一种高表面张力的pe薄膜及其制备方法和应用

Also Published As

Publication number Publication date
NO994048D0 (no) 1999-08-23
NO994048L (no) 1999-08-23
PL335377A1 (en) 2000-04-25
EP0963410A1 (fr) 1999-12-15
KR20000075475A (ko) 2000-12-15
BR9807778A (pt) 2000-02-22
CA2279900A1 (fr) 1998-08-27
TR199902046T2 (xx) 1999-12-21
IL131345A0 (en) 2001-01-28
AU6438798A (en) 1998-09-09
JP2001512404A (ja) 2001-08-21

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