WO2005059024A2 - Heat seal modifiers for linear polyethylenes - Google Patents

Heat seal modifiers for linear polyethylenes Download PDF

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Publication number
WO2005059024A2
WO2005059024A2 PCT/US2004/043064 US2004043064W WO2005059024A2 WO 2005059024 A2 WO2005059024 A2 WO 2005059024A2 US 2004043064 W US2004043064 W US 2004043064W WO 2005059024 A2 WO2005059024 A2 WO 2005059024A2
Authority
WO
WIPO (PCT)
Prior art keywords
heat seal
acid copolymer
resin
ethylene acid
present
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.)
Ceased
Application number
PCT/US2004/043064
Other languages
English (en)
French (fr)
Other versions
WO2005059024A3 (en
Inventor
Geraldine M. Lenges
Timothy A. Libert
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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 EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to BRPI0417109-8A priority Critical patent/BRPI0417109A/pt
Priority to DE602004017899T priority patent/DE602004017899D1/de
Priority to AU2004298628A priority patent/AU2004298628B2/en
Priority to CA002547606A priority patent/CA2547606A1/en
Priority to EP04815178A priority patent/EP1694766B1/en
Priority to JP2006545596A priority patent/JP5384792B2/ja
Publication of WO2005059024A2 publication Critical patent/WO2005059024A2/en
Publication of WO2005059024A3 publication Critical patent/WO2005059024A3/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08L23/08Copolymers of ethene
    • 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
    • C08L23/08Copolymers of ethene
    • C08L23/0807Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0815Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
    • 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
    • C08L23/08Copolymers of ethene
    • C08L23/0846Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • 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
    • C08L23/08Copolymers of ethene
    • C08L23/0846Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • C08L23/0876Salts thereof, i.e. ionomers

Definitions

  • This invention relates to polyethylene compositions for use in packaging.
  • This invention particularly relates to metallocene polyolefin compositions comprising a heat seal modifier.
  • Description of the Prior Art Polyethylene polymers are useful in packaging, as well as in other applications.
  • the use of linear polyolefins is not without problems to a manufacturer, however.
  • One problem that a manufacturer may be faced with is finding a proper balance between the cost of manufacture and the performance of the manufactured product.
  • Linear polyethylenes produced using a single site metallocene catalyst can have many performance benefits.
  • linear polyethylenes can also be difficult to process in a cost-efficient manner.
  • linear (metallocene) polyethylenes can have less than desirable heat seal properties.
  • linear polyethylenes often do not provide sufficient adhesion between the sealing layers of polyethylene to result in a good adhesive seal for a package.
  • the present invention is linear polyethylene composition suitable for use as a heat seal resin, wherein the resin comprises: (a) from about 70 wt% to about 90 wt% of a linear polyethylene having a density of from about 0.88 to about 0.95 g/cm 3 ; (b) from about 0 to about 30 wt% of a copolymer selected from: an ethylene acid copolymer; an ethylene acid copolymer ionomer; or a mixture thereof; and, (c) from about 2 wt% to about 10 wt% of a tackifier.
  • the present invention is a heat seal modifier composition
  • a heat seal modifier composition comprising: (a) from about 0 wt% to about 90 wt% of an ethylene acid copolymer, an ethylene acid copolymer ionomer, or a mixture thereof; (b) from about 10 wt% to about 100 wt% of a tackifier; and, optionally, (c) up to about 10 wt% of a metallocene polyethylene polymer.
  • the present invention is a process for manufacturing a package comprising the step: including with a polyethylene resin having a density of from about 0.88 g/cm 3 to about 0.95 g/cm 3 , a heat seal modifier wherein the modifier comprises (a) from about 0 wt% to about 90 wt% of a copolymer comprising an ethylene acid copolymer, an ethylene acid copolymer ionomer, or a mixture thereof, and preferably comprising an at least partially neutralized ethylene acid copolymer; (b) from about 10 wt% to about 90 wt% of a tackifier; and, optionally, (c) up to about 10 wt% of a metallocene polyethylene polymer.
  • the present invention is a package comprising a polyethylene heat seal resin, wherein the resin comprises: (a) from about
  • the term “about” means that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art. In general, an amount, size, formulation, parameter or other quantity or characteristic is “about” or “approximate” whether or not expressly stated to be such.
  • the present invention is a linear polyethylene composition.
  • linear polyethylene refers to a polyethylene resin obtained by using a single site (metallocene) catalyst.
  • the linear polyethylene composition of the invention is useful as a heat seal resin, for example.
  • Linear polyethylenes suitable for use in the practice of the present invention have a density of from about 0.88 g/cm 3 to about 0.95 g/cm 3 .
  • the linear polyethylene has a density of from about 0.90 g/cm 3 to about 0.94 g/cm 3 .
  • the linear polyethylene has a density of from about 0.91 g/cm 3 to about 0.93 g/cm 3 .
  • the linear polyethylene composition of the invention preferably comprises about 70 wt% to about 90 wt% of the linear polyethylene, based on the total weight of the linear polyethylene composition. Of note are compositions comprising 75 wt% to 85 wt% and about 80 wt% of the linear polyethylene.
  • the linear polyethylene composition of the invention also includes at least one copolymer selected from an ethylene acid copolymer; an ethylene acid copolymer ionomer; or a mixture thereof (collectively referred to herein as "acid copolymer").
  • Suitable and preferred ethylene acid copolymers and ionomers are as set forth below with respect to the heat seal resin modifier compositions of the invention.
  • the acid copolymer can be present in the linear polyethylene composition in an amount of from about 0 to about 30 wt%, based on the total weight of the linear polyethylene composition.
  • the acid copolymer is present in the linear polyethylene composition in a finite amount up to about 30 wt%, more preferably in an amount of from about 10 to about 30 wt%, more preferably in an amount of from about 10 to about 25 wt%, and still more preferably in an amount of from about 12 to about 23 wt%, based on the weight of the linear polyethylene composition.
  • the linear polyethylene composition of the invention also includes a tackifier. Suitable and preferred tackifiers are as set forth below with respect to the heat seal resin modifier compositions of the invention.
  • the linear polyethylene composition includes from about 2 wt% to about 10 wt% of the tackifier, based on the total weight of the linear polyethylene composition.
  • the tackifier is present in an amount of from about 3 to about 10 wt%, and still more preferably in an amount of from about 4 to about 8 wt% in the heat seal resin.
  • compositions comprising about 2 wt% to about 5 wt% and about 2 wt% of the tackifier.
  • the components of the linear polyethylene composition may be blended by any suitable means known in the art. Preferably the components are melt-blended, e.g., in an extruder.
  • the linear polyethylene composition may be applied to the packaging material to be sealed, and the seal may be formed, by any suitable means known in the art. See, e.g., the Wiley Encyclopedia of Packaging Technology, 2d edition, A.L.
  • heat seal resin compositions have heat seal initiation temperatures that vary depending on the resin composition. Typically, it is preferable to use a resin with a heat seal temperature that is as low as possible but that will still provide a seal strength that is desirable for the desired application. For example, if a heat seal of 1500 g/inch is desirable in a particular application, a manufacturer may find it advantageous to choose a material that can provide a seal of that strength at a temperature of 250°F rather than a material that can provide that seal strength at a temperature of 280°F.
  • a heat seal composition capable of providing equivalent heat seal strength at lower temperatures improves economic efficiency by allowing faster processing times and lower energy costs.
  • the linear polyethylene composition of the present invention may possess a lower heat seal initiation temperature than a similar or identical unmodified linear polyethylene resin, each providing about the same heat seal strength.
  • a heat seal resin modifier of the present invention may be useful for lowering the heat seal initiation temperature of a polyethylene resin.
  • the polyethylene resin is a linear polyethylene resin.
  • the polyethylene resin has a density of from about 0.88 to about 0.92 g/cm 3 .
  • the modified resin attains a seal strength of greater than about 25 g/inch and up to about 6000 g/inch within a temperature range of from about 150°F to about 350°F. Desirable heat seal characteristics can vary depending upon the application for which the sealing is intended.
  • the heat seal initiation temperature for the modified resins of the present invention is within a range of from about 175°F to about 300°F, more preferably within a range of from about 180°F to about 290°F, and still more preferably within a range of from about 200°F to about 290°F.
  • the modified resin of the present invention has a heat seal strength in the range of from about 25 grams/inch to about 6,000 grams/inch over the desirable heat seal initiation temperature range of from about 150°F to about 350°F.
  • the modified heat seal resin has a heat seal strength of from about 1000 grams/inch to about 4,000 grams/inch, and still more preferably from about 1500 grams/inch to about 4,000 grams/inch. Seal strength is determined according to ASTM F-88.
  • the heat seal resin modifier of the present invention is a composition comprising (a) an ethylene acid copolymer; (b) a tackifier; and, optionally, (c) a metallocene polyethylene polymer.
  • Ethylene acid copolymers suitable for use in the present invention include copolymers, for example, dipolymers and terpolymers, of ethylene and ⁇ , ⁇ -unsaturated carboxylic acids and/or derivatives thereof.
  • ⁇ , ⁇ -Unsaturated carboxylic acids and derivatives suitable for use herein include, without limitation, acrylic acid and/or methacryiic acid (genericaWy referred to herein singularly or in combination as (meth)acrylic acid); acrylic esters such as methyl (meth)acrylate, ethyl(meth)acrylate, isobutylacrylate or mixtures thereof.
  • Terpolymers are preferably ethylene/methacrylic acid/isobutyl acrylate copolymers. lonomers of the ethylene acid copolymers are preferred for use in the present invention, lonomers are well known in the polymer art, and are the fully or at least partially neutralized salts of ethylene acid copolymers.
  • an ionomer is in the form of the sodium salt, the zinc salt, or a mixture of salts of these two metal ions.
  • the modifier composition can comprise from about 0 to about 90 wt% of the acid copolymer.
  • the acid copolymer is present in the modifier composition a finite amount up to about 90 wt%, or in an amount of from about 40 to about 90 wt%, more preferably in an amount of from about 50 to about 90 wt%, and still more preferably in an amount of from about 60 to about 90 wt%, based on the total weight of the modifier composition.
  • a heat seal resin modifier of the present invention further comprises a tackifier.
  • tackifiers When used conventionally, tackifiers are generally materials which provide tack, or adhesiveness, to a composition at room or ambient temperatures. In the practice of the present invention, however, use of a tackifier is not conventional. Heat seal properties desirable in a linear polyethylene heat seal resin of this invention are required to be exhibited at temperatures much greater than ambient. Because most tackifiers become liquid and lose tack at the temperatures contemplated in the practice of this invention, it is surprising that conventional tackifiers can be made to provide the heat seal properties obtained when combined with linear polyethylenes. Suitable tackifiers for use in the present invention can be selected from conventional tackifiers, and mixtures thereof.
  • tackifiers of the present invention can be selected from polyterpenes, hydrogenated aromatic 9-carbon esters, or mixtures thereof.
  • the heat seal resin modifier composition comprises the tackifier in an amount of from about 10 to about 90 wt% based on the total weight of the modifier composition.
  • the tackifier is present in the modifier composition in an amount of from about 10 to about 60 wt%, more preferably in an amount of from about 15 to about 50 wt%, and still more preferably in an amount of from about 20 to about 40 wt% of the modifier composition.
  • a modifier of the present invention can optionally comprise from about 0 to about 10 wt%, based on the weight of the modifier composition, of a metallocene polyethylene plastomer, having a density of from about 0.87 to about 0.90 g/cm 3 .
  • the metallocene polyethylene plastomer is present in a finite amount up to about 10 wt%.
  • a heat seal resin modifier of the present invention can be prepared by blending the components by conventional methods, such as by melt blending, dry blending and coextruding, or using a batch mixing process. Any known method of making a blend of the present invention is contemplated as suitable for use herein.
  • the heat seal resin modifier and the heat seal resin to be modified may be blended by any suitable means known in the art.
  • the components are melt- blended, for example in an extruder.
  • a package comprising a linear polyethylene composition or a heat seal resin modifier of the invention.
  • the package may comprise any packaging material to which the linear polyethylene composition or a heat seal resin modifier of the invention will adhere.
  • the package may be made and sealed by any suitable means known in the art. See, e.g., the Wiley Encyclopedia of Packaging Technology.
  • Also provided by the present invention is a method of manufacturing a package comprising the step of including with a polyethylene resin having a density of from about 0.88 g/cm 3 to about 0.95 g/cm 3 , a heat seal modifier according to the invention.
  • the package may be made and sealed by any suitable means known in the art.
  • EXAMPLES The Examples are for illustrative purposes only, and are not intended to limit the scope of the invention.
  • a series of blends was prepared by melt blending the components in the proportions listed in Table 1.
  • the heat seal strength of the blends was measured according to ASTM F-88.
  • the heat seal strength results which are also shown in Table 1 , demonstrate that the heat seal initiation temperature of the examples of the invention is in general significantly lower than the heat seal initiation temperature of the comparative example.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)
  • Wrappers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
PCT/US2004/043064 2003-12-16 2004-12-16 Heat seal modifiers for linear polyethylenes Ceased WO2005059024A2 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BRPI0417109-8A BRPI0417109A (pt) 2003-12-16 2004-12-16 composição de polietileno linear, composição modificadora de vedação a quente, processo de manufatura de uma embalagem e embalagem
DE602004017899T DE602004017899D1 (de) 2003-12-16 2004-12-16 Heisssiegelmodifizierungsmittel für lineare polyethylene
AU2004298628A AU2004298628B2 (en) 2003-12-16 2004-12-16 Heat seal modifiers for linear polyethylenes
CA002547606A CA2547606A1 (en) 2003-12-16 2004-12-16 Heat seal modifiers for linear polyethylenes
EP04815178A EP1694766B1 (en) 2003-12-16 2004-12-16 Heat seal modifiers for linear polyethylenes
JP2006545596A JP5384792B2 (ja) 2003-12-16 2004-12-16 線状ポリエチレン用ヒートシール変性剤

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US53008003P 2003-12-16 2003-12-16
US60/530,080 2003-12-16

Publications (2)

Publication Number Publication Date
WO2005059024A2 true WO2005059024A2 (en) 2005-06-30
WO2005059024A3 WO2005059024A3 (en) 2005-09-15

Family

ID=34700090

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2004/043064 Ceased WO2005059024A2 (en) 2003-12-16 2004-12-16 Heat seal modifiers for linear polyethylenes

Country Status (9)

Country Link
US (1) US7635736B2 (https=)
EP (1) EP1694766B1 (https=)
JP (1) JP5384792B2 (https=)
CN (1) CN100503711C (https=)
AU (1) AU2004298628B2 (https=)
BR (1) BRPI0417109A (https=)
CA (1) CA2547606A1 (https=)
DE (1) DE602004017899D1 (https=)
WO (1) WO2005059024A2 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008022828A1 (de) 2006-08-25 2008-02-28 Henkel Ag & Co. Kgaa Schmelzklebstoff mit verbesserter haftung

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100120313A1 (en) * 2005-06-29 2010-05-13 Bohme Reinhard D Packaging Material
US8826959B2 (en) 2006-06-29 2014-09-09 Graphic Packaging International, Inc. Heat sealing systems and methods, and related articles and materials
US20100273017A1 (en) * 2006-06-29 2010-10-28 Files John C Hybrid Packaging Material
US20100273377A1 (en) * 2006-06-29 2010-10-28 Files John C High Strength Packages and Packaging Materials
US8753012B2 (en) 2006-06-29 2014-06-17 Graphic Flexible Packaging, Llc High strength packages and packaging materials

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JPS578234A (en) * 1980-06-17 1982-01-16 Du Pont Mitsui Polychem Co Ltd Heat-sealable resin composition
US4337298A (en) * 1980-11-19 1982-06-29 Gulf Oil Corporation Polymer compositions and laminates produced by bonding or coextrusion
SE465778B (sv) * 1988-01-22 1991-10-28 Teno Ab Plastfilm innehaallande en llpe och en etensampolymer samt dess anvaendning till foerpackning
JPH0349923A (ja) * 1989-07-19 1991-03-04 Tosoh Corp 積層体の製造方法
JPH0760921A (ja) * 1993-08-26 1995-03-07 Mitsui Petrochem Ind Ltd 積層体
US6120887A (en) * 1995-02-23 2000-09-19 H. B. Fuller Licensing & Financing, Inc. Disposable articles having a continuous thermoplastic coating comprising a metallocene polyolefin
JP3681488B2 (ja) * 1996-11-19 2005-08-10 三井・デュポンポリケミカル株式会社 エチレン共重合体組成物及びそれを用いた易開封性シール材料
US6593407B2 (en) * 2001-02-06 2003-07-15 National Starch And Chemical Investment Holding Corporation Hot melt adhesive composition
CN100364767C (zh) * 2002-03-14 2008-01-30 三井化学株式会社 容器
JP2002317080A (ja) * 2002-04-01 2002-10-31 Showa Denko Kk ヒートシール性樹脂組成物

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008022828A1 (de) 2006-08-25 2008-02-28 Henkel Ag & Co. Kgaa Schmelzklebstoff mit verbesserter haftung
CN101506323A (zh) * 2006-08-25 2009-08-12 汉高两合股份公司 具有改进粘合性的热熔性粘合剂
RU2453572C2 (ru) * 2006-08-25 2012-06-20 Хенкель Аг Унд Ко. Кгаа Термоклей с улучшенной адгезией
CN101506323B (zh) * 2006-08-25 2013-06-19 汉高两合股份公司 具有改进粘合性的热熔性粘合剂

Also Published As

Publication number Publication date
JP5384792B2 (ja) 2014-01-08
CA2547606A1 (en) 2005-06-30
US7635736B2 (en) 2009-12-22
WO2005059024A3 (en) 2005-09-15
AU2004298628B2 (en) 2010-05-13
BRPI0417109A (pt) 2007-02-06
US20050203249A1 (en) 2005-09-15
CN1894331A (zh) 2007-01-10
EP1694766A2 (en) 2006-08-30
CN100503711C (zh) 2009-06-24
DE602004017899D1 (de) 2009-01-02
JP2007514852A (ja) 2007-06-07
AU2004298628A1 (en) 2005-06-30
EP1694766B1 (en) 2008-11-19

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