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WO1999064500A1 - Films conservant la forme qui leur est donnee, fabriques a partir d'interpolymeres aromatiques alpha-olefiniques/vinyliques et/ou vinyliques ou vinylideniques aliphatiques ou cycloaliphatiques - Google Patents

Films conservant la forme qui leur est donnee, fabriques a partir d'interpolymeres aromatiques alpha-olefiniques/vinyliques et/ou vinyliques ou vinylideniques aliphatiques ou cycloaliphatiques Download PDF

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Publication number
WO1999064500A1
WO1999064500A1 PCT/US1999/011429 US9911429W WO9964500A1 WO 1999064500 A1 WO1999064500 A1 WO 1999064500A1 US 9911429 W US9911429 W US 9911429W WO 9964500 A1 WO9964500 A1 WO 9964500A1
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WIPO (PCT)
Prior art keywords
polymer
component
ethylene
styrene
vinyl
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PCT/US1999/011429
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English (en)
Inventor
Yunwa W. Cheung
Martin J. Guest
William R. Van Volkenburgh
Original Assignee
The Dow Chemical Company
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Publication date
Application filed by The Dow Chemical Company filed Critical The Dow Chemical Company
Priority to JP2000553501A priority Critical patent/JP2002517583A/ja
Priority to EP99925780A priority patent/EP1086167A1/fr
Priority to AU41998/99A priority patent/AU4199899A/en
Publication of WO1999064500A1 publication Critical patent/WO1999064500A1/fr

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00Polyalkenes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00Polyalkenes
    • B32B2323/10Polypropylene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2325/00Polymers of vinyl-aromatic compounds, e.g. polystyrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2353/00Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers

Definitions

  • This invention pertains to films or sheets or extruded profiles prepared from polymers which comprise at least one substantially random interpolymer comprising polymer units derived from one or more ⁇ -olefin monomers with specific amounts of one or more vinyl aromatic monomers or aliphatic or cycloaliphatic vinyl or vinylidene monomers, or a combination thereof, or blend compositions therefrom with other polymers.
  • Films or sheets or extruded profiles prepared from such interpolymers exhibit dead-fold properties as measured by their having a high force relaxation (> 40 percent) in either the machine or cross direction or both.
  • the invention covers films, sheets, and multi-layer laminates.
  • the films according to the invention may be obtained also as co-extruded and multi-layer films, such as one side sealable films, two sides sealable films, coated films, tinted films, cavitated films, untreated films, one side treated films, two sides treated films, and metallized plastic films.
  • the inventive films can also be laminated to conventional oriented polypropylene, polyethylene or polyester films, aluminum foil, paper, foam and others to impart dead fold properties to such multilayer composite structures.
  • the films and sheets of the present invention may be successfully employed for packaging in general and for packaging small items in particular.
  • Potential applications include, but are not limited to, tooth paste tubes, twist ties, candy twist wrapping, meat overwrap, paper replacement, table cloths and shower curtains .
  • Dead fold properties are especially important in a number of packaging application areas including consumer food wraps for enclosing and preparing foods, candy twist wraps, and in closeable flexible walled containers such as for example tooth paste tubes.
  • Aluminum foil possesses excellent dead fold and shaping characteristics. That is, once the foil is wrapped around an item it maintains its shape and does not unfold. However aluminum foil is somewhat expensive, is not transparent, and is not suitable for use in microwave ovens. Paper (including glassine paper and waxed paper) although easy to cut, is limited in many packaging applications due to a combination of strength, optical properties, operating temperature range and lack of water resistance properties.
  • Plastic films such as those made from polystyrene, flexible PVC and acrylic polymers are typically used for wrapping foods because of their transparency and relatively low cost. Additionally some plastic wraps based on PVC can be used in microwave applications. However flexible PVC, requires formulation with significant levels of plasticizer and contain chlorine which is not environmentally sound. In addition films made from polystyrene, flexible PVC and acrylic polymers typically are brittle and do not demonstrate the toughness required for many packaging applications. Polypropylene and polyethylene films, which would have cost advantages with respect to the above mentioned materials, cannot, on the other hand, be employed in an unmodified form because of their lack of twist retention, and moderate permeability.
  • US Patent No. 5,128,183 (P. Buzio, assigned to Borden, Inc), the entire contents, is directed to modified polyolefin films with stable twist retention and dead fold properties to be employed in wrapping in general, and particularly in wrapping small items.
  • the inventive films are obtained by extrusion and stretching of a ternary mixture comprising (1) isotactic polypropylene; (2) high density polyethylene; and (3) a glassy amorphous low molecular weight resin.
  • Japanese Patent 59-68212 (Mitsui Toatsu Chemical Co.) is directed to a polyolefin film with improved rigidity and twist retention obtained by mono-axial longitudinal orientation. Such a film, however, has poor properties in the transverse direction and has a tendency to tearing and Assuring, and its use is therefore limited to longitudinal twist wrapping.
  • German Patent DE 3514398A1 (Hoechst) a biaxially oriented film is described consisting of polypropylene, inorganic fillers and polymers such as polyamides or polymethylmethacrylate. This type of film, however, shows poor twist retention.
  • U.S. Pat. No. 4,842,187 issued Jun. 27, 1989 to Janocha, et al describes an opaque, biaxially draw-oriented thermoplastic film for candy twist wrapping.
  • the film is formed from a polymer mixture comprising from 40 to 60 percent by weight of polypropylene and from 35 to 55 percent by weight of polystyrene, and from 5 to 15 percent by weight of an inorganic or organic filler.
  • the polypropylene base layer additionally contains a low molecular weight hydrocarbon resin in an amount of 10 to 40 percent by weight.
  • the polypropylene therein is preferably an isotactic propylene homopolymer or a copolymer of ethylene and propylene having an ethylene content of less than 10 percent by weight. This is a two component base layer.
  • U.S. Pat. No. 4,916,025 by L. Pang-Chia issued April 10, 1990 describes high density polyethylene films having good dead fold and water vapor transmission characteristics which characteristics are achieved by the film containing blends of HDPE or microcrystalline wax being oriented up to two times in the machine direction and six times or more in the transverse direction.
  • U.S. Pat. No. 4,659,408 by D. D. Redding issued April 21, 1987 describes a multilayer sheet structure having improved deadfold and strength properties which properties are achieved by the sheet having an oriented substructure comprising a combination of polymer layers, including a uniaxially oriented polypropylene or high density polyethylene layer.
  • R. Grace and Co. describes films comprising one or more layers a thermoplastic, homogeneous alpha-olefin/vinyl aroamatic copolymer having improved impact resistance, printability, RF sealability, shrink and optical properties.
  • Bradfute is open ended as to the amount of substantially random interpolymer in the blend as well as the optimum amounts of ethylene/vinyl and ⁇ -olefin monomers in the ethylene/vinylidene aromatic interpolymer blend component and silent to any dead fold properties in the film compositions.
  • the present invention relates to films prepared from polymers which comprise at least one substantially random interpolymer comprising polymer units derived from one or more ⁇ -olefin monomers with specific amounts of one or more vinyl aromatic monomers or aliphatic or cycloaliphatic vinyl or vinylidene monomers, or a combination thereof, or blend compositions therefrom with other engineering thermoplastics.
  • Films prepared from such interpolymers exhibit dead- fold properties as measured by a high force relaxation of > 40 percent in the machine direction or cross direction or both. In applications such as tapes, labels or laminating films, such a high force relaxation allows conformability to uneven or irregular surfaces, and over edges, curves, folds, .
  • extruded profiles such as toy tracks, tubes, gaskets may be twisted, bent or otherwise formed into shapes which will be retained after removal of the shaping force.
  • the invention also covers sheets, and multi-layer laminates.
  • the films according to the invention may be obtained also as co-extruded and multi-layer films, such as one side sealable films, two sides sealable films, coated films, tinted films, cavitated films, untreated films, one side treated films, two sides treated films, and metallized plastic films.
  • the inventive films can also be laminated to conventional polyester films, styrenic polymer films, polyethylene films, oriented polypropylene films, and others to impart dead fold properties to such multilayer composite films.
  • the films or sheets or extruded profiles of the present invention may be successfully employed for packaging in general and for packaging small items in particular.
  • Other potential applications include, but are not limited to, meat over-wrap, paper replacement, stand-up or flat bottomed bags, table cloths and shower curtains, collapsible bottles or containers, tubes such as toothpaste tubes, fold-down structures, boxes, cartons, window boxes, surgical drapes, formable membranes, toys, tubing and clothing, tapes, laminating films, pressure sensitive labels .
  • the present invention pertains to a film, or sheet or extruded profile having at least one layer comprising; (A) at least one substantially random interpolymer, which comprises;
  • the present invention also pertains to a multilayer film or sheet or extruded profile comprising at least two layers wherein at least one of said layers is a film or sheet or extruded profile having a force relaxation in the cross direction or machine direction or both of greater than or equal to 40 percent, comprising; (A) at least one substantially random interpolymer, which comprises;
  • any numerical values recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value.
  • the amount of a component or a value of a process variable such as, for example, temperature, pressure, time is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc. are expressly enumerated in this specification.
  • one unit is considered to be 0.0001, 0.001 , 0.01 or 0.1 as appropriate.
  • hydrocarbyl as employed herein means any aliphatic, cycloaliphatic, aromatic, aryl substituted aliphatic, aryl substituted cycloaliphatic, aliphatic substituted aromatic, or aliphatic substituted cycloaliphatic groups.
  • hydrocarbyloxy means a hydrocarbyl group having an oxygen linkage between it and the carbon atom to which it is attached.
  • interpolymer is used herein to indicate a polymer wherein at least two different monomers are polymerized to make the interpolymer. This includes copolymers, terpolymers, etc.
  • film as used herein is defined as having a thickness less than or equal to 12 mils.
  • sheet as used herein is defined as having a thickness greater than 12 mils.
  • extruded profile as used herein is defined as a polymer composition, which has undergone a profile extrusion process for use in a shape specific application.
  • deformation as used herein is defined as bending, elongation, or compression.
  • dead fold property is defined as a measure of the film's ability to retain its shape or fold or crease permanently once it is folded or wrapped about an item and not spring back to an unfolded state.
  • a measure of the degree of such dead fold behavior is the magnitude of the films force relaxation in the machine or cross direction or both.
  • a film should have a high force relaxation of > 40 percent in the machine or cross direction or both.
  • dead fold film as used herein is defined as a film having dead fold properties.
  • structure as used herein is defined as a polymer composition which has undergone a molding process, a film forming process, a sheet forming process, or a foamed film forming process or a foamed sheet forming process or a lamination process to a plastic film, or aluminum foil, or paper, or foam.
  • fabricated article as used herein is defined as a polymer composition in the form of a finished article which may be formed from an intermediate comprising one of the films described herein.
  • substantially random in the substantially random interpolymer comprising polymer units derived from one or more ⁇ -olefin monomers with one or more vinyl aromatic monomers or aliphatic or cycloaliphatic vinyl or vinylidene monomers, or a combination thereof
  • substantially random means that the distribution of the monomers of said interpolymer can be described by the Bernoulli statistical model or by a first or second order Markovian statistical model, as described by J. C. Randall in POLYMER SEQUENCE DETERMINATION, Carbon- 13 NMR Method. Academic Press New York, 1977, pp. 71-78.
  • substantially random interpolymers do not contain more than 15 percent of the total amount of vinyl aromatic monomer in blocks of vinyl aromatic monomer of more than 3 units. More preferably, the interpolymer is not characterized by a high degree of either isotacticity or syndiotacticity. This means that in the carbon "13 NMR spectrum of the substantially random interpolymer the peak areas corresponding to the main chain methylene and methine carbons representing either meso diad sequences or racemic diad sequences should not exceed 75 percent of the total peak area of the main chain methylene and methine carbons.
  • the interpolymers used to prepare the films or sheets or extruded profiles of the present invention include the substantially random interpolymers prepared by polymerizing one or more ⁇ -olefins with one or more vinyl aromatic monomers or one or more aliphatic or cycloaliphatic vinyl or vinylidene monomers or a combination thereof, and optionally other polymerizable monomers.
  • Suitable ⁇ -olefins include for example, ⁇ -olefins containing from 2 to 20, preferably from 2 to 12, more preferably from 2 to 8 carbon atoms. Particularly suitable are ethylene, propylene, butene-1, 4-methyl-l -pentene, hexene-1 or octene-1 or ethylene in combination with one or more of propylene, butene- 1 , 4-methyl- 1 - pentene, hexene-1 or octene-1. These ⁇ -olefins do not contain an aromatic moiety.
  • Other optional polymerizable ethylenically unsaturated monomer(s) include norbornene and C,. 10 alkyl or C 6 . 10 aryl substituted norbornenes, with an exemplary interpolymer being ethylene/styrene/norbornene.
  • Suitable vinyl aromatic monomers which can be employed to prepare the interpolymers include, for example, those represented by the following formula:
  • R i _ C C(R ) 2
  • R 1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl
  • each R 2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl
  • Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, C,. 4 -alkyl, and C 1 . 4 -haloalkyl
  • n has a value from zero to 4, preferably from zero to 2, most preferably zero.
  • Exemplary vinyl aromatic monomers include styrene, vinyl toluene, ⁇ -methylstyrene, t-butyl styrene, chlorostyrene, including all isomers of these compounds, .
  • Particularly suitable such monomers include styrene and lower alkyl- or halogen-substituted derivatives thereof.
  • Preferred monomers include styrene, ⁇ -methyl styrene, the lower alkyl- (C, - C 4 ) or phenyl-ring substituted derivatives of styrene, such as for example, ortho-, meta-, and para-methylstyrene, the ring halogenated styrenes, para-vinyl toluene or mixtures thereof, .
  • a more preferred aromatic vinyl monomer is styrene.
  • aliphatic or cycloaliphatic vinyl or vinylidene compounds it is meant addition polymerizable vinyl or vinylidene monomers corresponding to the formula:
  • R i — C C(R 2 ) 2
  • a 1 is a sterically bulky, aliphatic or cycloaliphatic substituent of up to 20 carbons
  • R 1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl
  • each R 2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl
  • R 1 and A 1 together form a ring system.
  • Preferred aliphatic or cycloaliphatic vinyl or vinylidene compounds are monomers in which one of the carbon atoms bearing ethylenic unsaturation is tertiary or quaternary substituted.
  • substituents include cyclic aliphatic groups such as cyclohexyl, cyclohexenyl, cyclooctenyl, or ring alkyl or aryl substituted derivatives thereof, tert- butyl, norbornyl, .
  • Most preferred aliphatic or cycloaliphatic vinyl or vinylidene compounds are the various isomeric vinyl- ring substituted derivatives of cyclohexene and substituted cyclohexenes, and 5-ethylidene-2-norbornene.
  • 1-, 3-, and 4-vinylcyclohexene are especially suitable.
  • the substantially random interpolymers may be modified by typical grafting, hydrogenation, functionalizing, or other reactions well known to those skilled in the art.
  • the polymers may be readily sulfonated or chlorinated to provide functionalized derivatives according to established techniques.
  • the substantially random interpolymers may also be modified by various chain extending or cross-linking processes including, but not limited to peroxide-, silane-, sulfur-, radiation-, or azide-based cure systems.
  • chain extending or cross-linking processes including, but not limited to peroxide-, silane-, sulfur-, radiation-, or azide-based cure systems.
  • Dual cure systems which use a combination of heat, moisture cure, and radiation steps, may be effectively employed. Dual cure systems are disclosed and claimed in U. S. Patent Application Serial No. 536,022, filed on September 29, 1995, in the names of K. L. Walton and S. V. Karande. For instance, it may be desirable to employ peroxide crosslinking agents in conjunction with silane crosslinking agents, peroxide crosslinking agents in conjunction with radiation, sulfur-containing crosslinking agents in conjunction with silane crosslinking agents, etc.
  • the substantially random interpolymers may also be modified by various cross-linking processes including, but not limited to the incorporation of a diene component as a termonomer in its preparation and subsequent cross linking by the aforementioned methods and further methods including vulcanization via the vinyl group using sulfur for example as the cross linking agent.
  • One method of preparation of the substantially random interpolymers includes polymerizing a mixture of polymerizable monomers in the presence of one or more metallocene or constrained geometry catalysts in combination with various cocatalysts.
  • the substantially random interpolymers can be prepared as described in EP-A- 0,416,815 by James C. Stevens et al. and US Patent No. 5,703,187 by Francis J. Timmers.
  • Such a method of preparation of the substantially random interpolymers includes polymerizing a mixture of polymerizable monomers in the presence of one or more metallocene or constrained geometry catalysts in combination with various cocatalysts.
  • Preferred operating conditions for such polymerization reactions are pressures from atmospheric up to 3000 atmospheres and temperatures from -30°C to 200°C. Polymerizations and unreacted monomer removal at temperatures above the autopolymerization temperature of the respective monomers may result in formation of some amounts of homopolymer polymerization products resulting from free radical polymerization.
  • substantially random ⁇ -olefin/vinyl aromatic interpolymers can also be prepared by the methods described in JP 07/278230 employing compounds shown by the general formula
  • Cp 1 and Cp 2 are cyclopentadienyl groups, indenyl groups, fluorenyl groups, or substituents of these, independently of each other;
  • R 1 and R 2 are hydrogen atoms, halogen atoms, hydrocarbon groups with carbon numbers of 1-12, alkoxyl groups, or aryloxyl groups, independently of each other;
  • M is a group IV metal, preferably Zr or Hf, most preferably Zr; and
  • R 3 is an alkylene group or silanediyl group used to crosslink Cp 1 and Cp 2 ).
  • the substantially random ⁇ -olefin/vinyl aromatic interpolymers can also be prepared by the methods described by John G. Bradfute et al. (W. R.
  • these new signals are due to sequences involving two head- to-tail vinyl aromatic monomer insertions preceded and followed by at least one ⁇ - olefin insertion, for example an ethylene/styrene/styrene/ethylene tetrad wherein the styrene monomer insertions of said tetrads occur exclusively in a 1,2 (head to tail) manner.
  • interpolymers can be prepared by conducting the polymerization at temperatures of from -30°C to 250°C in the presence of such catalysts as those represented by the formula
  • hydrocarbyl substituted 1,3- butadiene m is 1 or 2; and optionally, but preferably in the presence of an activating cocatalyst.
  • suitable substituted cyclopentadienyl groups include those illustrated by the formula:
  • each R is independently, each occurrence, H, hydrocarbyl, silahydrocarbyl, or hydrocarbylsilyl, containing up to 30 preferably from 1 to 20 more preferably from 1 to 10 carbon or silicon atoms or two R groups together form a divalent derivative of such group.
  • R independently each occurrence is (including where appropriate all isomers) hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl or silyl or (where appropriate) two such R groups are linked together forming a fused ring system such as indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, or octahydrofluorenyl.
  • catalysts include, for example, racemic- (dimethylsilanediyl)-bis-(2-methyl-4-phenylindenyl)zirconium dichloride, racemic- (dimethylsilanediyl)-bis-(2-methyl-4-phenylindenyl)zirconium 1 ,4-diphenyl- 1,3- butadiene, racemic-(dimethylsilanediyl)-bis-(2-methyl-4-phenylindenyl)zirconium di- Cl-4 alkyl, racemic-(dimethylsilanediyl)-bis-(2-methyl-4-phenylindenyl)zirconium di-Cl-4 alkoxide, or any combination thereof .
  • titanium-based constrained geometry catalysts [N-(l , 1 -dimethylethyl)- 1 , 1 -dimethyl- 1 -[(1 ,2,3,4,5- ⁇ )- 1 ,5,6,7-tetrahydro-s- indacen-l-yl]silanaminato(2-)-N]titanium dimethyl; (l-indenyl)(tert- butylamido)dimethyl- silane titanium dimethyl; ((3-tert-butyl)(l,2,3,4,5- ⁇ )-l- indenyl)(tert-butylamido) dimethylsilane titanium dimethyl; and ((3-iso- propyl)(l,2,3,4,5- ⁇ )-l-indenyl)(tert-butyl amido)dimethylsilane titanium dimethyl, or any combination thereof .
  • ⁇ -olefin/vinyl aromatic monomer interpolymers such as propylene/styrene and butene/styrene are described in United States patent number 5,244,996, issued to Mitsui Petrochemical Industries Ltd or United States patent number 5,652,315 also issued to Mitsui Petrochemical Industries Ltd or as disclosed in DE 197 11 339 Al to Denki Kagaku Kogyo KK.
  • an amount of atactic vinyl aromatic homopolymer may be formed due to homopolymerization of the vinyl aromatic monomer at elevated temperatures.
  • the presence of vinyl aromatic homopolymer is in general not detrimental for the purposes of the present invention and can be tolerated.
  • the vinyl aromatic homopolymer may be separated from the interpolymer, if desired, by extraction techniques such as selective precipitation from solution with a non solvent for either the interpolymer or the vinyl aromatic homopolymer.
  • Blend Compositions Comprising the Substantially Random Interpolymers
  • the present invention also provides films prepared from blends of the substantially random ⁇ -olefin/ vinyl or vinylidene interpolymers with one or more other polymer components which span a wide range of compositions.
  • the other polymer component of the blend can include, but is not limited to, one or more of an engineering thermoplastic, an ⁇ -olefm homopolymer or interpolymer, a thermoplastic olefin, a styrenic block copolymer, a styrenic homo- or copolymer, an elastomer, or a vinyl halide polymer.
  • Engineering thermoplastics include acetal and acrylic resins, polyamides (for example nylon-6, nylon 6,6,), polyimides, polyetherimides, cellulosics, polyesters, poly(arylate), aromatic polyesters, poly(carbonate), poly(butylene) and polybutylene and polyethylene terephthalates, liquid crystal polymers, and selected polyolefins, blends, or alloys of the foregoing resins, and some examples from other resin types (including for example polyethers) high temperature polyolefins such as polycyclopentanes, its copolymers, and polymethylpentane.).
  • polyamides for example nylon-6, nylon 6,6,
  • polyimides for example nylon-6, nylon 6,6,
  • polyetherimides polyetherimides
  • cellulosics polyesters
  • poly(arylate) aromatic polyesters
  • poly(carbonate) poly(butylene) and polybutylene and polyethylene terephthalates
  • liquid crystal polymers and selected polyolefins, blends,
  • MMA methyl methacrylate
  • MMA is usually copolymerized with other acrylates such as methyl- or ethyl acrylate using four basic polymerization processes, bulk, suspension, emulsion and solution.
  • Acrylics can also be modified with various ingredients including butadiene, vinyl and butyl acrylate.
  • the ⁇ -olefin homopolymers and interpolymers comprise polypropylene, propylene/C 4 -C 20 ⁇ - olefin copolymers, polyethylene, and ethylene/C 3 -C 20 ⁇ - olefin copolymers
  • the interpolymers can be either heterogeneous ethylene/ ⁇ -olefin interpolymers or homogeneous ethylene/ ⁇ -olefm interpolymers, including the substantially linear ethylene/ ⁇ -olefin interpolymers.
  • aliphatic ⁇ - olefins having from 2 to 20 carbon atoms and containing polar groups.
  • Suitable aliphatic ⁇ -olefin monomers which introduce polar groups into the polymer include, for example, ethylenically unsaturated nitriles such as acrylonitrile, methacrylonitrile, ethacrylonitrile, etc.; ethylenically unsaturated anhydrides such as maleic anhydride; ethylenically unsaturated amides such as acrylamide, methacrylamide etc.; ethylenically unsaturated carboxylic acids (both mono- and difunctional) such as acrylic acid and methacrylic acid, etc.; esters (especially lower, for example C,-C 6 , alkyl esters) of ethylenically unsaturated carboxylic acids such as methyl methacrylate, ethyl acrylate, hydroxyethylacrylate, n-butyl acrylate or methacrylate, 2-ethyl-hexylacrylate, or ethylene-vinyl acetate
  • Such monomers containing polar groups are acrylic acid, vinyl acetate, maleic anhydride and acrylonitrile.
  • Halogen groups which can be included in the polymers from aliphatic ⁇ -olefm monomers include fluorine, chlorine and bromine; preferably such polymers are chlorinated polyethylenes (CPEs)
  • Heterogeneous interpolymers are differentiated from the homogeneous interpolymers in that in the latter, substantially all of the interpolymer molecules have the same ethylene/comonomer ratio within that interpolymer, whereas heterogeneous interpolymers are those in which the interpolymer molecules do not have the same ethylene/comonomer ratio.
  • the term "broad composition distribution" used herein describes the comonomer distribution for heterogeneous interpolymers and means that the heterogeneous interpolymers have a "linear" fraction and that the heterogeneous interpolymers have multiple melting peaks (that is, exhibit at least two distinct melting peaks) by DSC.
  • the heterogeneous interpolymers have a degree of branching less than or equal to 2 methyls/1000 carbons in 10 percent (by weight) or more, preferably more than 15 percent (by weight), and especially more than 20 percent (by weight).
  • the heterogeneous interpolymers also have a degree of branching equal to or greater than 25 methyls/1000 carbons in 25 percent or less (by weight), preferably less than 15 percent (by weight), and especially less than 10 percent (by weight).
  • the Ziegler catalysts suitable for the preparation of the heterogeneous component of the current invention are typical supported, Ziegler-type catalysts.
  • Examples of such compositions are those derived from organomagnesium compounds, alkyl halides or aluminum halides or hydrogen chloride, and a transition metal compound. Examples of such catalysts are described in U.S. Pat Nos. 4,314,912 (Lowery, Jr. et al.), 4,547,475 (Glass et al.), and 4,612,300 (Coleman, III).
  • Suitable catalyst materials may also be derived from a inert oxide supports and transition metal compounds. Examples of such compositions are described in U.S. Pat No. 5,420,090 (Spencer, et al).
  • the heterogeneous polymer component can be an ⁇ -olefin homopolymer preferably polyethylene or polypropylene, or, preferably, an interpolymer of ethylene with at least one C3-C20 ⁇ -olefin or C4-C18 dienes or a combination thereof.
  • Heterogeneous copolymers of ethylene, and propylene, 1-butene, 1-hexene, 4-methyl- 1 -pentene and 1-octene are especially preferred.
  • the homogeneous interpolymers useful for forming the compositions described herein have homogeneous branching distributions. That is, the polymers are those in which the comonomer is randomly distributed within a given interpolymer molecule and wherein substantially all of the interpolymer molecules have the same ethylene/comonomer ratio within that interpolymer.
  • the homogeneity of the polymers is typically described by the SCBDI (Short Chain Branch Distribution Index) or CDBI (Composition Distribution Branch Index) and is defined as the weight percent of the polymer molecules having a comonomer content within 50 percent of the median total molar comonomer content.
  • the CDBI of a polymer is readily calculated from data obtained from techniques known in the art, such as, for example, temperature rising elution fractionation (abbreviated herein as "TREF") as described, for example, in Wild et al, Journal of Polymer Science, Poly. Phys. Ed, Vol. 20, p. 441 (1982), in U.S. Patent 4,798,081 (Hazlitt et al.), or as is described in USP 5,008,204 (Stehling).
  • the technique for calculating CDBI is described in USP 5,322,728 (Davey et al. ) and in USP 5,246,783 (Spenadel et al). or in U.S. Patent 5,089,321 (Chum et al).
  • the SCBDI or CDBI for the homogeneous interpolymers used in the present invention is preferably greater than 30 percent, especially greater than 50 percent.
  • the homogeneous interpolymers used in this invention essentially lack a measurable "high density" fraction as measured by the TREF technique (that is, the homogeneous ethylene/ ⁇ -olefin interpolymers do not contain a polymer fraction with a degree of branching less than or equal to 2 methyls/1000 carbons).
  • the homogeneous interpolymers also do not contain any highly short chain branched fraction (that is, they do not contain a polymer fraction with a degree of branching equal to or more than 30 methyls/1000 carbons).
  • substantially linear ethylene/ ⁇ -olefin polymers and interpolymers of the present invention are also homogeneous interpolymers but are further herein defined as in U.S. Patent No. 5,272,236 (Lai et al.), and in U.S. Patent No.
  • substantially linear ethylene/ ⁇ -olefin interpolymer means that the polymer backbone is substituted with 0.01 long chain branches/1000 carbons to 3 long chain branches/1000 carbons, more preferably from 0.01 long chain branches/1000 carbons to 1 long chain branches/1000 carbons, and especially from 0.05 long chain branches/1000 carbons to 1 long chain branches/1000 carbons.
  • Long chain branching is defined herein as a chain length of at least one carbon more than two carbons less than the total number of carbons in the comonomer, for example, the long chain branch of an ethylene/octene substantially linear ethylene interpolymer is at least seven (7) carbons in length (that is, 8 carbons less 2 equals 6 carbons plus one equals seven carbons long chain branch length).
  • the long chain branch can be as long as about the same length as the length of the polymer back-bone.
  • Long chain branching is determined by using ⁇ C nuclear magnetic resonance (NMR) spectroscopy and is quantified using the method of Randall (Rev. Macromol. Chem. Phys., C29 (2&3), p. 285-297).
  • Long chain branching is to be distinguished from short chain branches which result solely from incorporation of the comonomer, so for example the short chain branch of an ethylene/octene substantially linear polymer is six carbons in length, while the long chain branch for that same polymer is at least seven carbons in length.
  • the catalysts used to prepare the homogeneous interpolymers for use as blend components in the present invention are metallocene catalysts.
  • metallocene catalysts include the bis(cyclopentadienyl)-catalyst systems and the mono(cyclopentadienyl) Constrained Geometry catalyst systems (used to prepare the substantially linear ethylene/ ⁇ -olefin polymers).
  • Constrained geometry metal complexes and methods for their preparation are disclosed EP-A-416,815EP-A- 468,651; EP-A-514,828; as well as US-A-5,055,438, US-A-5,057,475, US-A- 5,096,867, US-A-5,064,802, US-A-5,132,380, US-A-5,721,185, US-A-5,374,696 and US-A-5,470,993
  • Patents and published European Patent Applications are herein inco ⁇ orated in their entirety by reference thereto.
  • the homogeneous polymer component can be an ⁇ -olefin homopolymer preferably polyethylene or polypropylene, or, preferably, an interpolymer of ethylene with at least one C3-C20 ⁇ -olefin C4-C18 dienes.
  • Homogeneous copolymers of ethylene, and propylene, 1-butene, 1-hexene, 4-methyl-l -pentene and 1-octene are especially preferred.
  • TPOs Thermoplastic olefins
  • EPM ethylene/propylene rubber
  • EPDM ethylene/propylene diene monomer terpolymer
  • Other materials or components can be added into the formulation depending upon the application, including oil, fillers, and cross- linking agents.
  • TPOs are characterized by a balance of stiffness (modulus) and low temperature impact, good chemical resistance and broad use temperatures. Because of features such as these, TPOs are used in many applications, including automotive facia and instrument panels, and also potentially in wire and cable
  • the polypropylene is generally in the isotactic form of homopolymer polypropylene, although other forms of polypropylene can also be used (for example, syndiotactic or atactic).
  • Polypropylene impact copolymers for example, those wherein a secondary copolymerization step reacting ethylene with the propylene is employed
  • random copolymers also reactor modified and usually containing 1.5-7 percent ethylene copolymerized with the propylene
  • TPO formulations disclosed herein In-reactor TPO's can also be used as blend components of the present invention.
  • a complete discussion of various polypropylene polymers is contained in Modern Plastics Encyclopedia/89, mid October 1988 Issue, Volume 65, Number 11, pp.
  • the molecular weight of the polypropylene for use in the present invention is conveniently indicated using a melt flow measurement according to ASTM D- 1238, Condition 230°C/2.16 kg (formerly known as "Condition (L)” and also known as 12). Melt flow rate is inversely proportional to the molecular weight of the polymer. Thus, the higher the molecular weight, the lower the melt flow rate, although the relationship is not linear.
  • the melt flow rate for the polypropylene useful herein is generally from 0.1 grams/10 minutes (g/10 min) to 35 g/10 min, preferably from 0.5 g/10 min to 25 g/10 min, and especially from 1 g/10 min to 20 g/10 min.
  • block copolymers having unsaturated rubber monomer units including, but not limited to, styrene-butadiene (SB), styrene-isoprene(SI), styrene- butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), ⁇ -methylstyrene-butadiene- ⁇ -methylstyrene and ⁇ -methylstyrene-isoprene- ⁇ -methylstyrene.
  • SB styrene-butadiene
  • SI styrene-isoprene
  • SI styrene-butadiene
  • SI styrene-isoprene-styrene
  • SIS styrene-isoprene-styrene
  • the styrenic portion of the block copolymer is preferably a polymer or interpolymer of styrene and its analogs and homologs including ⁇ -methylstyrene and ring-substituted styrenes, particularly ring-methylated styrenes.
  • the preferred styrenics are styrene and ⁇ -methylstyrene, and styrene is particularly preferred.
  • Block copolymers with unsaturated rubber monomer units may comprise homopolymers of butadiene or isoprene or they may comprise copolymers of one or both of these two dienes with a minor amount of styrenic monomer.
  • Preferred block copolymers with saturated rubber monomer units comprise at least one segment of a styrenic unit and at least one segment of an ethylene- butene or ethylene-propylene copolymer.
  • Preferred examples of such block copolymers with saturated rubber monomer units include styrene/ethylene-butene copolymers, styrene/ethylene-propylene copolymers, styrene/ethylene- butene/styrene (SEBS) copolymers, styrene/ethylene-propylene/styrene (SEPS) copolymers.
  • block copolymers In addition to the block copolymers are the various styrene homopolymers and copolymers and rubber modified styrenics. These include polystyrene, high impact polystyrene and copolymers such as acrylonitrile-butadiene-styrene (ABS) polymers, styrene-acrylonitrile (SAN).
  • ABS acrylonitrile-butadiene-styrene
  • SAN styrene-acrylonitrile
  • the elastomers include, but are not limited to, rubbers such as polyisoprene, polybutadiene, natural rubbers, ethylene/propylene rubbers, ethylene/propylene diene (EPDM) rubbers, styrene/butadiene rubbers, thermoplastic polyurethanes.
  • rubbers such as polyisoprene, polybutadiene, natural rubbers, ethylene/propylene rubbers, ethylene/propylene diene (EPDM) rubbers, styrene/butadiene rubbers, thermoplastic polyurethanes.
  • the vinyl halide polymer component of the blends of the present invention include but are not limited to homopolymers and copolymers of vinyl halides with copolymerizable monomers such as ⁇ -olefins including but not limited to ethylene, propylene, vinyl esters of organic acids containing 1 to 18 carbon atoms, for example vinyl acetate, vinyl stearate and so forth; vinyl chloride, vinylidene chloride, symmetrical dichloroethylene; acrylonitrile, methacrylonitrile; alkyl acrylate esters in which the alkyl group contains 1 to 8 carbon atoms, for example methyl acrylate and butyl acrylate; the corresponding alkyl methacrylate esters; dialkyl esters of dibasic organic acids in which the alkyl groups contain 1 - 8 carbon atoms, for example dibutyl fumarate, diethyl maleate, and so forth.
  • ⁇ -olefins including but not limited to ethylene, propylene,
  • the vinyl halide polymers are homopolymers or copolymers of vinyl chloride or vinylidene chloride.
  • Poly (vinyl chloride) polymers PVC can be further classified into two main types by their degree of rigidity. These are “rigid” PVC and “flexible” PVC. Flexible PVC is distinguished from rigid PVC primarily by the presence of and amount of plasticizers in the resin. Flexible PVC typically has improved processability, lower tensile strength and higher elongation than rigid PVC.
  • PVDC vinylidene chloride homopolymers and copolymers
  • typically the copolymers with vinyl chloride, acrylates or nitriles are used commercially and are most preferred. The choice of the comonomer significantly affects the properties of the resulting polymer. Perhaps the most notable properties of the various PVDC's are their low permeability to gases and liquids, barrier properties; and chemical resistance.
  • CPVC chlorinated PVC
  • CPVC chlorinated PVC
  • compositions comprising at least one substantially random inte ⁇ olymer used to prepare the films or sheets or extruded profiles of the present invention in addition to optionally comprising one or more of another polymer components can optionally comprise one or more fillers.
  • organic and inorganic fillers are also included as a potential component of the polymer compositions used in the present invention.
  • Representative examples of such fillers include organic and inorganic fibers such as those made from asbestos, boron, graphite, ceramic, glass, metals (such as stainless steel) or polymers (such as aramid fibers) talc, carbon black, carbon fibers, calcium carbonate, alumina trihydrate, glass fibers, marble dust, cement dust, clay, feldspar, silica or glass, fumed silica, alumina, magnesium oxide, magnesium hydroxide, antimony oxide, zinc oxide, barium sulfate, aluminum silicate, calcium silicate, titanium dioxide, titanates, aluminum nitride, B 2 O 3 , nickel powder or chalk.
  • organic and inorganic fibers such as those made from asbestos, boron, graphite, ceramic, glass, metals (such as stainless steel) or polymers (such as aramid fibers) talc, carbon black, carbon fibers, calcium carbonate,
  • organic or inorganic, fiber or mineral, fillers include carbonates such as barium, calcium or magnesium carbonate; fluorides such as calcium or sodium aluminum fluoride; hydroxides such as aluminum hydroxide; metals such as aluminum, bronze, lead or zinc; oxides such as aluminum, antimony, magnesium or zinc oxide, or silicon or titanium dioxide; silicates such as asbestos, mica, clay (kaolin or calcined kaolin), calcium silicate, feldspar, glass (ground or flaked glass or hollow glass spheres or microspheres or beads, whiskers or filaments), nepheline, perlite, pyrophyllite, talc or wollastonite; sulfates such as barium or calcium sulfate; metal sulfides; cellulose, in forms such as wood or shell flour; calcium terephthalate; and liquid crystals, or ground up plastrics such as thermoset polymers. Mixtures of more than one such filler may be used as well. These fillers could be employed in amounts from 0,
  • Additives such as antioxidants (for example, hindered phenols such as, for example, IrganoxTM 1010, and phosphites, for example, IrgafosTM 168, (both are registered trademarks of, and supplied by Ciba-Geigy Corporation, NY), u.v.
  • antioxidants for example, hindered phenols such as, for example, IrganoxTM 1010, and phosphites, for example, IrgafosTM 168, (both are registered trademarks of, and supplied by Ciba-Geigy Corporation, NY), u.v.
  • TinuvinTM 328 and ChimassorbTM 944 both are registered trademarks of, and supplied by Ciba-Geigy Corporation, NY
  • cling additives for example, polyisobutylene
  • slip agents such as erucamide stearamide
  • antiblock additives antifogging agents, colorants, pigments
  • colorants colorants, pigments
  • Processing aids which are also referred to herein as plasticizers, are optionally provided to reduce the viscosity of a composition, and include the phthalates, such as dioctyl phthalate and diisobutyl phthalate, natural oils such as lanolin, and paraffin, naphthenic and aromatic oils obtained from petroleum refining, and liquid resins from rosin or petroleum feedstocks.
  • Suitable modifiers which can be employed herein as the plasticizer include at least one plasticizer selected from the group consisting of phthalate esters, trimellitate esters, benzoates, adipate esters, epoxy compounds, phosphate esters (triaryl, trialkyl, mixed alkyl aryl phosphates), glutarates and oils.
  • Particularly suitable phthalate esters include, for example, dialkyl C4-C18 phthalate esters such as diethyl, dibutyl phthalate, diisobutyl phthalate, butyl 2-ethylhexyl phthalate, dioctyl phthalate, diisooctyl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diisodecyl phthalate, diundecyl phthalate, mixed aliphatic esters such as heptyl nonyl phthalate, di(n-hexyl, n-octyl, n-decyl) phthalate (P610), di(n-octyl, n-decyl) phthalate (P810), and aromatic phthalate esters such as diphenyl phthalate ester, or mixed aliphatic-aromatic esters such as benzyl
  • oils useful as processing aids include white mineral oil (such as KaydolTM oil (available from Witco), and ShellflexTM 371 naphthenic oil (available from Shell Oil Company). Another suitable oil is TufloTM oil (available from Lyondell).
  • Antifogging or antistatic agents can be added to the films and sheets of the present invention to increase surface conductivity and prevention of water droplet formation and attraction of dust and dirt on the film surface. These antifogging agents include, but are not limited to, glycerol mono-stearate, glycerol mono-oleate, lauric diphthalamides, ethoxylated amines, ethoxylated esters, and other additives known in the industry.
  • Tackifiers can also be added to the polymer compositions used to prepare the films or sheets or extruded profiles of the present invention in order to alter the Tg and thus extend the available application temperature window of the film.
  • tackifiers include, but are not limited to, aliphatic resins, polyte ⁇ ene resins, hydrogenated resins, mixed aliphatic-aromatic resins, styrene/ ⁇ -methylene styrene resins, pure monomer hydrocarbon resin, hydrogenated pure monomer hydrocarbon resin, modified styrene copolymers, pure aromatic monomer copolymers, and hydrogenated aliphatic hydrocarbon resins.
  • Exemplary aliphatic resins include those available under the trade designations EscorezTM, PiccotacTM, MercuresTM, WingtackTM, Hi-RezTM, QuintoneTM, TackirolTM, etc.
  • Exemplary polyte ⁇ ene resins include those available under the trade designations NirezTM, PiccolyteTM, WingtackTM, ZonarezTM, etc.
  • Exemplary hydrogenated resins include those available under the trade designations EscorezTM, ArkonTM, ClearonTM, etc.
  • Exemplary mixed aliphatic-aromatic resins include those available under the trade designations EscorezTM, RegaliteTM, HercuresTM, ARTM, ImprezTM, NorsoleneTM M, MarukarezTM, ArkonTM M, QuintoneTM, WingtackTM, etc.
  • One particularly preferred class of tackifiers includes the styrene/ ⁇ -methylene stryene tackifiers available from Hercules.
  • Particularly suitable classes of tackifiers include WingtackTM 86 and HercotacTM 1149, Eastman H-130, and styrene/ ⁇ -methyl styrene tackifiers.
  • the amount of antioxidant employed is that amount which prevents the polymer or polymer blend from undergoing oxidation at the temperatures and environment employed during storage and ultimate use of the polymers.
  • Such amount of antioxidants is usually in the range of from 0.01 to 10, preferably from 0.05 to 5, more preferably from 0.1 to 2 percent by weight based upon the weight of the polymer or polymer blend.
  • the amounts of any of the other enumerated additives are the functionally equivalent amounts such as the amount to render the polymer or polymer blend antiblocking, to produce the desired result, to provide the desired color from the colorant or pigment.
  • Such additives can suitably be employed in the range of from 0.05 to 50, preferably from 0.1 to 35, more preferably from 0.2 to 20 percent by weight based upon the weight of the polymer or polymer blend.
  • the blended polymer compositions used to prepare the films or sheets or extruded profiles of the present invention can be prepared by any convenient method, including dry blending the individual components and subsequently melt mixing or melt compounding in a Haake torque rheometer or by dry blending without melt blending followed by part fabrication, either directly in the extruder or mill used to make the finished article (for example, the automotive part), or by pre-melt mixing in a separate extruder or mill (for example, a Banbury mixer), or by solution blending, or by compression molding, or by calendering.
  • the dead fold films of the present invention can be made using conventional fabrication techniques, for example simple bubble extrusion (usually with a high blow-up ratio (BUR)), biaxial orientation processes (such as tenter frames or double bubble processes), simple cast/sheet extrusion, coextrusion, lamination, etc.
  • BUR blow-up ratio
  • Conventional simple bubble extrusion processes also known as hot blown film processes are described, for example, in The Encyclopedia of Chemical Technology. Kirk-Othmer, Third Edition, John Wiley & Sons, New York, 1981, Vol 16, pp. 416- 417 and Vol. 18, pp. 191-192.
  • Biaxial orientation film manufacturing processes such as described in the "double bubble" process of USP 3,456,044 (Pahlke), and the processes described in USP 4,352,849 (Mueller), USP 4,820,557 and 4,837,084 (both to Warren), USP 4,865,902 (Golike et al), USP 4,927,708 (Herran et al.), USP 4.952,451 (Mueller), and USP 4,963,419 and 5,059,481 (both to Lustig et al), can also be used to make the novel film structures of this invention.
  • Biaxially oriented film structures can also be made by a tenter-frame technique, such as that used for oriented polypropylene.
  • thermo forming Injection molding, thermo forming, extrusion coating, profile extrusion, and sheet extrusion processes are described, for example, in Plastics Materials and
  • tapes and ribbons of the present invention can be prepared by the primary extrusion process itself or by known post-extrusion slitting, cutting or stamping techniques.
  • Profile extrusion is an example of a primary extrusion process that is particularly suited to the preparation of tapes, bands, ribbons .
  • the dead fold films of the present invention can also be rendered pervious or "breathable" by any method well known in the art including by apperturing, slitting, microperforating, mixing with fibers or foams, or the like and combinations thereof.
  • Examples of such methods include, USP 3,156,242 by Crowe, Jr., USP 3,881,489 by Hartwell, USP 3,989,867 by Sisson and USP 5,085,654 by Buell, the disclosures of all of which are inco ⁇ orate herein by reference.
  • the film structure and the substantially random inte ⁇ olymer selected for use in the practice of this invention will depend in large part upon the particulars of the application, for example the preferred properties of a film used in a shrink wrap are different than the preferred properties of a film used in a stretch overwrap.
  • the present dead fold film structures can be monolayer film or a multilayer film in which one or more film layers comprises at least one substantially random inte ⁇ olymer.
  • the film structure is multilayer, it can be of any conventional structure, for example 2-ply, 3-ply, 4-ply, 5-ply, 6-ply, 7-ply, etc.
  • the structure will generally have an odd number of layers, and the film layer(s) comprising a substantially random inte ⁇ olymer can be one or both outer layers one or more core layers.
  • Those layer(s) constructed from polymer other than a substantially random inte ⁇ olymer can comprise any suitable material generally compatible with a film constructed from a substantially random inte ⁇ olymer, for example one or more conventional LDPE, LLDPE, ULDPE, EVA, EAA, .
  • Additives such as those described above with respect to monolayer films can also be used in these multilayer films, and these additives can be inco ⁇ orated into any of the film layers as desired, for example tackifiers and slip agents into one or both outer layers, fillers in one or more core layers, etc.
  • plastic films used in this invention include, depending on the nature of the other film layers in the structure, ease of fabrication and good oxygen permeability (particularly with respect to films made from such copolymers as EVA and EAA), oxygen impermeability (particularly with respect to films containing an oxygen barrier such as SARAN or ethylene vinyl alcohol), dart impact, puncture resistance, tensile strength, low modulus, tear resistance, shrinkability, high clarity and a low affect on the taste and odor properties of the packaged food.
  • the plastic films of this invention are well suited for stretch overwrap packaging various fresh foods, for example retail-cut red meats, fish, poultry, vegetables, fruits, cheeses, and other food products destined for retail display and that benefit from access to environmental oxygen.
  • These films are preferably prepared as nonshrink films (for example, without biaxial orientation induced by double bubble processing) with good oxygen permeability, stretch, elastic recovery and hot tack characteristics, and can be made available to wholesalers and retailers in any conventional form, for example stock rolls, and used on all conventional equipment.
  • plastic films of this invention can be used as shrink, skin and vacuum form packages for foods.
  • the films comprising the shrink packages are typically biaxially oriented, exhibit low shrink tension, are of a density greater than 0.89 g/cm ⁇ , and are typically 0.6 to 2 mil in thickness.
  • the elastic film structures used in vacuum skin packaging can be multilayered, are typically 5 to 12 mil in thickness.
  • the dead fold films of the present invention can also be formed by extrusion processes and, most preferably, by art-known coextrusion methods. Following coextrusion the film is cooled to a solid state by, for example, cascading water or chilled air quenching.
  • a precursor film layer or layers may be formed by extrusion with additional layers thereafter being extrusion coated thereon to form multilayer films.
  • Two multilayer tubes may also be formed with one of the tubes thereafter being coated or laminated onto the other.
  • the polymer compositions used to prepare the films or sheets or extruded profiles of the present invention comprise from 25 to 100, preferably from 40 to 95, more preferably from 50 to 95 wt percent, (based on the combined weights of this component and the polymer component other than the substantially random inte ⁇ olymer) of one or more inte ⁇ olymers of one or more ⁇ -olefins and one or more monovinyl aromatic monomers or one or more aliphatic or cycloaliphatic vinyl or vinylidene monomers, or a combination thereof.
  • substantially random inte ⁇ olymers usually contain from 29 to 65 preferably from 33 to 65, more preferably from 35 to 65 mole percent of at least one vinyl aromatic monomer or aliphatic or cycloaliphatic vinyl or vinylidene monomer, or combination thereof, and from 35 to 71, preferably from 35 to 67, more preferably from 35 to 65 mole percent of at least one aliphatic ⁇ -olefin having from 2 to 20 carbon atoms.
  • the number average molecular weight (Mn) of the substantially random inte ⁇ olymer used to prepare the films or sheets or extruded profiles of the present invention is greater than 10,000, preferably from 20,000 to 500,000, more preferably
  • the melt index (I 2 ) of the substantially random inte ⁇ olymer used to prepare the films or sheets or extruded profiles of the present invention is from 0.01 to 100, preferably of from 0.1 to 20, more preferably of from 0.1 to 5 g/10 min.
  • the molecular weight distribution (MJM n ) of the substantially random inte ⁇ olymer used to prepare the films or sheets or extruded profiles of the present invention is from 1.5 to 20, preferably of from 1.8 to 10, more preferably of from 2 to
  • the density of the substantially random inte ⁇ olymer used to prepare the films or sheets or extruded profiles of the present invention is greater than 0.930, preferably from 0.930 to 1.045, more preferably of from 0.930 to 1.040, most preferably of from 0.930 to 1.030 g/cm 3 .
  • the polymer compositions used to prepare the films or sheets or extruded profiles of the present invention can also comprise from 0 to 75, preferably from 5 to 60, more preferably from 5 to 50 weight percent of at least one polymer other than the substantially random inte ⁇ olymer (based on the combined weights of this component and the substantially random inte ⁇ olymer) which can comprise a homogenous ⁇ - olefin homopolymer or inte ⁇ olymer comprising polypropylene, propylene/C 4 -C 20 ⁇ - olefin copolymers, polyethylene, and ethylene/C 3 -C 20 ⁇ - olefin copolymers, the inte ⁇ olymers can be either heterogeneous ethylene/ ⁇ -olefm inte ⁇ olymers , preferably a heterogenous ethylene/ C 3 -C 8 ⁇ -olefin inte ⁇ olymer, most preferably a heterogenous ethylene/ octene-1 inte ⁇ olymer or homo
  • the films or sheets or extruded profiles according to the present invention may be successfully employed for packaging in general and for packaging small items in particular.
  • Other potential applications include, but are not limited to, meat over-wrap, paper replacement, stand-up or flat bottomed bags, table cloths and shower curtains, collapsible bottles or containers, tubes such as toothpaste tubes, fold-down structures, boxes, cartons, window boxes, surgical drapes, formable membranes, toys, tubing and clothing, tapes, laminating films, pressure sensitive labels
  • the molecular weight of the polymer compositions for use in the present invention is conveniently indicated using a melt index measurement according to ASTM D-1238, Condition 190°C/2.16 kg (formally known as "Condition (E)” and also known as 12) was determined. Melt index is inversely proportional to the molecular weight of the polymer. Thus, the higher the molecular weight, the lower the melt index, although the relationship is not linear.
  • Also useful for indicating the molecular weight of the substantially random inte ⁇ olymers used in the present invention is the Gottfert melt index (G, cm 3 / 10 min) which is obtained in a similar fashion as for melt index (I 2 ) using the ASTM D1238 procedure for automated plastometers, with the melt density set to 0.7632, the melt density of polyethylene at 190°C.
  • melt density to styrene content for ethylene-styrene inte ⁇ olymers was measured, as a function of total styrene content, at 190°C for a range of 29.8 percent to 81.8 percent by weight styrene. Atactic polystyrene levels in these samples was typically 10 percent or less. The influence of the atactic polystyrene was assumed to be minimal because of the low levels. Also, the melt density of atactic polystyrene and the melt densities of the samples with high total styrene are very similar.
  • the method used to determine the melt density employed a Gottfert melt index machine with a melt density parameter set to 0.7632, and the collection of melt strands as a function of time while the I2 weight was in force. The weight and time for each melt strand was recorded and normalized to yield the mass in grams per 10 minutes. The instrument's calculated I2 melt index value was also recorded. The equation used to calculate the actual melt density is
  • S weight percentage of styrene in the polymer.
  • S weight percentage of styrene in the polymer.
  • the relationship of total styrene to melt density can be used to determine an actual melt index value, using these equations if the styrene content is known.
  • the density of the substantially random inte ⁇ olymers used in the present invention was determined in accordance with ASTM D-792.
  • Inte ⁇ olymer styrene content and atactic polystyrene concentration were determined using proton nuclear magnetic resonance ( ⁇ N.M.R). All proton NMR samples were prepared in 1, 1, 2, 2-tetrachloroethane-d 2 (TCE-d 2 ). The resulting solutions were 1.6 - 3.2 percent polymer by weight. Melt index (I 2 ) was used as a guide for determining sample concentration. Thus when the I 2 was greater than 2 g/10 min, 40 mg of inte ⁇ olymer was used; with an I 2 between 1.5 and 2 g/10 min, 30 mg of inte ⁇ olymer was used; and when the I 2 was less than 1.5 g/10 min, 20 mg of inte ⁇ olymer was used.
  • the inte ⁇ olymers were weighed directly into 5 mm sample tubes. A 0.75 mL aliquot of TCE-d 2 was added by syringe and the tube was capped with a tight-fitting polyethylene cap. The samples were heated in a water bath at 85°C to soften the inte ⁇ olymer. To provide mixing, the capped samples were occasionally brought to reflux using a heat gun.
  • Proton NMR spectra were accumulated on a Varian VXR 300 with the sample probe at 80°C, and referenced to the residual protons of TCE-d 2 at 5.99 ppm. The delay times were varied between 1 second, and data was collected in triplicate on each sample. The following instrumental conditions were used for analysis of the inte ⁇ olymer samples:
  • VXR-300 standard ⁇ : Sweep Width, 5000 Hz Acquisition Time, 3.002 sec
  • Pulse Width 8 ⁇ sec Frequency, 300 MHz Delay, 1 sec Transients, 16
  • the total analysis time per sample was 10 minutes.
  • Integrals were measured around the protons labeled in Figure 1 ; the 'A' designates aPS. Integral A 7 , (aromatic, around 7.1 ppm) is believed to be the three ortho/para protons; and integral A 66 (aromatic, around 6.6 ppm) the two meta protons.
  • the two aliphatic protons labeled ⁇ resonate at 1.5 ppm; and the single proton labeled b is at 1.9 ppm.
  • the aliphatic region was integrated from 0.8 to 2.5 ppm and is referred to as A al .
  • the theoretical ratio for A 7 , : A 66 : A al is 3 : 2: 3, or 1.5 : 1 : 1.5, and correlated very well with the observed ratios for the StyronTM 680 sample for several delay times of 1 second.
  • the ratio calculations used to check the integration and verify peak assignments were performed by dividing the appropriate integral by the integral A 66 Ratio A r is A 7 , / A 66 .
  • Region A 6 _ was assigned the value of 1.
  • Ratio Al is integral A al / A 66 . All spectra collected have the expected 1.5: 1: 1.5 integration ratio of (o+p): m: ( ⁇ +b). The ratio of aromatic to aliphatic protons is 5 to 3. An aliphatic ratio of 2 to 1 is predicted based on the protons labeled ⁇ and b respectively in Figure 1. This ratio was also observed when the two aliphatic peaks were integrated separately.
  • the ⁇ NMR spectra using a delay time of one second had integrals C 7 ,, C 66 , and C aI defined, such that the integration of the peak at 7.1 ppm included all the aromatic protons of the copolymer as well as the o & p protons of aPS.
  • integration of the aliphatic region C al in the spectrum of the inte ⁇ olymers included aliphatic protons from both the aPS and the inte ⁇ olymer with no clear baseline resolved signal from either polymer.
  • s c and e c are styrene and ethylene proton fractions in the inte ⁇ olymer, respectively, and S c and E are mole fractions of styrene monomer and ethylene monomer in the inte ⁇ olymer, respectively.
  • ESI #'s 1 - 7 are substantially random ethylene/styrene inte ⁇ olymers prepared using the following catalyst and polymerization procedures.
  • Indan (94.00 g, 0.7954 moles) and 3-chloropropionyl chloride (100.99 g, 0.7954 moles) were stirred in CH 2 C1 2 (300 mL) at 0°C as A1C1 3 (130.00 g, 0.9750 moles) was added slowly under a nitrogen flow. The mixture was then allowed to stir at room temperature for 2 hours. The volatiles were then removed. The mixture was then cooled to 0°C and concentrated H 2 S0 4 (500 mL) slowly added. The forming solid had to be frequently broken up with a spatula as stirring was lost early in this step. The mixture was then left under nitrogen overnight at room temperature. The mixture was then heated until the temperature readings reached 90°C.
  • N-(l,l-Dimethylethyl)-l,l-dimethyl-l-(l,5,6,7-tetrahydro-3-phenyl-s-indacen- l-yl)silanamine (10.6551 g, 0.02947 moles) was stirred in hexane (100 mL) as nBuLi (0.070 moles, 35.00 mL of 2.0 M solution in cyclohexane) was added slowly. This mixture was then allowed to stir overnight during which time no salts crashed out of the dark red solution. After the reaction period the volatiles were removed and the residue quickly washed with hexane (2 x 50 mL). The dark red residue was then pumped dry and used without further purification or analysis (9.6517 g, 87.7 percent yield).
  • the residue was slurried in 60 ml of mixed hexanes at 20 °C for approximately 16 hours. The mixture was cooled to -25 °C for 1 h. The solids were collected on a glass frit by vacuum filtration and dried under reduced pressure. The dried solid was placed in a glass fiber thimble and solid extracted continuously with hexanes using a soxhlet extractor. After 6 h a crystalline solid was observed in the boiling pot. The mixture was cooled to -20 °C, isolated by filtration from the cold mixture and dried under reduced pressure to give 1.62 g of a dark crystalline solid. The filtrate was discarded. The solids in the extractor were stirred and the extraction continued with an additional quantity of mixed hexanes to • give an additional 0.46 gm of the desired product as a dark crystalline solid.
  • ARMEEN ® M2HT bis(hydrogenated-tallowalkyl)methylamine
  • the flask was equipped with a 6" Vigreux column topped with a distillation apparatus and the mixture was heated (140 °C external wall temperature). A mixture of ether and methylcyclohexane was distilled from the flask. The two-phase solution was now only slightly hazy. The mixture was allowed to cool to room temperature, and the contents were placed in a 4 L separatory funnel. The aqueous layer was removed and discarded, and the organic layer was washed twice with H 2 0 and the aqueous layers again discarded. The H 2 0 saturated methylcyclohexane solutions were measured to contain 0.48 weight percent diethyl ether (Et 2 0).
  • the solution (600 mL) was transferred into a 1 L flask, sparged thoroughly with nitrogen, and transferred into the drybox.
  • the solution was passed through a column (1" diameter, 6" height) containing 13X molecular sieves. This reduced the level of Et 2 0 from 0.48 weight percent to 0.28 weight percent.
  • the material was then stirred over fresh 13X sieves (20 g) for four hours.
  • the Et 2 0 level was then measured to be 0.19 weight percent.
  • the mixture was then stirred overnight, resulting in a further reduction in Et 2 0 level to approximately 40 ppm.
  • ESI #'s 1 - 7 were prepared in a 6 gallon (22.7 L), oil jacketed, Autoclave continuously stirred tank reactor (CSTR).
  • CSTR Autoclave continuously stirred tank reactor
  • a magnetically coupled agitator with Lightning A-320 impellers provided the mixing.
  • the reactor ran liquid full at 475 psig (3,275 kPa).
  • Process flow was in at the bottom and out of the top.
  • a heat transfer oil was circulated through the jacket of the reactor to remove some of the heat of reaction.
  • At the exit of the reactor was a micromotion flow meter that measured flow and solution density. All lines on the exit of the reactor were traced with 50 psi (344.7 kPa) steam and insulated.
  • Toluene solvent was supplied to the reactor at 30 psig (207 kPa).
  • the feed to the reactor was measured by a Micro-Motion mass flow meter.
  • a variable speed diaphragm pump controlled the feed rate.
  • a side stream was taken to provide flush flows for the catalyst injection line (1 lb/hr (0.45 kg/hr)) and the reactor agitator (0.75 lb/hr ( 0.34 kg/ hr)). These flows were measured by differential pressure flow meters and controlled by manual adjustment of micro- flow needle valves.
  • Uninhibited styrene monomer was supplied to the reactor at 30 psig (207 kpa).
  • the feed to the reactor was measured by a Micro-Motion mass flow meter.
  • a variable speed diaphragm pump controlled the feed rate.
  • the styrene stream was mixed with the remaining solvent stream.
  • Ethylene was supplied to the reactor at 600 psig (4,137 kPa).
  • the ethylene stream was measured by a Micro-Motion mass flow meter just prior to the Research valve controlling flow.
  • a Brooks flow meter/controller was used to deliver hydrogen into the ethylene stream at the outlet of the ethylene control valve.
  • the ethylene/hydrogen mixture combines with the solvent/styrene stream at ambient temperature.
  • the temperature of the solvent/monomer as it enters the reactor was dropped to ⁇ 5 °C by an exchanger with - 5°C glycol on the jacket. This stream entered the bottom of the reactor.
  • the three component catalyst system and its solvent flush also entered the reactor at the bottom but through a different port than the monomer stream.
  • Preparation of the catalyst components took place in an inert atmosphere glove box.
  • the diluted components were put in nitrogen padded cylinders and charged to the catalyst run tanks in the process area. From these run tanks the catalyst was pressured up with piston pumps and the flow was measured with Micro-Motion mass flow meters. These streams combine with each other and the catalyst flush solvent just prior to entry through a single injection line into the reactor.
  • the stream was condensed with a glycol jacketed exchanger and entered the suction of a vacuum pump and was discharged to a glycol jacket solvent and styrene/ethylene separation vessel. Solvent and styrene were removed from the bottom of the vessel and ethylene from the top.
  • the ethylene stream was measured with a Micro-Motion mass flow meter and analyzed for composition. The measurement of vented ethylene plus a calculation of the dissolved gasses in the solvent/styrene stream were used to calculate the ethylene conversion.
  • the polymer separated in the devolatilizer was pumped out with a gear pump to a ZSK-30 devolatilizing vacuum extruder. The dry polymer exits the extruder as a single strand. This strand was cooled as it was pulled through a water bath. The excess water was blown from the strand with air and the strand was chopped into pellets with a strand chopper.
  • Catalyst A is d ⁇ methyl[N-(l l-d ⁇ methylethyl)-l,l-d ⁇ methyl-l-[(l,2,3,4,5- ⁇ )-l,5,6,7-tetrahydro-3-phenyl-s-mdacen-l- yl]s ⁇ lanammato(2-)-N]- titanium
  • Catalyst B is ,(lH-cyclopenta[l]phenanthrene-2-yl)d ⁇ methyl(t-butylam ⁇ do)-s ⁇ lanet ⁇ tan ⁇ um 1,4-d ⁇ phenylbutad ⁇ ene)
  • Catalyst C is (t-butylam ⁇ do)d ⁇ methyl(tetramethylcyclopentad ⁇ enyI)s ⁇ lane-t ⁇ tan ⁇ um (II) 1,3-pentadiene prepared as described in U S Patent * 5,556,928, Example 17 d Cocatalyst
  • Example 3 A sample ESI 3 containing 43.6 mol percent styrene (74.6 weight percent) and having a Gottfert melt index (G#) of 1.3 cm7l 0 min was fabricated into film and tested as for Example 1. The results are summarized in Table 4 and demonstrate the desired percent force relaxation of greater than 40 percent in the MD or CD or both.
  • G# Gottfert melt index
  • percent force relaxation is defined as: (average of five measurements is reported below)
  • the material In order to exhibit dead-fold behavior the material should have a percent force relaxation of greater than or equal to 40 percent the machine cross directions.
  • Examples 2 and 3 both show excellent dead-fold properties with high percent force relaxation in both the CD and MD due to their high styrene content.
  • Example 1 also show good dead-fold properties with acceptable percent force relaxation in both the CD and MD.
  • Comparative Examples 1 2, 3 and 4 all show poor dead-fold properties with low percent force relaxation in both the CD and MD due to their low styrene contents.

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

Abstract

L'invention concerne un film ou une feuille ou un profil extrudé possédant au moins une couche comprenant: (A) au moins un interpolymère sensiblement aléatoire qui comprend : (1) des motifs polymères dérivés de: (I) au moins un monomère vinylique aromatique, ou (ii) au moins un monomère vinylique ou vinylidénique aliphatique ou cycloaliphatique, ou (iii) une combinaison d'au moins un monomère vinylique aromatique et d'au moins un monomère vinylique ou vinylidénique aliphatique ou cycloaliphatique, et (2) des motifs polymères dérivés d'au moins une α-oléfine C2-20; et éventuellement (3) des motifs polymères dérivés d'un ou plusieurs monomères polymérisables insaturés en éthylène, autres que ceux de (1) et (2); ou (B) un mélange du Composant A et d'au moins un polymère autre que celui du composant A. Ledit film, ladite feuille ou ledit profilé possèdent une recouvrance dans le sens transversal ou dans le sens machine ou les deux, supérieure ou égale à 40 pour cent. L'invention porte aussi sur un film ou une feuille multicouche ou un profilé extrudé comprenant au moins deux couches et possédant une recouvrance dans le sens transversal, dans le sens machine ou les deux supérieure ou égale à 40 pour cent, comprenant: (A) au moins un interpolymère sensiblement aléatoire qui comprend (1) des motifs polymères dérivés de (i) au moins un monomère aromatique vinylique, ou (ii) au moins un monomère vinylique ou vinylidénique aliphatique ou cycloaliphatique, ou une combinaison d'au moins un monomère vinylique aromatique et au moins un monomère vinylique ou vinylidénique aliphatique ou cycloaliphatique, et (2) des motifs polymères dérivés d'au moins une α-oléfine C2-20; et (3) des motifs polymères dérivés d'un ou plusieurs monomères polymérisables insaturés en éthylène autres que ceux de (1) et (2); ou (B) un mélange du composant A avec au moins un polymère autre que celui du Composant A.
PCT/US1999/011429 1998-06-11 1999-05-24 Films conservant la forme qui leur est donnee, fabriques a partir d'interpolymeres aromatiques alpha-olefiniques/vinyliques et/ou vinyliques ou vinylideniques aliphatiques ou cycloaliphatiques WO1999064500A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2000553501A JP2002517583A (ja) 1998-06-11 1999-05-24 アルファオレフィン/ビニル芳香族及び/又は脂肪族又は脂環式ビニル又はビニリデンインターポリマーから作られた永久折り目特性を有するフィルム
EP99925780A EP1086167A1 (fr) 1998-06-11 1999-05-24 Films conservant la forme qui leur est donnee, fabriques a partir d'interpolymeres aromatiques alpha-olefiniques/vinyliques et/ou vinyliques ou vinylideniques aliphatiques ou cycloaliphatiques
AU41998/99A AU4199899A (en) 1998-06-11 1999-05-24 Films having dead-fold properties made from alpha-olefin/vinyl aromatic and/or aliphatic or cycloaliphatic vinyl or vinylidene interpolymers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US8890498P 1998-06-11 1998-06-11
US60/088,904 1998-06-11

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000059723A1 (fr) * 1999-04-01 2000-10-12 The Dow Chemical Company Structures multicouche
JP2002146048A (ja) * 2000-11-07 2002-05-22 Idemitsu Petrochem Co Ltd ポリオレフィン系装飾シート
US12129088B2 (en) 2019-08-23 2024-10-29 Sonoco Development, Inc. Polymeric wrapper

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995005418A1 (fr) * 1993-08-17 1995-02-23 The Dow Chemical Company Materiaux elastiques et articles fabriques a partir de ceux-ci
WO1995033006A1 (fr) * 1994-06-01 1995-12-07 The Dow Chemical Company Compositions pour melanges thermoelastiques
US5739200A (en) * 1996-12-17 1998-04-14 The Dow Chemical Company Plasticizied α-olefin/vinylidene aromatic monomer of hindered aliphatic or cycloaliphatic vinylidene monomer interpolymers
WO1998016582A1 (fr) * 1996-10-15 1998-04-23 The Dow Chemical Company Melanges d'un copolymere sequence elastomere, d'un monomere aromatique alpha-olefino/nonovinylidene et/ou d'un interpolymere monomere vinylidene aliphatique inhibe
WO1999019398A1 (fr) * 1997-10-15 1999-04-22 The Dow Chemical Company COMPOSITIONS THERMOPLASTIQUES D'INTERPOLYMERES DE MONOMERES D'α-OLEFINES AVEC UN OU PLUSIEURS MONOMERES VINYLIQUES OU VINYLIDENE AROMATIQUES ET/OU UN OU PLUSIEURS MONOMERES VINYLIQUES OU VINYLYDENE ALIPHATIQUES OU CYCLOALIPHATIQUES ENTRAVES MELANGES A DES HOMOPOLYMERES ET DES COPOLYMERES D'HALOGENURE DE VINYLE
WO1999031176A1 (fr) * 1997-12-16 1999-06-24 The Dow Chemical Company Joints realises en matieres a base d'alpha-olefine/vinylidene aromatique et/ou vinylidene aliphatique empeche/interpolymere et systemes d'etancheite y relatifs

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995005418A1 (fr) * 1993-08-17 1995-02-23 The Dow Chemical Company Materiaux elastiques et articles fabriques a partir de ceux-ci
WO1995033006A1 (fr) * 1994-06-01 1995-12-07 The Dow Chemical Company Compositions pour melanges thermoelastiques
WO1998016582A1 (fr) * 1996-10-15 1998-04-23 The Dow Chemical Company Melanges d'un copolymere sequence elastomere, d'un monomere aromatique alpha-olefino/nonovinylidene et/ou d'un interpolymere monomere vinylidene aliphatique inhibe
US5739200A (en) * 1996-12-17 1998-04-14 The Dow Chemical Company Plasticizied α-olefin/vinylidene aromatic monomer of hindered aliphatic or cycloaliphatic vinylidene monomer interpolymers
WO1999019398A1 (fr) * 1997-10-15 1999-04-22 The Dow Chemical Company COMPOSITIONS THERMOPLASTIQUES D'INTERPOLYMERES DE MONOMERES D'α-OLEFINES AVEC UN OU PLUSIEURS MONOMERES VINYLIQUES OU VINYLIDENE AROMATIQUES ET/OU UN OU PLUSIEURS MONOMERES VINYLIQUES OU VINYLYDENE ALIPHATIQUES OU CYCLOALIPHATIQUES ENTRAVES MELANGES A DES HOMOPOLYMERES ET DES COPOLYMERES D'HALOGENURE DE VINYLE
WO1999031176A1 (fr) * 1997-12-16 1999-06-24 The Dow Chemical Company Joints realises en matieres a base d'alpha-olefine/vinylidene aromatique et/ou vinylidene aliphatique empeche/interpolymere et systemes d'etancheite y relatifs

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000059723A1 (fr) * 1999-04-01 2000-10-12 The Dow Chemical Company Structures multicouche
JP2002146048A (ja) * 2000-11-07 2002-05-22 Idemitsu Petrochem Co Ltd ポリオレフィン系装飾シート
US12129088B2 (en) 2019-08-23 2024-10-29 Sonoco Development, Inc. Polymeric wrapper

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JP2002517583A (ja) 2002-06-18
AR019648A1 (es) 2002-02-27
AU4199899A (en) 1999-12-30

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