EP1322469A2 - Film en polyolefine a orientation biaxiale presentant une meilleure aptitude au scellage contre des vernis et revetements en acrylate et pvdc - Google Patents

Film en polyolefine a orientation biaxiale presentant une meilleure aptitude au scellage contre des vernis et revetements en acrylate et pvdc

Info

Publication number
EP1322469A2
EP1322469A2 EP01980369A EP01980369A EP1322469A2 EP 1322469 A2 EP1322469 A2 EP 1322469A2 EP 01980369 A EP01980369 A EP 01980369A EP 01980369 A EP01980369 A EP 01980369A EP 1322469 A2 EP1322469 A2 EP 1322469A2
Authority
EP
European Patent Office
Prior art keywords
film according
polyolefin film
weight
cover layer
wax
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01980369A
Other languages
German (de)
English (en)
Inventor
Susanne Holzer
Gerhard Wieners
Wilfried Tews
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Treofan Germany GmbH and Co KG
Original Assignee
Trespaphan GmbH and Co KG
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 Trespaphan GmbH and Co KG filed Critical Trespaphan GmbH and Co KG
Publication of EP1322469A2 publication Critical patent/EP1322469A2/fr
Withdrawn legal-status Critical Current

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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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/91—Product with molecular orientation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y10T428/24967—Absolute thicknesses specified
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249987—With nonvoid component of specified composition
    • Y10T428/249991—Synthetic resin or natural rubbers
    • Y10T428/249992—Linear or thermoplastic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31801—Of wax or waxy material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31913—Monoolefin polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31928—Ester, halide or nitrile of addition polymer

Definitions

  • the invention relates to a polyolefin film with improved sealability against PVDC and acrylate lacquers and coatings.
  • This tube is dimensioned such that its two ends are then hammered four to twelve times over the center of the circular end faces and are heat-sealed so as to overlap. Both the inside is sealed against the inside as well as the inside against the outside in order to achieve largely tightly sealed packaging.
  • the fin seam can be carried out in such a way that one edge projects slightly beyond the other edge of the sealed outer surface, the fin seam is folded over laterally and the overhang is sealed with the inside of the tube material against the outside thereof.
  • the packaging material from which such roll-wrap packaging is formed must be designed in such a way that both the inside can be sealed against the inside and the inside can be sealed against the outside of the film, whereby in cases in which fragile packaged goods such as cookies are to be packed, advantageously sealing takes place even at low sealing pressures.
  • numerous other forms of packaging are known in which similar requirements are made.
  • BOPP film that is printed over and on the opposite side, i.e. can be coated on both sides with a coating of PVDC or acrylic paints.
  • a coating of PVDC or acrylic paints Depending on the system, such coatings require the use of solvents, some of which are released into the environment during drying, or which have to be retained and refurbished using technical means, or a high application weight and thus a high level of material use. This involves costs for the materials used and for the provision and operation of the application systems and the corresponding auxiliary units.
  • British application GB 2 223 446 describes a BOPP film which consists of at least two layers, the comparatively thinner layer consisting of a blend of a material which has a low seal seam strength against PVDC and a material which is composed of a copolymer consists of an alkene and an unsaturated monobasic acid or its ester.
  • materials with a low seal seam strength against high and low density PVDC polyethylenes come into consideration, as copolymers those of ethylene with acrylic acid esters, wherein in particularly preferred embodiments these copolymers can contain unsaturated dibasic acids or their anhydrides such as maleic anhydride as further monomers.
  • Corresponding copolymers or terpolymers have been described in EP 0 065 898.
  • the object of the present invention was therefore to provide a biaxially oriented polyolefin film which is composed of readily available and inexpensive components and which is distinguished in that it seals on the one hand with a cover layer against coatings or lacquers based on PVDC or acrylates, on the other hand can be produced without the formation of deposits on the rollers of the longitudinal drafting system.
  • the usual properties of use and the appearance of the film should not be adversely affected.
  • a multilayer biaxially oriented polyolefin film composed of a base layer and at least one first cover layer, this first cover layer containing at least 80% by weight of a copolymer or terpolymer I and at most 20% by weight of a wax, the details being in% by weight refer to the weight of the first cover layer.
  • the copolymer or terpolymer I is composed of olefin and unsaturated carboxylic acid or their esters.
  • composition of the first cover layer according to the invention shows the desired sealing properties against itself (AA or BB seals) and against lacquers based on PVDC or acrylic (AB sealing), as are required for the roll-wrap packaging.
  • AA or BB seals AA or BB seals
  • lacquers based on PVDC or acrylic AB sealing
  • the film according to the invention can be processed very well and shows no undesired pick-off when the coated film is unrolled, i.e. the adhesion of the first covering layer to the PVDC or acrylate coating is not so great that this coating is detached from the opposite surface and adheres to the first covering layer.
  • the first covering layer contains, as constituents essential to the invention, a copolymer or terpolymer I composed of an olefin and an unsaturated carboxylic acid or its ester and a wax. If necessary, the first cover layer additionally contains antiblocking agents and / or a polyethylene. In general, the first cover layer contains at least 80% by weight, preferably 90 to 99.5% by weight, in particular 96 to 99% by weight of the copolymer or terpolymer I and at most 20% by weight, preferably 0.5 up to 10% by weight, in particular 1 to 4% by weight, of the wax.
  • the copolymer or terpolymer I is essential for the sealing of the first Top layer against PVDC and / or against acrylate lacquers and coatings.
  • Suitable copolymers or terpolymers I are composed of olefins and unsaturated carboxylic acids or their esters as monomers. Olefins are, for example, ethylene, propylene or butene-1, and possibly also higher homologs such as hexene or octene.
  • Unsaturated carboxylic acids include unsaturated mono- and dicarboxylic acids as well as their esters or anhydrides. Acrylic acid or methacrylic acid and their esters are preferred as unsaturated carboxylic acids.
  • the copolymer or terpolymer I can be composed of various olefins and various unsaturated carboxylic acids or their esters / anhydrides. Copolymers I of ethylene and acrylic acid ester are particularly advantageous.
  • Terpolymers I are generally composed of the olefins mentioned above, and an unsaturated monocarboxylic acid or its ester and an unsaturated dicarboxylic acid or its ester / anhydride.
  • Preferred unsaturated dicarboxylic acids or their anhydride are maleic acid or maleic anhydride.
  • Terpolymers of ethylene, acrylic acid or methacrylic acid or their esters and maleic anhydride are particularly advantageous.
  • esters of the unsaturated carboxylic acids described are derived from one or more lower alcohols.
  • methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl or tert-butyl esters are suitable.
  • Copolymers I generally contain at least 60% by weight, preferably 70 to 97% by weight of olefin, preferably ethylene and at most 40% by weight, preferably 3 to 30% by weight of unsaturated carboxylic acids or their esters, preferably acrylic acid or methacrylic acid or their esters.
  • Terpolymers I generally contain 65 to 96% by weight, preferably 72 to 93% by weight of olefin, preferably ethylene and 3 to 34% by weight, preferably 5 to 26% by weight of unsaturated carboxylic acids or their esters, preferably acrylic acid or methacrylic acid or their esters and 1 to 32% by weight, preferably 2 to 23% by weight, of unsaturated dicarboxylic acid or its ester / anhydride, preferably maleic anhydride.
  • the above-described copolymers or terpolymers I of the first cover layer generally have a melting point of 40 to 120 ° C., preferably 60 to 100 ° C.
  • the Vicat point is preferably in the range from 30 to 90 ° C.
  • the melt index is generally 0.1 to 20 g / 10min (190 ° C, 21.6N), preferably 0.1 to 15 g / 10min.
  • the first cover layer contains a wax, preferably polyethylene waxes or paraffins.
  • Polyethylene waxes are low molecular weight polymers that essentially consist of
  • Ethylene units are built up and are partially or highly crystalline.
  • Polymer chains from the ethylene units are elongated molecules that can be branched, with shorter side chains predominating.
  • polyethylene waxes are obtained by direct polymerization of the
  • the polyethylene waxes preferably have an average molecular weight Mn
  • the melting point is generally in the range from 70 to 150 ° C., preferably 80 to 100 ° C.
  • Paraffins include macrocrystalline paraffins (paraffin waxes) and microcrystalline paraffins (microwaxes).
  • the macrocrystalline paraffins are derived from the vacuum distillate fractions during their processing Lubricating oils won.
  • the microcrystalline paraffins come from the residues of vacuum distillation and the sediments of paraffinic crude oils (excretion paraffins).
  • the macrocrystalline paraffins mainly consist of n-paraffins, which additionally contain iso-paraffins, naphthenes and alkyl aromatics, depending on the degree of refining.
  • the microcrystalline paraffins consist of a mixture of hydrocarbons, which are predominantly solid at room temperature. Unlike macrocrystalline paraffins, iso-paraffins and naphthenic paraffins are predominant.
  • microcrystalline paraffins are characterized by the presence of crystallization-inhibiting, highly branched iso-paraffins and naphthenes. Paraffins with a melting point of 60 to 100 ° C., preferably 60 to 85 ° C., are particularly suitable for the purposes of the invention.
  • the first cover layer can additionally contain a further component which is compatible with the copolymer or terpolymer I and which itself has a low seal seam strength compared to PVDC or acrylic lacquers and coatings.
  • the proportion of such components is generally between 0 and 30% by weight, preferably 1 to 20% by weight, in particular 3 to 10% by weight, the proportion of co- or terpolymer I in the composition of the cover layer reduced accordingly.
  • Suitable components of this type are polyethylenes, polypropylenes, polystyrene, polyesters or polyamides. Polyethylenes are preferred, both linear and branched polyethylenes being suitable in principle, for example LLDPE, LDPE or HDPE.
  • the suitable polyethylenes have a much higher molecular weight compared to the polyethylene waxes.
  • the number average Mn is generally over 10,000 and is preferably 30,000 to 300,000, in particular 40,000 to 200,000.
  • the melting point of the preferred polyethylenes is generally 90-150 ° C, preferably 110-140 ° C.
  • the melt flow index is generally 1 to 50 g / 10 min, preferably 10 to 30 g / 10 min.
  • Embodiments which additionally contain polyethylenes are even more advantageous with regard to the tendency to stick in the manufacturing process and the detachment of PVDC or acrylate coating that occurs is more reliably avoided. It is surprising that the polyethylenes, which are similar in structure to the waxes, further increase the advantageous effect of the waxes, whereas a further increase in the wax content does not achieve this effect.
  • the first cover layer can additionally contain conventional additives such as neutralizing agents, stabilizers, antistatic agents, antiblocking agents and / or lubricants in effective amounts.
  • conventional additives such as neutralizing agents, stabilizers, antistatic agents, antiblocking agents and / or lubricants in effective amounts.
  • the following data in% by weight relate to the weight of the first cover layer.
  • embodiments are preferred which additionally contain antiblocking agents in the first cover layer.
  • Suitable antiblocking agents are inorganic additives such as silicon dioxide, calcium carbonate, magnesium silicate, aluminum silicate, calcium phosphate and the like and / or incompatible organic polymers such as polyamides, polyesters, polycarbonates and the like or crosslinked polymers such as crosslinked polymethyl methacrylate or crosslinked silicone oils. Silicon dioxide and calcium carbonate are preferred.
  • the average particle size is between 1 and 6 ⁇ m, in particular 2 and 5 ⁇ m.
  • the effective amount of antiblocking agent is in the range of 0.1 to 5% by weight, preferably 0.5 to 3% by weight, in particular 0.8 to 2% by weight.
  • the antiblocking agent also has a favorable effect in terms of low pickoff.
  • the surface of the first cover layer is corona, plasma or flame treated.
  • films which are equipped with the first cover layer described above have seal seam strengths compared to PVDC lacquers of over 1.5 N / 15 mm, measured at 110 ° C / 10 N / mm 2 sealing pressure / 0.5 sec sealing time. (Specify area for seal seam strength)
  • the thickness of the first cover layer is generally greater than 0.3 ⁇ m and is preferably in the range from 0.5 to 5 ⁇ m, in particular 1 to 3 ⁇ m.
  • the first cover layer described above with the composition according to the invention can advantageously be applied to transparent or opaque base layers. It has also been found that opaque embodiments of the film according to the invention, in particular those with a vacuole-containing base layer, surprisingly have particularly good sealing properties, in particular also with AB seals.
  • opaque film means an opaque film whose light transmission (ASTM-D 1003-77) is at most 70%, preferably at most 50%.
  • the base layer of the film generally contains at least 85% by weight, preferably 90 to ⁇ 100% by weight, in particular 95 to 99% by weight, in each case based on the base layer, of a polyolefin.
  • Polyolefins are, for example, polyethylenes, polypropylenes, polybutylenes or copolymers of olefins with two to eight carbon atoms, of which polyethylenes and polyproyplenes are preferred.
  • the propylene polymer contains at least 90% by weight, preferably 94 to 100% by weight, in particular 98 to ⁇ 100% by weight, of propylene.
  • the corresponding comonomer content of at most 10% by weight or 0 to 6% by weight or 0 to 2% by weight generally consists, if present, of ethylene. The percentages by weight relate to the propylene polymer.
  • Isotactic propylene homopolymers with a melting point of 140 to 170 ° C., preferably 155 to 165 ° C., and a melt flow index (measurement DIN 53 735 at 21.6 N load and 230 ° C.) of 1.0 to 10 g / 10 are preferred min, preferably from 1.5 to 6.5 g / 10 min.
  • the n-heptane-soluble fraction of the polymer is generally 1 to 10% by weight, preferably 2 to 5% by weight, based on the starting polymer.
  • the molecular weight distribution of the propylene polymer can vary.
  • the ratio of the weight average M w to the number average M n is generally between 1 and 15, preferably 2 to 10, very particularly preferably 2 to 6.
  • Such a narrow molecular weight distribution of the propylene homopolymer of the base layer can be achieved, for example, by its peroxidic degradation or by production of polypropylene using suitable metallocene catalysts.
  • the base layer is opaque by adding fillers.
  • the base layer in this embodiment contains at least 70% by weight, preferably 75 to 99% by weight, in particular 80 to 98% by weight, in each case based on the weight of the base layer of the polyolefins or propylene polymers described above, where the propylene homopolymers described are also preferred.
  • the opaque base layer contains fillers in an amount of at most 30% by weight, preferably 1 to 25% by weight, in particular 2 to 20% by weight, based on the weight of the base layer.
  • fillers are pigments and / or vacuole-initiating particles.
  • pigments are incompatible particles which essentially do not lead to the formation of vacuoles when the film is stretched.
  • the coloring effect of the pigments is due to the particles themselves caused.
  • Pigments generally have an average particle diameter of 0.01 to a maximum of 1 ⁇ m, preferably 0.01 to 0.7 ⁇ m, in particular 0.01 to 0.4 ⁇ m.
  • Pigments comprise both so-called “white pigments”, which the films know coloring, as well as “colored pigments”, which give the film a bright or black color.
  • pigments are materials such as aluminum oxide, aluminum sulfate, barium sulfate, calcium carbonate, magnesium carbonate, silicates such as aluminum silicate (kaolin clay) and magnesium silicate (talc), silicon dioxide and titanium dioxide, white pigments such as calcium carbonate, silicon dioxide, titanium dioxide and barium sulfate are preferably used.
  • the titanium dioxide particles generally consist of at least 95% by weight of rutile and are preferably used with a coating of inorganic oxides and / or of organic compounds with polar and nonpolar groups. Such coatings of TiO2 are known in the prior art.
  • vacuole-initiating fillers are solid particles which are incompatible with the polymer matrix and lead to the formation of vacuole-like cavities when the films are stretched, the size, type and number of vacuoles depending on the size and amount of the solid particles and the stretching conditions how the stretch ratio and stretch temperature are dependent.
  • the vacuoles reduce the density and give the films a characteristic pearlescent, opaque appearance, which is caused by light scattering at the interfaces "vacuole / polymer matrix".
  • the vacuole-initiating fillers have a minimum size of 1 ⁇ m in order to lead to an effective, ie opaque, amount of vacuoles
  • the average particle diameter of the particles is 1 to 6 ⁇ m ! , preferably 1.5 to 5 ⁇ m the particle plays one subordinate role.
  • Usual vacuole-initiating fillers are inorganic and / or organic materials incompatible with polypropylene such as aluminum oxide, aluminum sulfate, barium sulfate, calcium carbonate, magnesium carbonate, silicates such as aluminum silicate (kaolin clay) and magnesium silicate (talc) and silicon dioxide, among which calcium carbonate and silicon dioxide are preferably used.
  • polypropylene such as aluminum oxide, aluminum sulfate, barium sulfate, calcium carbonate, magnesium carbonate, silicates such as aluminum silicate (kaolin clay) and magnesium silicate (talc) and silicon dioxide, among which calcium carbonate and silicon dioxide are preferably used.
  • Suitable organic fillers are the customarily used polymers which are incompatible with the polymer of the base layer, in particular those such as HDPE, copolymers of cyclic olefins such as norbomene or tetracyclododecene with ethylene or propene, polyesters, polystyrenes, polyamides, halogenated organic polymers, polyesters such as, for example Polybutylene terephthalates are preferred.
  • “Incompatible materials or incompatible polymers” in the sense of the present invention means that the material or the polymer is present in the film as a separate particle or as a separate phase.
  • the opaque base layer contains pigments in an amount of 0.5 to 10% by weight, preferably 1 to 8% by weight, in particular 1 to 5% by weight.
  • Vacuum-initiating fillers are present in an amount of 0.5 to 30% by weight, preferably 1 to 15% by weight, in particular 1 to 10% by weight.
  • the information relates to the weight of the base layer.
  • the density of the opaque embodiments can vary in further ranges and is between 0.5 and 0.96 g / cm 3 .
  • a vacuole-containing base layer reduces the density of the film, which is then in the range from 0.55 to 0.8 g / cm 3 , preferably 0.6 to 0.75 g / cm 3 .
  • the films with a vacuole-containing base layer are particularly advantageous with regard to sealing.
  • the base layer both in a transparent and in an opaque embodiment, customary additives such as neutralizing agents, Stabilizers, antistatic agents and / or lubricants contained in effective amounts.
  • customary additives such as neutralizing agents, Stabilizers, antistatic agents and / or lubricants contained in effective amounts. The following percentages by weight relate to the weight of the base layer.
  • Preferred antistatic agents are alkali alkane sulfonates, polyether-modified, i.e. H. ethoxylated and / or propoxylated polydiorganosiloxanes (polydialkylsiloxanes, polyalkylphenylsiloxanes and the like) and / or the essentially straight-chain and saturated aliphatic, tertiary amines with an aliphatic radical having 10 to 20 carbon atoms, which with ⁇ -hydroxy- (C ⁇ C) -alkyl- Groups are substituted, with N, N-bis (2-hydroxyethyl) alkylamines having 10 to 20 carbon atoms, preferably 12 to 18 carbon atoms, being particularly suitable in the alkyl radical.
  • the effective amount of antistatic is in the range of 0.05 to 0.5% by weight.
  • Lubricants are higher aliphatic acid amides, higher aliphatic acid esters, waxes and metal soaps as well as polydimethylsiloxanes.
  • the effective amount of lubricant is in the range of 0.01 to 3% by weight, preferably 0.02 to 1% by weight.
  • the addition of higher aliphatic acid amides in the range from 0.01 to 0.25% by weight in the base layer is particularly suitable.
  • a particularly suitable aliphatic acid amide are erucic acid amide and stearylamide.
  • the addition of polydimethylsiloxanes in the range from 0.02 to 2.0% by weight is preferred, in particular polydimethylsiloxanes with a viscosity of 5,000 to 1,000,000 mm 2 / s.
  • the usual stabilizing compounds for ethylene, propylene and other ⁇ -olefin polymers can be used as stabilizers.
  • the amount added is between 0.05 and 2% by weight.
  • Phenolic and phosphitic stabilizers are particularly suitable. Phenolic stabilizers with a molecular weight of more than 500 g / mol are preferred, in particular pentaerythrityl-tetrakis-3- (3,5-di-tertiary-butyl-4-hydroxyphenyl) propionate or 1,3,5-trimethyl-2,4,6-tris (3,5-di-tertiary-butyl-4-hydroxybenzyl) benzene.
  • Phenolic stabilizers are used in an amount of 0.1 to 0.6% by weight, in particular 0.1 to 0.3% by weight, phenolic and phosphitic stabilizers in a ratio of 1: 4 to 2: 1 and in one Total amount of 0.1 to 0.4 wt .-%, in particular 0.1 to 0.25 wt .-% used.
  • Neutralizing agents are preferably dihydrotalcite, calcium stearate and / or calcium carbonate with an average particle size of at most 0.7 ⁇ m, an absolute particle size of less than 10 ⁇ m and a specific surface area of at least 40 m 2 / g. (What are the usual amounts?)
  • the outer surface of the base layer is surface-treated by means of corona, plasma or flame.
  • the polyolefin film according to the invention preferably has a second cover layer, which shows good adhesion to conventional printing inks, adhesives, and coatings and / or lacquers based on PVDC or acrylic.
  • This second cover layer is preferably applied to the opposite surface of the base layer and is referred to below as "second cover layer".
  • second cover layer it is preferred to carry out a corona, plasma or flame treatment of the surface of the second cover layer.
  • the second cover layer is generally composed of polymers from olefins having 2 to 10 carbon atoms.
  • the second cover layer generally contains 95 to 100% by weight of polyolefin, preferably 98 to ⁇ 100% by weight of polyolefin, in each case based on the weight of the cover layer / s.
  • Suitable olefinic polymers of the top layer / s are Propylene homopolymers, copolymers or terpolymers II made of ethylene-propylene and / or butylene units or mixtures of the polymers mentioned. These copolymers or terpolymers II contain no carboxylic acid monomers. They are polyolefins.
  • Preferred polymers include statistical ethylene-propylene copolymers with an ethylene content of 1 to 10% by weight, preferably 2.5 to 8% by weight, or statistical propylene-butylene-1 copolymers with a butylene content of 2 to 25% by weight .-%, preferably 4 to 20 wt .-%, or statistical ethylene-propylene-butylene-1 terpolymers with an ethylene content of 1 to 10 wt .-% and a butylene-1 content of 2 to 20 wt .-% , or a mixture or a blend of ethylene-propylene-butylene-1 terpolymers and propylene-butylene-1 copolymers with an ethylene content of 0.1 to 7% by weight and a propylene content of 50 to 90% by weight and a butylene 1 content of 10 to 40 wt .-%.
  • the percentages by weight relate to the weight of the polymer.
  • the copolymers and / or terpolymers II described above used in the second top layer and which are composed only of olefins generally have a melt flow index of 1.5 to 30 g / 10 min, preferably 3 to 15 g / 10 min , The melting point is in the range from 120 to 140 ° C.
  • the blend of copolymers and terpolymers II described above has a melt flow index of 5 to 9 g / 10 min and a melting point of 120 to 150 ° C. All melt flow indices given above are measured at 230 ° C and a force of 21.6 N (DIN 53 735). If appropriate, all of the cover layer polymers described above can be degraded peroxidically, the degradation factor generally being in a range from 1 to 15, preferably 1 to 8.
  • the additives described above can be added to the second cover layer (s) and / or stabilizers, and optionally additional antiblocking agents are added.
  • the data in% by weight then relate accordingly to the weight of the second cover layer.
  • Suitable antiblocking agents have already been described in connection with the first cover layer. These antiblocking agents are also suitable for the second top layer.
  • the preferred amount of antiblocking agent for the second cover layer is in the range from 0.1 to 2% by weight, preferably 0.1 to 0.8% by weight.
  • the thickness of the second cover layer is greater than 0.1 ⁇ m and is preferably in the range from 0.1 to 5 ⁇ m, in particular 0.5 to 3 ⁇ m.
  • the film according to the invention comprises at least the base layer described above and the first cover layer, made of co- or terpolymer I and wax. If necessary, a second cover layer of purely olefinic polymers is applied to the opposite surface. If necessary, one or both sides of the intermediate layer (s) can also be present between the base layer and the cover layer (s).
  • the intermediate layer (s) can be composed of the olefinic polymers, preferably propylene polymers, described for the base layer or for the cover layers.
  • the intermediate layer (s) can contain the usual additives described for the individual layers, such as antistatic agents, neutralizing agents, lubricants and / or stabilizers.
  • wax can also be added to that intermediate layer which is arranged between the base layer and the first cover layer.
  • the waxes described above for the first cover layer are suitable as waxes.
  • the wax content in the Intermediate layer is in the range of at most 20% by weight, preferably 0.5 to 10% by weight, in particular 1 to 4% by weight, in each case based on the weight of the intermediate layer.
  • the thickness of this intermediate layer is greater than 0.5 ⁇ m and is preferably in the range from 0.6 to 4 ⁇ m, in particular 0.8 to 3 ⁇ m.
  • the intermediate layer between the second cover layer and the base layer can contain vacuole-initiating fillers and / or pigments for embodiments with an opaque appearance.
  • the thickness of this opaque intermediate layer is greater than 0.3 ⁇ m and is preferably in the range from 1.0 to 15 ⁇ m, in particular 1.5 to 10 ⁇ m.
  • the total thickness of the polypropylene film according to the invention can vary within wide limits and depends on the intended use. It is preferably 4 to 60 ⁇ m, in particular 5 to 30 ⁇ m, preferably 6 to 25 ⁇ m, the base layer accounting for approximately 40 to 99% of the total film thickness.
  • the invention further relates to a method for producing the polyolefin film according to the invention by the coextrusion method known per se.
  • the melts corresponding to the individual layers of the film are coextruded through a flat die, the film obtained in this way is drawn off for consolidation on one or more rollers, the film is then stretched (oriented), the stretched film is heat-set and optionally on the Treatment provided surface layer plasma-corona or flame treated.
  • Biaxial stretching (orientation) is carried out sequentially or simultaneously.
  • the sequential stretching is generally carried out sequentially, with the sequential biaxial stretching, in which the first longitudinal (in Machine direction) and then stretched transversely (perpendicular to the machine direction) is preferred.
  • the further description of the film production takes place using the example of a flat film extrusion with subsequent sequential stretching.
  • the polymer or the polymer mixture of the individual layers is compressed and liquefied in an extruder, it being possible for the additives which may have been added to be present in the polymer or in the polymer mixture.
  • the melts are then pressed simultaneously through a flat die (slot die), and the pressed multilayer film is drawn off on one or more take-off rolls at a temperature of 10 to 100 ° C., preferably 10 to 50 ° C., where it cools and solidifies.
  • the film thus obtained is then stretched longitudinally and transversely to the direction of extrusion, which leads to an orientation of the molecular chains.
  • the longitudinal stretching is preferably carried out at a temperature of 70 to 120 ° C., expediently with the aid of two rollers running at different speeds corresponding to the desired stretching ratio, and the transverse stretching is preferably carried out at a temperature of 120 to 180 ° C. with the aid of an appropriate tenter frame.
  • the longitudinal stretching ratios are in the range from 3 to 8, preferably 4 to 6.
  • the transverse stretching ratios are in the range from 5 to 10, preferably 7 to 9.
  • the stretching of the film is followed by its heat setting (heat treatment), the film being held at a temperature of 100 to 160 ° C. for about 0.1 to 10 s.
  • the film is then wound up in a conventional manner using a winding device.
  • one or both surfaces of the film are / are preferably plasma, corona or flame treated by one of the known methods.
  • the treatment intensity is generally in the range from 35 to 50 mN / m, preferably 37 to 45 mN / m.
  • the corona treatment is expediently carried out in such a way that the film is passed between two conductor elements serving as electrodes, such a high voltage, usually alternating voltage (approximately 5 to 20 kV and 5 to 30 kHz) being applied between the electrodes that Spray or corona discharges can take place.
  • alternating voltage approximately 5 to 20 kV and 5 to 30 kHz
  • the melt flow index was measured according to DIN 53 735 at 21.6 N load and 230 ° C.
  • the haze of the film was measured according to ASTM-D 1003-52.
  • the gloss was determined in accordance with DIN 67 530. The was measured
  • Reflector value as an optical parameter for the surface of a film. Based on the standards ASTM-D 523-78 and ISO 2813, the angle of incidence was set at 60 ° or 85 °. A light beam hits under the set one Angle of incidence on the flat test surface and is reflected or scattered by it. The light rays striking the photoelectronic receiver are displayed as a proportional electrical quantity. The measured value is dimensionless and must be specified with the angle of incidence.
  • the corona-treated films were printed 14 days after their production (short-term assessment) or 6 months after their production (long-term assessment).
  • the color adhesion was assessed using an adhesive tape test. If little color could be removed using adhesive tape, the color adhesion was assessed as moderate and, if the color was clearly separated, poor.
  • One or more film samples that are to be examined for their block behavior are alternately stacked with a film sample that is coated on its surface with PVDC or acrylate varnish so that the outside of the film sample to be tested with the PVDC - Lacquer or acrylate lacquer is in contact.
  • a strip a few centimeters wide is covered with paper, for example. If the film sample itself carries the PVDC or acrylate varnish, every second contact surface is completely covered in order to better separate the film samples for measurement.
  • the stack of samples is pressed using a rocker arm press under a pressure of 100 N / cm 2 at room temperature for 24 hours.
  • the Foil samples isolated, cut into 30 mm wide strips and clamped in a tensile testing machine (e.g. Zwick 1120.25) in such a way that the foil sample, which is to be examined for its blocking behavior, and the foil sample, which is coated on its surface with PVDC or acrylate varnish, be separated from each other at an angle of two 90 °.
  • the force required to separate the pieces of film is measured.
  • the average of three measurements and the extent of any transfer of PVDC or acrylic varnish to the film sample are used for evaluation.
  • the average molecular weights Mw and Mn and the average molecular weight dispersity Mw / Mn were determined in accordance with DIN 55 672, Part 1, by means of gel permeation chromatography. Instead of THF, orthodichlorobenzene was used as the eluent. Since the olefinic polymers to be examined are not soluble at room temperature, the entire measurement is carried out at elevated temperature (“* 135 ° C.).
  • a transparent three-layer film consisting of the base layer B and a first and second cover layers with a total thickness of 30 ⁇ m was produced by coextrusion and subsequent stepwise orientation in the longitudinal and transverse directions.
  • the first cover layers had a thickness of 2.0 ⁇ m and the second cover layer had a thickness of 0.7 ⁇ m.
  • SiO 2 as an antiblocking agent with an average particle size of 4 ⁇ m 10.0% by weight of a microcrystalline wax with a melting point of 76-81 ° C. and a viscosity of 13-18 mm 2 / s at 98 , 89 ° C
  • Second cover layer 99.54% by weight of random copolymer of ethylene and propylene with a melt flow index of 6.0 g / 10 min and an ethylene content of 6% by weight, based on the copolymer, of 0.22% by weight of SiO 2 as an antiblocking agent an average particle size of 4 ⁇ m 0.20% by weight stabilizer (Irganox / Irgafos)
  • Example 1 A three-layer film was produced as described in Example 1. In contrast to Example 1, an additional 5.1% by weight of calcium carbonate with an average particle diameter of 2 ⁇ m was incorporated into the base layer as vacuum-initiating particles (chalk) and 2.8% by weight of titanium dioxide as a pigment (rutile). The polypropylene content was reduced accordingly. The production conditions in the individual process steps were as in Example 1. The film was white opaque.
  • Example 3 A three-layer white-opaque film as described in Example 2 was produced. In contrast to Example 2, 10% by weight of a polyethylene wax with a molecular weight (number average) of 2000 was used in the top layer C instead of 10% by weight of paraffin wax. The production conditions in the individual process steps were as in Example 2.
  • Example 4 Example 4
  • Example 3 A three-layer white-opaque film as described in Example 3 was produced. In contrast to Example 3, instead of 10% by weight of the polyethylene wax with an Mn of 2000, 5% by weight of a polyethylene wax with a molecular weight Mn (number average) of 655 was used in the top layer C. The proportion of terpolymer in the top layer C was increased accordingly.
  • the production conditions in the individual process steps were as in Example 3.
  • Example 4 A three-layer white-opaque film as described in Example 4 was produced.
  • the top layer C was additionally 5 wt .-% of an HDPE with a melting point of 133 ° C and a density of 0.957 g / cm 3 , and an MFI of 15g / 10min (190 ° C / 21, 6N) added.
  • the production conditions in the individual process steps were as in Example 4.
  • Example 6 A three-layer white-opaque film as described in Example 5 was produced. In contrast to Example 5, the HDPE content was increased from 5 to 10% by weight and the SiO2 content was reduced from 1 to 0.5% by weight. The terpolymer content was adjusted accordingly. The production conditions in the individual process steps were as in Example 5.
  • Example 8 A three-layer white-opaque film as described in Example 6 was produced. In contrast to Example 6, the top layer C now contained no SiO2. The terpolymer content was adjusted accordingly. The production conditions in the individual process steps were as in Example 6. Example 8
  • Example 5 A three-layer white-opaque film as described in Example 5 was produced.
  • a copolymer of ethylene and ethyl acrylate (without maleic anhydride) with an ethylene content of 96% by weight and an ethyl acrylate content of 4% by weight was used instead of a terpolymer.
  • the melt flow index of the copolymer was 5.0 g / 10min [at 190 ° C., 21.6N].
  • the production conditions in the individual process steps were as in Example 5.
  • Example 5 A three-layer white-opaque film was produced as described in Example 5. In contrast to Example 5, the top layer C now contained no wax. The terpolymer content was adjusted accordingly. The production conditions in the individual process steps were as in Example 5.
  • Example 5 A three-layer white-opaque film was produced as described in Example 5.
  • the top layer C now contained an ethylene-propylene copolymer with a melt flow index of 6 g / 10 min and an ethylene content of 6% by weight instead of the copolymer with ethyl acrylate described.
  • the production conditions in the individual process steps were as in Example 5.
  • Example 5 A three-layer white-opaque film was produced as described in Example 5. In contrast to Example 5, the top layer C now contained no wax and no HDPE. The terpolymer content was adjusted accordingly. The production conditions in the individual process steps were as in Example 5.
  • the films according to the examples all have good sealing properties against acrylate coatings and PVDC lacquers and against themselves. The films do not stick to the rollers during the manufacturing process and can also be handled well during subsequent processing. When unwinding the coated rolls, the surfaces in contact can be easily separated. There is little or no pick-off, ie the coating made of acrylates or PVDC does not stick to the surface of the first cover layer.
  • the films are very suitable for roll-wrap packaging.
  • the film according to Comparative Example 1 shows the desired sealing against PVDC or acrylate coatings, but when the coated film is unrolled there is a heavy pick-off, which considerably impairs the function of the coating.
  • the film according to Comparative Example 2 shows no sealing against the PVDC or acrylate coatings.
  • the film according to Comparative Example 3 can only be produced under extremely difficult conditions.
  • the film shows a very strong tendency to stick to the rollers.
  • the pick off when unwinding the coated film is considerable. In fact, the film cannot be used for the intended purpose.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)

Abstract

La présente invention concerne un film en polyoléfine multicouche, à orientation biaxiale, qui est constitué d'une couche de base et d'au moins une couche de protection. Cette couche de protection comprend, en tant que composant principal, un copolymère ou un terpolymère, qui se scelle contre des vernis et revêtements en PVDC et contre des vernis et revêtements en acrylate et est constitué d'une oléfine et d'acides carboxyliques insaturés ou d'esters de ceux-ci, ainsi que de faibles quantités de cire. Ce film est pourvu sur un côté d'un revêtement en PVDC ou en acrylate, afin d'être utilisé en tant que matériau d'emballage en rouleau.
EP01980369A 2000-09-19 2001-09-11 Film en polyolefine a orientation biaxiale presentant une meilleure aptitude au scellage contre des vernis et revetements en acrylate et pvdc Withdrawn EP1322469A2 (fr)

Applications Claiming Priority (3)

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DE10046543 2000-09-19
DE10046543 2000-09-19
PCT/EP2001/010473 WO2002024375A2 (fr) 2000-09-19 2001-09-11 Film en polyolefine a orientation biaxiale presentant une meilleure aptitude au scellage contre des vernis et revetements en acrylate et pvdc

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EP (1) EP1322469A2 (fr)
AU (2) AU1222902A (fr)
CA (1) CA2421983C (fr)
IL (2) IL154623A0 (fr)
MX (1) MXPA03002360A (fr)
RU (1) RU2297331C2 (fr)
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WO2002098658A1 (fr) * 2001-06-02 2002-12-12 Trespaphan Gmbh Film ayant une aptitude au scellement et une adherence ameliorees
JP4439378B2 (ja) * 2004-11-17 2010-03-24 日本たばこ産業株式会社 包装紙及び包装紙を使用したシガレットパッケージ並びに包装紙の製造方法及び装置
US20060211801A1 (en) * 2005-03-16 2006-09-21 Fina Technology, Inc. Polyolefin film and production thereof
GB2444761A (en) * 2005-11-25 2008-06-18 Amcor Flexibles Winterbourne L Polymeric films
ITMI20110770A1 (it) 2011-05-06 2012-11-07 Irplast Spa Film multistrato
ITUA20163676A1 (it) * 2016-05-23 2017-11-23 Taghleef Ind S P A Pellicola multistrato
EP3272524A1 (fr) * 2016-07-21 2018-01-24 Omya International AG Carbonate de calcium comme agent de cavitation pour films de polypropylène orientés bi-axialement
CN110429229A (zh) * 2019-07-31 2019-11-08 宁德新能源科技有限公司 多层隔离膜及使用其的装置
IT202200002636A1 (it) * 2022-02-14 2023-08-14 Esse C I Societa´ Costruzioni Ind S R L Strutture polimeriche per imballaggi

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US4681803A (en) * 1985-10-18 1987-07-21 Mobil Oil Corporation Pigmented, heat-sealable coating composition for application to oriented polyolefin films
GB2223446B (en) 1988-08-26 1993-01-06 Courtaulds Films & Packaging Polymeric films for packaging
US6077602A (en) 1996-03-21 2000-06-20 Mobil Oil Corporation Heat sealable film
DE19836657A1 (de) * 1998-08-13 2000-02-17 Hoechst Trespaphan Gmbh Mehrschichtig biaxial orientierte Polypropylenfolie mit verbesserter Barriere, Verfahren zu ihrer Herstellung und ihre Verwendung
US6503611B1 (en) 1998-12-02 2003-01-07 Toray Plastics (America), Inc. Cold seal release biaxially oriented polypropylene film for packaging with stable release properties
DE10018442A1 (de) 2000-04-13 2001-10-18 Trespaphan Gmbh Biaxial orientierte Polyolefinfolie mit verminderter Blockneigung gegen Kaltsiegelmassen
WO2002098658A1 (fr) * 2001-06-02 2002-12-12 Trespaphan Gmbh Film ayant une aptitude au scellement et une adherence ameliorees

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US20040033378A1 (en) 2004-02-19
IL154623A0 (en) 2003-09-17
AU1222902A (en) 2002-04-02
IL154623A (en) 2008-08-07
MXPA03002360A (es) 2003-06-30
RU2297331C2 (ru) 2007-04-20
CA2421983A1 (fr) 2003-03-18
AU2002212229B2 (en) 2006-02-23
WO2002024375A3 (fr) 2002-06-27
CA2421983C (fr) 2010-11-30
US7011882B2 (en) 2006-03-14
ZA200303031B (en) 2004-03-10
WO2002024375A2 (fr) 2002-03-28

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