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WO2000061679A1 - Film a orientation biaxiale, prepare a partir de polypropylene catalyse aux metallocenes - Google Patents

Film a orientation biaxiale, prepare a partir de polypropylene catalyse aux metallocenes Download PDF

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Publication number
WO2000061679A1
WO2000061679A1 PCT/US1999/008000 US9908000W WO0061679A1 WO 2000061679 A1 WO2000061679 A1 WO 2000061679A1 US 9908000 W US9908000 W US 9908000W WO 0061679 A1 WO0061679 A1 WO 0061679A1
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WO
WIPO (PCT)
Prior art keywords
polypropylene
film
molecular weight
films
low molecular
Prior art date
Application number
PCT/US1999/008000
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English (en)
Inventor
Mark T. Demeuse
Original Assignee
Applied Extrusion Technologies, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Applied Extrusion Technologies, Inc. filed Critical Applied Extrusion Technologies, Inc.
Priority to PCT/US1999/008000 priority Critical patent/WO2000061679A1/fr
Priority to AU37451/99A priority patent/AU3745199A/en
Publication of WO2000061679A1 publication Critical patent/WO2000061679A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered 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
    • B32B27/08—Layered 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/41—Opaque
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B32B2323/10—Polypropylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C08L57/02—Copolymers of mineral oil hydrocarbons

Definitions

  • This invention relates to improved polypropylene films and the manufacture thereof. More specifically, it relates to polypropylene films prepared from a new and improved polypropylene, which films exhibit improved properties as compared with polypropylene films heretofore known in the art.
  • Isotactic polypropylene is a well known article of commerce prepared by the polymerization of propylene in the presence of a catalyst comprised of an alkyl aluminum chloride and titanium tetrachloride. Such polypropylene is well suited to the preparation of packaging films and a large industry has grown up about polypropylene packaging films.
  • Metallocene catalysts are defined as bridged bisdicyclopentadienyl or bisindenyl Group 4,5 or 6 transition metal dihalide derivatives. Specific metallocene catalysts known to be useful for producing polypropylene are discussed, inter alia, in EPA 485,820; 485,821 ; 485,822; 485,823; 518,092 and 519,237 and in US 5,145,819 and 5,296,434. Other references that discuss the metallocene catalyzed process include EPA 351 ,932 and U.S. Patents 5,055,438; 5,234,800; 5,272,016; 5,272,236 and 5,278,272. All of the cited documents are incorporated hereinto by reference.
  • the polymers resulting from metallocene catalysis are said to be of extremely uniform steric structure.
  • the polymer can be of an isotactic structure wherein the pendant methyl groups on the polymer chain are located on alternating carbon atoms and are alternately oriented above and below the plane of the chain.
  • the polymer can be of syndiotactic structure wherein all of the pendant methyl groups are still located on alternate carbon atoms, but they are disposed predominantly on the same side of the chain.
  • the metallocene catalyst leads to a more even distribution of the comonomer or comonomers throughout the product.
  • Yet another good feature of the metallocene polymers is that they have a lower concentration of low molecular weight, xylene soluble materials.
  • the narrower molecular weight distribution and the more even distribution of the comonomer leads to greater uniformity of the properties of the product.
  • the metallocene catalyzed products exhibit a sharper melting point and a more uniform intrinsic viscosity throughout the product.
  • the cast films exhibit very poor properties in terms of their optical qualities. Specifically, the films cast preparatory to drawing to effect orientation are extremely hazy, bordering on being translucent. In addition, they have a rough, sand paper-like surface.
  • films prepared with a metallocene catalyzed polypropylene containing up to about 15% by weight of a low molecular weight hydrocarbon resin have excellent optical properties. That is to say, the high level of haze and the rough surface previously noted in the cast films are substantially completely absent in cast films prepared with the composition of metallocene catalyzed polypropylene and low molecular weight hydrocarbon resin according to this invention. Moreover, the optical properties of the film following biaxial orientation are improved as compared to those of unmodified isotactic polypropylene prepared via metallocene catalysis.
  • the improvement of the optical properties of both the cast film and the drawn film is a totally unexpected and surprising effect of the polymer compositions of this invention.
  • the addition of another polymeric or resinous type material in any significant amount is usually detrimental to the optical properties of the polypropylene. This effect is less noticeable with the low molecular weight hydrocarbon resins than with most other polymeric additives. Nonetheless, it was very surprising to discover that these properties can be improved by adding the hydrocarbon resins.
  • the optical properties of the metallocene polymers containing low molecular weight hydrocarbon resin are comparable to those of conventional isotactic polypropylene containing no low molecular weight hydrocarbon resin.
  • the invention defined in this application is a composition useful for preparing oriented films, said composition comprising metallocene catalyzed polypropylene and a low molecular weight hydrocarbon resin, said resin being present in an amount up to about 15% by weight based on the total weight of the polypropylene and the resin.
  • the low molecular weight hydrocarbon resin is present in an amount up to about 10%.
  • the low molecular weight hydrocarbon resin is present in an amount of about 1 to 5%.
  • the invention is an oriented polypropylene film comprised of metallocene catalyzed polypropylene and a low molecular weight hydrocarbon resin, said resin being present in an amount up to about 15% by weight based on the total weight of the polypropylene and the resin.
  • the low molecular weight hydrocarbon resin is present in an amount up to about 10%. In a most preferred embodiment, the low molecular weight hydrocarbon resin is present in an amount of about 1 to 5%.
  • Films according to the invention can be either uniaxially or biaxially oriented. Preferably, the films will be biaxially oriented. Moreover, the films can be monolayer or multilayer (composite) structures.
  • the metallocene catalyzed polypropylene employed in the manufacture of the films of this invention can be either an isotactic or a syndiotactic polymer.
  • the preferred polymer is the isotactic species because this species has a higher melting point and accordingly, can be employed in higher temperature environments than can the syndiotactic species.
  • a preferred metallocene catalyzed isotactic polypropylene is one having a melt flow rate between about 1 and 10 and more preferably, between about 1 and 5 dg/minute at 230°C under a loading of 2.16 kg.
  • the low molecular weight hydrocarbon resins employed in the compositions and films of this invention are hydrogenated or unhydrogenated resins derived from olef in monomers, such as the resins derived from terpene monomers, coal tar fractions and petroleum feedstocks.
  • Suitable resins include those prepared from terpene monomers (e.g., limonene, alpha and beta pinene, such as Piccolyte resins from Hercules Incorporated, Wilmington, DE, and Zonatac resins from Arizona Chemical Company, Panama City, FL.).
  • low molecular weight resins are prepared from hydrocarbon monomers and mixtures thereof, such as C 5 monomers (e.g., piperylene, cyclopentene, cyclopentadiene, and isoprene), oligomerized C 5 monomers, particularly the thermally oligomerized C 5 monomers such as the hydrogenated thermally oligomerized cyclopentadiene resins sold under the trade name Escorez (for example Escorez 5300) by Exxon Chemical Co. of Baytown, TX.
  • C 5 monomers e.g., piperylene, cyclopentene, cyclopentadiene, and isoprene
  • oligomerized C 5 monomers particularly the thermally oligomerized C 5 monomers
  • the hydrogenated thermally oligomerized cyclopentadiene resins sold under the trade name Escorez (for example Escorez 5300) by Exxon Chemical Co. of Baytown, TX.
  • C 9 monomers particularly the monomers derived from C 9 petroleum fractions which are mixtures of aromatics, including styrene, methyl styrene, alpha methyl styrene, vinyl naphthalene, the indenes and methyl indenes and, additionally, pure aromatic monomers, including styrene, ⁇ -methyl-styrene and vinyltoluene.
  • these resins include hydrogenated ⁇ -methyl styrene-vinyl toluene resins sold under the trade name Regalrez by Hercules Incorporated of Wilmington, DE.
  • the hydrogenated C 9 and pure monomer resins are preferred. Particularly preferred are the hydrogenated cyclopentadiene resins and the hydrogenated aromatic resins derived from pure aromatic monomers, e.g., the hydrogenated ⁇ -methyl styrene— vinyltoluene copolymers.
  • the low molecular weight resins useful in this invention are characterized by a molecular weight less than about 5000, a T g of about 50 to 100 ° C and a softening point less than about 140 ° C.
  • the films of the invention can exist as stand-alone films of the blend of the metallocene catalyzed polypropylene-low molecular weight resin composition. These can be mono- layer structures or they can be composite (multilayer) structures wherein the inventive film serves as a core having one or more functional layers on at least one of its surfaces. Most commercial polypropylene films are of the composite structure type and that is the preferred structure for the films of the invention.
  • the invention also contemplates an oriented composite film comprised of a polypropylene core layer having, on one or both of its surfaces, a film comprised of the polypropylene-low molecular weight hydrocarbon resin composition as described hereinabove.
  • the film is an oriented composite film comprised of a polypropylene core having on one of its surfaces a thin layer of the metallocene polypropylene-low molecular weight resin composition and, on the other surface, a different functional layer.
  • a film depending on the context in which it is used, can refer to either a stand alone, self-supporting film or to a thin film employed as a functional layer on a self-supporting core.
  • the thickness of the film following orientation is typically in the range of about 0.25 to 1.0 mil (25 to 100 gauge).
  • a preferred film thickness is from about 0.5 to about 0.8 mil (50 to 80 gauge).
  • the thickness of the core layer is preferably about 0.23 to 0.9 mil (23 to 90 gauge), while that of the individual functional surface layers is about 0.1 to 0.15 mil (10 to 15 gauge).
  • the thickness of that film is about 0.1 to 0.15 mil (10 to 15 gauge).
  • the core in the case of composite films, can be clear or it can be opaque.
  • the core layer of the film can be rendered opaque by incorporating a particulate organic or inorganic opacifier into the polymer composition.
  • Certain opacifiers impart opacity by causing microvoiding of the polymer matrix about the opacifier particles during the orientation drawing operation. Examples of such opacifiers include calcium carbonate, silicon dioxide, aluminum silicate and magnesium silicate.
  • Other materials such as certain coloring pigments can cause opacity without voiding if present in sufficiently high loading.
  • An example of such a coloring pigment is titanium dioxide.
  • an opaque film is usually on the order of about 1 to 1.5 mil in thickness and preferably on the order of about 1 to 1.3 mil with the functional layers being of the same thickness as those on a clear film.
  • Composite films prepared making use of the metallocene polypropylene-low molecular weight hydrocarbon resin composition of this invention as a surface layer on a polypropylene core can have the said composition on either one or both surfaces of the core layer. If the composition is present on only one of the surfaces, the other surface can have a layer of a different material thereon.
  • a surface layer can be included on either one or both of its surfaces.
  • the composition of the functional layers is dictated by the purpose that these layers are intended to serve.
  • these layers may or may not be of the same composition as the core.
  • the functional layers need not even contain polypropylene.
  • composite films frequently carry a heat seal layer.
  • Such layers comprise material of lower melting point than the core so that when heat is applied to effect the seal, the orientation of the core layer will not be disturbed.
  • a commonly used heat seal layer is comprised of a terpolymer of propylene, ethylene and butene-1.
  • Other polymers that can be employed include polyvinyl or polyvinylidene chloride.
  • a cold seal layer Another frequently used functional layer is a cold seal layer.
  • the polymer component will frequently be the same as that of the core layer, though, here again, it need not be the same.
  • a cold seal adhesive such as, e.g., a rubber adhesive is applied to the surface of the polymer layer.
  • a slip layer to facilitate handling of the film during later converting operations.
  • Such a layer is comprised of a polypropylene containing a slip agent such as a high molecular weight fatty acid amide.
  • a functional layer may also contain an antiblock additive to facilitate unwinding of the film after it has been wound at the terminus of the film manufacturing process
  • the polypropylene content of such layers likewise may or may not comprise metallocene catalyzed polypropylene according to the invention.
  • Films according to the invention are found to have improved properties in several respects as compared to films prepared with the presently known isotactic polypropylenes.
  • the films according to the invention have a higher tensile modulus than do either the conventionally known isotactic polypropylene films or films of the metallocene polypropylene containing no low molecular resin.
  • a biaxially oriented film of conventional polypropylene drawn 6X in the bubble process at 140°C will typically have a tensile modulus on the order of about 300,000 psi
  • a metallocene polymer containing a low molecular weight hydrocarbon resin according to the invention drawn under similar conditions, typically has a tensile modulus about 25% higher. This greater stiffness is significant as it allows one to prepare a thinner film of the same modulus when preparing films with the compositions of the invention. Likewise, it allows one to prepare a stiffer film at the same thickness.
  • MVTR moisture vapor transmission rate
  • the good optical properties i.e., gloss, haze and clarity, to which reference has been made hereinabove, are significant film quality parameters and are essential to commercial acceptance of the film.
  • the good clarity and haze are less significant, but the good gloss values are essential to the commercial acceptance of the film.
  • Films according to the invention can be prepared by extruding the composition of the invention at a temperature of about 230 to 250° C, quenching the extrudate to form a cast film, then reheating the cast film to about 130 to 150°C, drawing the said cast film to a draw of about 6 to 10X in both the machine and the cross direction and recovering a biaxially oriented film.
  • the energy required to draw the films is reduced as compared with that required to drawfilms of straight metallocene polypropylene.
  • the reduction of the energy required is indicated by the stress required to accomplish the drawing. This reduction of the stress is shown in the following table wherein stress to draw at several combinations of draw temperature and low molecular weight hydrocarbon resin level is shown.
  • the low molecular weight hydrocarbon resin employed was Hercules Regalrez 1128, a hydrogenated copolymer of vinyl toluene and ⁇ -methyl styrene (Hercules Incorporated, Wilmington, DE)..
  • Films according to the invention can be prepared by methods conventionally employed in the film making art. With specific reference to the multilayer films of the invention, there can be employed coextrusion, extrusion coating or lamination. The preferred method is coextrusion wherein the various layers are extruded simultaneously through a multi-layer die and immediately brought together in the molten state so that they are permanently bonded upon solidifying.
  • the films can be monoaxially or biaxially drawn to effect molecular orientation thereof and improve their properties, specifically, their tensile strength and tensile modulus (stiffness). Most commercially desirable films are biaxially oriented and that is preferred for the films of the invention. Film forming and drawing to effect orientation can be carried out by conventional techniques, i.e. the well known tubular (bubble) process or the equally well known tenter process can be employed.
  • the draw is effected simultaneously and uniformly in the machine and cross directions to about 6X.
  • drawing is carried out sequentially to about 5X in the machine direction and to about 10X in the cross direction.
  • Conventional additives in conventional amounts, can be included in the compositions of the invention and in the various layers of the composite films, provided that no additive should be included that can negatively affect the performance of the layer into which it is incorporated or that can migrate into another layer and negatively affect the performance of that layer in carrying out its intended function.
  • Suitable conventional additives include antioxidants, pigments, orientation stress modifiers, flame retardants, antistatic agents, antiblocking agents, antifoggants and slip agents.
  • the films of the invention are useful in any of the applications in which conventional isotactic polypropylene is presently employed. They are particularly useful as packaging films, either as shrinkable films or as barrier or printable films after suitable treatment to render the surface polar so that a polar coating material will adhere thereto. They can also be used as the dielectric component in electrical condensers and as label stock due to their greater stiffness as compared to conventional polypropylene. Other suitable applications will be apparent to the practitioner.
  • films were prepared by initially melt extruding the metallocene polypropylene-low molecular weight hydrocarbon resin composition through a Killion single screw extruder (Killion Extruders, Inc., Verona, N.J.) at about 240°C onto a casting roll maintained at about 55°C for quenching. Extrusion was carried out at about 3.3 fpm. A quenched cast film of about 23 mil thickness was recovered.
  • Killion Extruders, Inc., Verona, N.J. Killion Extruders, Inc., Verona, N.J.
  • the cast film was subjected to a 6X by 6X draw on a T.M. Long stretcher (T.M. Long Corporation, Somerville, N.J.). Drawing was effected at about 140°C.
  • EXAMPLE 1 The film of this example was prepared with a metallocene polypropylene designated EOD 96-12 (Fina Oil and Chemical Co., Deer Park, TX). This polymer had properties as follows:
  • Recrystallization Temp. 107 This polymer was blended with a hydrogenated copolymer of vinyl toluene and ⁇ -methyl styrene (Regalrez 1128 from Hercules Incorporated, Wilmington, DE) to prepare two blends. One of these blends contained 5% by weight of the resin and the other contained 10% by weight, based on the weight of the blend.
  • a control specimen containing none of the resin was also drawn 6X by 6X using the same conditions as were used for the 5% resin sample.
  • a second series of samples was prepared wherein smaller amounts of the hydrocarbon resin were added to the polymer.
  • the same polymer as was employed in Example 1 was employed in this example.
  • Example 2 Another series of films of the compositions used in Example 2 were prepared and in this example these were drawn 7X by 7X.
  • the control sample was preheated for 30 seconds at 140°C and drawn at this temperature.
  • the polypropylene/hydrocarbon blends were preheated for 35 seconds and drawn at 140°C. Property data for these sample are recorded in Table 3.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

On a constaté que des films préparés à partir de polypropylène aux métallocènes contenant une résine hydrocarbonée de faible poids moléculaire présentaient certaines propriétés améliorées comparativement aux films préparés avec des films ne renfermant pas une telle résine. En particulier, ces films présentent des propriétés optiques améliorées.
PCT/US1999/008000 1999-04-13 1999-04-13 Film a orientation biaxiale, prepare a partir de polypropylene catalyse aux metallocenes WO2000061679A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/US1999/008000 WO2000061679A1 (fr) 1999-04-13 1999-04-13 Film a orientation biaxiale, prepare a partir de polypropylene catalyse aux metallocenes
AU37451/99A AU3745199A (en) 1999-04-13 1999-04-13 Biaxially oriented film prepared from metallocent catalyzed polypropylene

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Application Number Priority Date Filing Date Title
PCT/US1999/008000 WO2000061679A1 (fr) 1999-04-13 1999-04-13 Film a orientation biaxiale, prepare a partir de polypropylene catalyse aux metallocenes

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6458470B1 (en) * 1999-07-08 2002-10-01 Exxonmobil Oil Corporation High barrier multilayer film
EP1398344A1 (fr) * 2001-05-11 2004-03-17 Toray Industries, Inc. Film en polypropylene a orientation biaxiale
WO2004090059A1 (fr) * 2003-04-11 2004-10-21 Treofan Germany Gmbh & Co. Kg Feuille de polypropylene a orientation biaxiale pourvue d'une colle de soudage a froid
WO2014195367A1 (fr) * 2013-06-04 2014-12-11 POLIFILM EXTRUSION GmbH Film multicouche muni d'une couche adhésive thermiquement activable

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0595252A1 (fr) * 1992-10-30 1994-05-04 SOTEN S.r.l. Feuille thermorétractable et son procédé de préparation
WO1996002388A1 (fr) * 1994-07-15 1996-02-01 Mobil Oil Corporation Film de polypropylene oriente constituant une barriere tres efficace contre l'humidite, contenant du polypropylene a haute cristallinite et un polymere terpenique
EP0716121A1 (fr) * 1994-12-06 1996-06-12 Mitsui Petrochemical Industries, Ltd. Composée de polypropylène et élastomère de propylène-butène
US5573717A (en) * 1994-03-26 1996-11-12 Hoechst Aktiengesellschaft Oriented polyolefin film with amorphous polymer, a process for its production and its use
EP0861877A1 (fr) * 1996-08-08 1998-09-02 New Japan Chemical Co.,Ltd. Cristal moleculaire a base de colophane, agent de nucleation destine a une resine polyolefinique, composition de resine polyolefinique et moulages de celle-ci

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0595252A1 (fr) * 1992-10-30 1994-05-04 SOTEN S.r.l. Feuille thermorétractable et son procédé de préparation
US5573717A (en) * 1994-03-26 1996-11-12 Hoechst Aktiengesellschaft Oriented polyolefin film with amorphous polymer, a process for its production and its use
WO1996002388A1 (fr) * 1994-07-15 1996-02-01 Mobil Oil Corporation Film de polypropylene oriente constituant une barriere tres efficace contre l'humidite, contenant du polypropylene a haute cristallinite et un polymere terpenique
EP0716121A1 (fr) * 1994-12-06 1996-06-12 Mitsui Petrochemical Industries, Ltd. Composée de polypropylène et élastomère de propylène-butène
EP0861877A1 (fr) * 1996-08-08 1998-09-02 New Japan Chemical Co.,Ltd. Cristal moleculaire a base de colophane, agent de nucleation destine a une resine polyolefinique, composition de resine polyolefinique et moulages de celle-ci

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6458470B1 (en) * 1999-07-08 2002-10-01 Exxonmobil Oil Corporation High barrier multilayer film
EP1398344A1 (fr) * 2001-05-11 2004-03-17 Toray Industries, Inc. Film en polypropylene a orientation biaxiale
EP1398344A4 (fr) * 2001-05-11 2009-08-19 Toray Industries Film en polypropylene a orientation biaxiale
WO2004090059A1 (fr) * 2003-04-11 2004-10-21 Treofan Germany Gmbh & Co. Kg Feuille de polypropylene a orientation biaxiale pourvue d'une colle de soudage a froid
WO2014195367A1 (fr) * 2013-06-04 2014-12-11 POLIFILM EXTRUSION GmbH Film multicouche muni d'une couche adhésive thermiquement activable

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