EP0977665A1 - Multi-layered stretched hot-sealable polypropylene film with a polyketone gas barrier layer - Google Patents

Multi-layered stretched hot-sealable polypropylene film with a polyketone gas barrier layer

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Publication number
EP0977665A1
EP0977665A1 EP98922756A EP98922756A EP0977665A1 EP 0977665 A1 EP0977665 A1 EP 0977665A1 EP 98922756 A EP98922756 A EP 98922756A EP 98922756 A EP98922756 A EP 98922756A EP 0977665 A1 EP0977665 A1 EP 0977665A1
Authority
EP
European Patent Office
Prior art keywords
layer
ethylene
composite film
film according
acid
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Withdrawn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
EP98922756A
Other languages
German (de)
French (fr)
Inventor
Bernd Sperlich
Rainer Brandt
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.)
Dow Produktions und Vertriebs GmbH and Co oHG
Original Assignee
Wolff Walsrode AG
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Filing date
Publication date
Application filed by Wolff Walsrode AG filed Critical Wolff Walsrode AG
Publication of EP0977665A1 publication Critical patent/EP0977665A1/en
Withdrawn legal-status Critical Current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
    • 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
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/516—Oriented mono-axially
    • 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
    • B32B2307/518—Oriented bi-axially
    • 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
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • 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
    • B32B2310/00—Treatment by energy or chemical effects
    • B32B2310/14—Corona, ionisation, electrical discharge, plasma treatment
    • 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
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—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

Definitions

  • the present invention relates to a sealable, stretched multilayer film which, owing to its gas barrier properties, is particularly suitable as packaging film for goods which require low gas permeability and aroma protection.
  • Polyamides as barrier materials have significantly poorer barrier properties, which are not sufficient for many applications.
  • a heat-sealable composite film made of a biaxially stretched polypropylene film as the base film, an adhesion promoter layer made of modified system polyolefin, a gas barrier layer of a copolymer of one or more olefins and carbon monoxide and a heat seal layer of olefin polymers, characterized in that the base film carries at least on one surface an optionally at least monoaxially oriented layer combination, which is composed of
  • the base film optionally carries a layer A, a layer combination A to E, A to D or B and C on at least one of its surfaces.
  • B and C or C and D can be combined to form a layer by mixing the corresponding polymers.
  • the biaxially stretched and heat sealable polypropylene film made by a sequential process contains a gas barrier layer made from a copolymer of carbon monoxide and one or more olefinically unsaturated compounds.
  • a gas barrier layer made from a copolymer of carbon monoxide and one or more olefinically unsaturated compounds.
  • all monomers of this class of compounds can be considered as olefinically unsaturated compounds.
  • Ethylene and C 3 - to Cio-alkenes such as propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-octene, 1-nonen, 1-decene are preferred. Are particularly preferred
  • the barrier layer material preferably consists of a copolymer of 25 to 50 mol% of ethylene, 0-25 mol% of propylene and 50 mol% of carbon monoxide, the olefinically unsaturated compounds and carbon monoxide are incorporated alternately in the copolymer.
  • the partial exchange of ethylene with higher olefins lowers the melting point and improves the stretchability of the copolymer.
  • the polypropylene of the core film is preferably an isotactic polypropylene with a density of 0.90 to 0.91 g / cm 3 and a melt flow index of 1 to 4 g / 10 min at 230 ° C / 2.16 kp / cm 2 pressure (DIN 53 735).
  • a propylene / ethylene copolymer is particularly preferably characterized in that it contains 1.0 to 10% by weight of polyethylene.
  • the density of the sealing layer polymer should preferably be in the range from 0.895 to 0.960 g / cm 3 and the crystallite melting point, depending on the type, in the range from 125 to 148 ° C.
  • Preferred antistatic agents are alkali alkane sulfonates, polyether-modified, ie 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 to 20 atoms which are substituted with ⁇ -hydroxy (C 1 -C 4 ) alkyl groups, 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.
  • Glycerol monostearate is also suitable and is used in an amount of 0.03% to 0.5% by weight as an antistatic.
  • 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, polyacrylates, polymethacrylates, polyesters, polycarbonates and the like; preference is given to using polymethacrylates and silicon dioxide.
  • the effective amount of antiblocking agent is in the range of 0.1 to 2% by weight, preferably 0.1 to 0.8% by weight.
  • the average particle size is between 1 and 6 ⁇ m, in particular 2 and 5 ⁇ m, particles with a spherical shape being particularly suitable.
  • 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 is particularly suitable.
  • a particularly suitable aliphatic acid amide is erucic acid amide.
  • polydimethylsiloxanes in the range from 0.02 to 2% by weight is preferred, in particular polydimethylsiloxanes with a viscosity of
  • Modified polyolefins are used to produce the adhesion promoter layer. These are preferably polyolefins with carboxyl groups, such as polypropylene or polyethylene, which contain copolymers of at least one monomer from the group of the ⁇ , ⁇ -monounsaturated dicarboxylic acids, such as maleic acid, fumaric acid, itaconic acid or their acid anhydrides, acid esters, acid amides and acid imides Ethylene with ⁇ , ß-monounsaturated carboxylic acids, such as acrylic acid, methacrylic acid and / or their metal salts (Zn, Na) and / or their alkyl (C 1 -C 4 ) esters or corresponding graft polymers on polyolefins such as polyethylene or polypropylene or already Saponified copolymers described which have been graft-polymerized with a monomer of the abovementioned unsaturated acids.
  • carboxyl groups such as polyprop
  • polyolefins such as polypropylene or copolymers of propylene and ethylene with a maximum of 1.0% by weight of grafted on ⁇ , ⁇ -monounsaturated dicarboxylic acid anhydride such as maleic anhydride or their saponified copolymers.
  • adhesion promoter polymer is incorporated either in the sealable layer A or in the gas barrier layer C, up to 40% by weight, preferably 25-30% by weight, based on layer-forming polymers, of the modified polyolefin are used to produce the corresponding polymers.
  • the invention further relates to packaging preferably for oxygen-sensitive foods made from the multilayer film according to the invention.
  • the films according to the invention can be prepared using the customary processes such as lamination,
  • Coating or melt coextrusion can be produced.
  • the film is stretched in the running direction (lengthways) with a stretching ratio of 4/1 to 7/1 at a temperature of 120 ° C - 150 ° C.
  • the stretch ratio in the transverse direction is preferably between 8/1 and 12/1 and the transverse stretching of the film is carried out at a temperature between 130 ° C. and 170 ° C.
  • the subsequent heat setting is preferably carried out at 1 ° C - 40 ° C below the transverse stretching temperature.
  • a corona (spray) pretreatment In order to ensure the affinity of the largely non-polar film surface for the printing inks, it is necessary to subject the film to a corona (spray) pretreatment.
  • the atmospheric oxygen is stored in the form of carbonyl, epoxy, ether or alcohol groups on the film surface.
  • Other methods of pretreating polypropylene films are flame, plasma and fluorine pretreatment. example
  • 98.7% by weight of a propylene-ethylene copolymer with 4.5% by weight of ethylene had a density of 0.90 g / cm 3 with a melt index of 5 g / 10 min for layer A 230 ° C / 2.16 kp / cm 2 and the crystalline melting point 140 ° C 0.5 wt .-% N, N-bis (2-hydroxyethyl) - (C 12 -C 16 ) alkylamine, 0, 3 wt .-% of a polydimethylsiloxane with a density of 0.985 g / cm 3 at 20 ° C.
  • a modified polypropylene such as a saponified copolymer with 0.7% by weight of grafted maleic anhydride and a melt index of 5 g / 10 min at 250 ° C / 216 kp / cm 2 for the adhesion promoter layers and an alternating carbon monoxide-ethylene copolymer (F.
  • the layer structure and the layer thicknesses are summarized in Table 1.
  • the oxygen barrier of the composite film is 15 cm 3 / m 2 d bar.

Landscapes

  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Thermal Sciences (AREA)
  • Laminated Bodies (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

The invention relates to a heat-sealable composite film with a biaxially stretched polypropylene base layer, a modified polyolefin adhesion-promoting layer, an ethylene and carbon monoxide copolymer gas barrier layer and an olefin polymer heat-seal layer. The base layer has optionally at least one monoaxially oriented layer combination on at least on one of its surfaces, comprising: A) an olefinic homo, co or terpolymer heat-sealable outer layer; B) a modified polyolefin adhesion-promoting layer; C) a one or more olefin or carbon monoxide (polyketone) gas barrier layer; D) a modified polyolefin adhesion-promoting layer and E) a polyethylene layer and an ethylene polymer with at least 3 wt. % ethylene. The base layer has optionally layer A, a combination of layers A-E, A-D or B and C on at least one of its surfaces.

Description

MEHRSCHICHTIGE, GERECKTE, HEISSSIEGELBARE POLYPROPYLENFOLIE MIT POLYKF TON-GASSPERRSCHICHT ruL. i ftji-MULTI-LAYER, STRETCHED, HOT-SEALABLE POLYPROPYLENE FILM WITH POLYKF TON GAS BARRIER ru L. if t ji -
Die vorliegende Erfindung betrifft eine siegelbare gereckte Mehrschichtfolie, die sich wegen ihrer Gassperreigenschaften besonders als Verpackungsfolie für solche Güter eignet, die geringe Gasdurchlässigkeit und Aromaschutz erfordern.The present invention relates to a sealable, stretched multilayer film which, owing to its gas barrier properties, is particularly suitable as packaging film for goods which require low gas permeability and aroma protection.
Die Verwendung von Verbundfolien aus Polyolefinen mit einer siegelbaren Schicht aus Ethylenhomo- oder copolymerisaten als Verpackungsfolie ist seit langem bekannt. Es wurde auch bereits versucht, die Gasdurchlässigkeit solcher Verbundfolien durch den Einbau verschiedener polarer Sperrschichtmaterialien zu verbessern. In DE-A-The use of composite films made of polyolefins with a sealable layer of ethylene homo- or copolymers as packaging film has long been known. Attempts have also already been made to improve the gas permeability of such composite films by incorporating various polar barrier layer materials. In DE-A-
2 644 209 und EP 0 062 815 Bl wird durch Einbau einer Schicht aus verseiftem Ethylenvinylacetat die Gasdurchlässigkeit erheblich verringert. Verseiftes Ethylenvi- nylacetat weist aber bezüglich seiner Verarbeitbarkeit erhebliche Nachteile auf. Infolge der hohen Metallhaftung und der geringen Temperaturstabilität führt es bei der Extrusion häufig zu polymeren Ablagerungen im Extruder und der Extrusionsdüse.2,644,209 and EP 0 062 815 B1, the gas permeability is considerably reduced by incorporating a layer of saponified ethylene vinyl acetate. Saponified ethylene vinyl acetate has considerable disadvantages with regard to its processability. Due to the high metal adhesion and the low temperature stability, it often leads to polymeric deposits in the extruder and the extrusion die during extrusion.
Um eine niedrige Gasdurchlässigkeit zu erzielen ist der Einsatz von Ethylenvinyl- alkohol Copolymeren mit relativ hohem Gehalt an Vinylalkohol notwendig. Dies hat zum Nachteil, daß Verbundfolien aus PP und EVOH nur geringe Reckbarkeit aufweisen und relativ hohe Recktemperaturen erfordern. Ein wesentlicher Nachteil von Barrierefolien mit Ethylenvinylalkohol Copolymeren als Sperrschicht ist deren geringe Knickbruchfestigkeit, die insbesondere bei der Herstellung von Schlauchbeuteln Schwierigkeiten bereitet.In order to achieve a low gas permeability, the use of ethylene vinyl alcohol copolymers with a relatively high content of vinyl alcohol is necessary. This has the disadvantage that composite films made of PP and EVOH have only low stretchability and require relatively high stretching temperatures. A major disadvantage of barrier films with ethylene vinyl alcohol copolymers as the barrier layer is their low resistance to kink fracture, which is particularly difficult in the manufacture of tubular bags.
Polyamide als Sperrschichtmaterialien weisen deutlich schlechtere Barriereeigenschaf- ten auf, die für viele Anwendungen nicht ausreichend sind.Polyamides as barrier materials have significantly poorer barrier properties, which are not sufficient for many applications.
Daher erwies es sich als notwendig, eine mehrschichtige, heißsiegelbare BOPP-Folie zu fertigen, die ein Sperrschichtmaterial enthält, welches eine hohe Sauerstoffbarriere aufweist, leicht zu verarbeiten ist und zu einer hohen Knickbruchfestigkeit des Folienverbundes führt.It has therefore proven necessary to produce a multilayer, heat-sealable BOPP film which contains a barrier layer material which has a high oxygen barrier, is easy to process and leads to a high resistance to kink breakage of the film composite.
Gelöst wird diese Aufgabe durch eine heißsiegelbare Verbundfolie aus einer biaxial gereckten Polypropylenfolie als Basisfolie, einer Haftvermittlerschicht aus modifizier- tem Polyolefin, einer Gassperrschicht aus einem Copolymer aus einem oder mehreren Olefinen und Kohlenmonoxid und einer Heißsiegelschicht aus Olefmpolymerisaten, dadurch gekennzeichnet, daß die Basisfolie mindestens auf einer Oberfläche eine gegebenenfalls wenigstens monoaxial orientierte Schichtkombination trägt, die sich zusammensetzt ausThis problem is solved by a heat-sealable composite film made of a biaxially stretched polypropylene film as the base film, an adhesion promoter layer made of modified system polyolefin, a gas barrier layer of a copolymer of one or more olefins and carbon monoxide and a heat seal layer of olefin polymers, characterized in that the base film carries at least on one surface an optionally at least monoaxially oriented layer combination, which is composed of
A) einer heißsiegelbaren Außenschicht aus einem olefinischen Homo-, Co- oder Terpolymerisat;A) a heat-sealable outer layer made of an olefinic homo-, co- or terpolymer;
B) einer Haftvermittlerschicht aus modifiziertem Polyolefin; C) einer Gassperrschicht aus einem Copolymer aus einem oder mehreren Olefinen und Kohlenmonoxid (Polyketon), bei dem das/die Olefin(e) und Kohlenmonoxid in alternierender Abfolge eingebaut sind;B) an adhesion promoter layer made of modified polyolefin; C) a gas barrier layer made of a copolymer of one or more olefins and carbon monoxide (polyketone), in which the olefin (s) and carbon monoxide are incorporated in an alternating sequence;
D) einer Haftvermittlerschicht aus modifiziertem Polyolefin undD) an adhesion promoter layer made of modified polyolefin and
E) einer Schicht aus Polyethylen einem Ethylenpolymerisat mit wenigstens 3 Gew. -% Ethylen,E) a layer of polyethylene an ethylene polymer with at least 3% by weight of ethylene,
die Basisfolie auf mindestens einer ihrer Oberflächen gegebenenfalls eine Schicht A, eine Schichtkombination A bis E, A bis D oder B und C trägt.the base film optionally carries a layer A, a layer combination A to E, A to D or B and C on at least one of its surfaces.
Gegebenenfalls können die Schichten A und B und/oder D und E oder die SchichtenOptionally, layers A and B and / or D and E or the layers
B und C bzw. C und D zu einer Schicht durch Vermischen der entsprechenden Polymeren vereinigt werden.B and C or C and D can be combined to form a layer by mixing the corresponding polymers.
Das bevorzugte Merkmal besteht darin, daß die mittels eines sequentiellen Verfahren hergestellte biaxial gereckte und heißsiegelbare Polypropylen-Folie eine Gassperrschicht aus einem Copolymer aus Kohlenmonoxid und einem oder mehreren olefinisch ungesättigten Verbindungen enthält. Als olefinisch ungesättigte Verbindungen kommen grundsätzlich alle Monomere dieser Verbindungsklasse in Betracht. Bevorzugt sind Ethylen und C3- bis Cio-Alkene wie beispielsweise Propylen, 1-Buten, 2-Buten, 1-Penten, 1 -Hexen, 1-Octen, 1-Nonen, 1-Decen. Besonders bevorzugt sindThe preferred feature is that the biaxially stretched and heat sealable polypropylene film made by a sequential process contains a gas barrier layer made from a copolymer of carbon monoxide and one or more olefinically unsaturated compounds. In principle, all monomers of this class of compounds can be considered as olefinically unsaturated compounds. Ethylene and C 3 - to Cio-alkenes such as propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-octene, 1-nonen, 1-decene are preferred. Are particularly preferred
Ethylen und Propylen. Das Sperrschichtmaterial besteht bevorzugt aus einem Copoly- merisat aus 25 bis 50 mol-% Ethylen, 0-25 mol-% Propylen und 50 mol-% Kohlenmonoxid, wobei die olefisch ungesättigten Verbindungen und Kohlenmonoxid alternierend in das Copolymerisat eingebaut sind. Durch den partiellen Austausch von Ethylen durch höhere Olefine sinkt der Schmelzpunkt und es verbessert sich die Reck- barkeit des Copolymeren.Ethylene and propylene. The barrier layer material preferably consists of a copolymer of 25 to 50 mol% of ethylene, 0-25 mol% of propylene and 50 mol% of carbon monoxide, the olefinically unsaturated compounds and carbon monoxide are incorporated alternately in the copolymer. The partial exchange of ethylene with higher olefins lowers the melting point and improves the stretchability of the copolymer.
Das Polypropylen der Kernfolie ist vorzugsweise ein isotaktisches Polypropylen mit einer Dichte von 0,90 bis 0,91 g/cm3 und einem Schmelzflußindex von 1 bis 4 g/ 10 min bei 230 °C/2,16 kp/cm2 Druck (DIN 53 735).The polypropylene of the core film is preferably an isotactic polypropylene with a density of 0.90 to 0.91 g / cm 3 and a melt flow index of 1 to 4 g / 10 min at 230 ° C / 2.16 kp / cm 2 pressure (DIN 53 735).
Unter den zahlreichen, für siegelfähige Schichten eingesetzten Materialien werden folgende bevorzugt eingesetzt:Among the numerous materials used for sealable layers, the following are preferred:
- statistische Propylen/Ethylen -Copolymere- statistical propylene / ethylene copolymers
- statistische Propylen/Olefin (1) -Copolymere- statistical propylene / olefin (1) copolymers
- statistische Propylen/Ethylen/Olefin-Terpolymere - Mischungen aus zwei oder drei der vorstehenden Polymere.- statistical propylene / ethylene / olefin terpolymers - mixtures of two or three of the above polymers.
Besonders bevorzugt wird ein Propylen/Ethylen-Copolymerisat dadurch gekennzeichnet, daß es 1,0 bis 10 Gew.-% Polyethylen enthält. Die Dichte des Siegelschicht- polymeren sollte vorzugsweise im Bereich von 0,895 bis 0,960 g/cm3 und der Kristallitschmelzpunkt je nach Typ im Bereich von 125 bis 148 °C liegen.A propylene / ethylene copolymer is particularly preferably characterized in that it contains 1.0 to 10% by weight of polyethylene. The density of the sealing layer polymer should preferably be in the range from 0.895 to 0.960 g / cm 3 and the crystallite melting point, depending on the type, in the range from 125 to 148 ° C.
Um eine gute Maschinengängigkeit von biaxial orientierten Polypropylenfolien zu gewährleisten, ist es notwendig mindestens die Siegel- bzw. Deckschichten mit Additiven, wie Gleitmittel, Antiblockmittel und Antistatika auszustatten.In order to ensure good machinability of biaxially oriented polypropylene films, it is necessary to equip at least the sealing or cover layers with additives such as lubricants, antiblocking agents and antistatic agents.
Bevorzugte Antistatika sind Alkali-alkansulfonate, polyethermodifizierte, d. h. ethoxy- lierte und/oder propoxylierte Polydiorganosiloxane (Polydialkylsiloxane, Polyalkyl- phenylsiloxane und dergleichen) und/oder die im wesentlichen geradkettigen und gesättigten aliphatischen, tertiären Amine mit einem aliphatischen Rest mit 10 bis 20 Kohlenstoffatomen, die mit ω-Hydroxy-(Cι-C4)-alkyl-Gruppen substituiert sind, wobei N,N-bis-(2-hydroxyethyl)-alkylamine mit 10 bis 20 Kohlenstoffatomen, vorzugsweise 12 bis 18 Kohlenstoffatomen, im Alkylrest besonders geeignet sind. Die wirksame Menge an Antistatikum liegt im Bereich von 0,05 bis 0,5 Ge .-%, Des weiteren ist Glycerinmonostearat geeignet und wird in einer Menge von 0,03 % bis 0,5 Gew.-% als Antistatikum eingesetzt.Preferred antistatic agents are alkali alkane sulfonates, polyether-modified, ie 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 to 20 atoms which are substituted with ω-hydroxy (C 1 -C 4 ) alkyl groups, 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. Glycerol monostearate is also suitable and is used in an amount of 0.03% to 0.5% by weight as an antistatic.
Geeignete Antiblockmittel sind anorganische Zusatzstoffe wie Siliciumdioxid, Cal- ciumcarbonat, Magnesiumsilicat, Aluminiumsilikat, Calciumphosphat und dergleichen und/oder unverträgliche organische Polymerisate wie Polyamide, Polyacrylate, Poly- methacrylate, Polyester, Polycarbonate und dergleichen, bevorzugt werden Poly- methacrylate und Siliciumdioxid eingesetzt. Die wirksame Menge an Antiblockmittel liegt im Bereich von 0,1 bis 2 Gew.-%, vorzugsweise 0,1 bis 0,8 Gew.-%. Die mittlere Teilchengröße liegt zwischen 1 und 6 μm, insbesondere 2 und 5 μm, wobei Teilchen mit einer kugelförmigen Gestalt besonders geeignet sind.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, polyacrylates, polymethacrylates, polyesters, polycarbonates and the like; preference is given to using polymethacrylates and silicon dioxide. The effective amount of antiblocking agent is in the range of 0.1 to 2% by weight, preferably 0.1 to 0.8% by weight. The average particle size is between 1 and 6 μm, in particular 2 and 5 μm, particles with a spherical shape being particularly suitable.
Gleitmittel sind höhere aliphatische Säureamide, höhere aliphatische Säureester, Wachse und Metallseifen sowie Polydimethylsiloxane. Die wirksame Menge an Gleitmittel liegt im Bereich von 0,01 bis 3 Gew.-%, vorzugsweise 0,02 bis 1 Gew.-%. Besonders geeignet ist der Zusatz von höheren aliphatischen Säureamiden im Bereich von 0,01 bis 0,25 Gew.-%. Ein insbesondere geeignetes aliphatisches Säureamid ist Erucasäureamid. Der Zusatz von Polydimethylsiloxanen ist im Bereich von 0,02 bis 2 Gew.-% bevorzugt, insbesondere Polydimethylsiloxane mit einer Viskosität vonLubricants 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 is particularly suitable. A particularly suitable aliphatic acid amide is erucic acid amide. The addition of polydimethylsiloxanes in the range from 0.02 to 2% by weight is preferred, in particular polydimethylsiloxanes with a viscosity of
5000 bis 1 000 000 mm2/ s.5000 to 1,000,000 mm 2 / s.
Zur Herstellung der Haftvermittlerschicht werden modifizierte Polyolefine eingesetzt. Vorzugsweise sind dies Polyolefine mit Carboxylgruppen, wie z.B. Polypropylen oder Polyethylen, die mit mindestens einem Monomer aus der Gruppe der α,ß-einfach ungesättigten Dicarbonsäuren, wie z.B. Maleinsäure, Fumarsäure, Itaconsäure oder deren Säureanhydride, Säureester, Säureamide und Säureimideaufgepfropft enthalten, Copolymerisate von Ethylen mit α,ß-einfach ungesättigten Carbonsäuren, wie Acryl- säure, Methacrylsäure und/oder deren Metallsalzen (Zn, Na) und/oder deren Alkyl- (Cι-C4)estern oder entsprechende Pfropfpolymere auf Polyolefine wie Polyethylen oder Polypropylen oder bereits beschriebene verseifte Mischpolymerisate, die mit einem Monomer der o.g. ungesättigten Säuren pfropfpolymerisiert sind. Besonders bevorzugt sind Polyolefine wie Polypropylen oder Copolymerisate von Propylen und Ethylen mit maximal 1,0 Gew.-% aufgepfropften α,ß-einfach ungesättigtem Dicarbonsäureanhydrid wie Maleinsäureanhydrid oder deren verseifte Mischpolymerisate.Modified polyolefins are used to produce the adhesion promoter layer. These are preferably polyolefins with carboxyl groups, such as polypropylene or polyethylene, which contain copolymers of at least one monomer from the group of the α, β-monounsaturated dicarboxylic acids, such as maleic acid, fumaric acid, itaconic acid or their acid anhydrides, acid esters, acid amides and acid imides Ethylene with α, ß-monounsaturated carboxylic acids, such as acrylic acid, methacrylic acid and / or their metal salts (Zn, Na) and / or their alkyl (C 1 -C 4 ) esters or corresponding graft polymers on polyolefins such as polyethylene or polypropylene or already Saponified copolymers described which have been graft-polymerized with a monomer of the abovementioned unsaturated acids. Particularly preferred are polyolefins such as polypropylene or copolymers of propylene and ethylene with a maximum of 1.0% by weight of grafted on α, β-monounsaturated dicarboxylic acid anhydride such as maleic anhydride or their saponified copolymers.
Wird das Haftvermittlerpolymere entweder in die siegelbare Schicht A oder in die Gassperrschicht C eingearbeitet, so werden von dem modifiziertem Polyolefin bis 40 Gew.-%, vorzugsweise 25-30 Gew.-%, bezogen auf schichtbildende Polymere, zur Herstellung der entsprechenden Polymerisate verwendet.If the adhesion promoter polymer is incorporated either in the sealable layer A or in the gas barrier layer C, up to 40% by weight, preferably 25-30% by weight, based on layer-forming polymers, of the modified polyolefin are used to produce the corresponding polymers.
Ein weiterer Gegenstand der Erfindung sind Verpackungen vorzugsweise für sauerstoffempfindliche Lebensmittel aus der erfindungsgemäßen Mehrschichtfolie.The invention further relates to packaging preferably for oxygen-sensitive foods made from the multilayer film according to the invention.
Die erfindungsgemäßen Folien können nach den üblichen Verfahren wie Laminierung,The films according to the invention can be prepared using the customary processes such as lamination,
Beschichtung oder Schmelzcoextrusion hergestellt werden. Nach der Extrusion und der Verfestigung des Dickfilms auf der Gießwalze wird der Film in Laufrichtung (längs) mit einem Verstreckungsquotienten von 4/1 bis 7/1 bei einer Temperatur von 120°C - 150°C gereckt. Das Reckverhältnis in Querrichtung liegt vorzugsweise zwi- sehen 8/1 und 12/1 und das Querrecken des Filmes wird bei einer Temperatur zwischen 130°C und 170°C vorgenommen. Die nachfolgende Thermofixierung wird vorzugsweise bei 1°C - 40°C unter der Querrecktemperatur durchgeführt. Um die Affinität der weitgehend unpolaren Folienoberfläche zu den Druckfarben zu gewährleisten, ist es nötig, die Folie einer Corona-(Sprüh) Vorbehandlung zu unterziehen. Dabei wird der Luftsauerstoff in Form von Carbonyl-, Epoxid-, Ether- oder Alkoholgruppen auf der Folienoberfläche eingelagert. Weitere Methoden der Vorbehandlung von Polypropylenfolien sind die Flamm-, Plasma- und Fluorvorbehandlung. BeispielCoating or melt coextrusion can be produced. After the extrusion and the solidification of the thick film on the casting roll, the film is stretched in the running direction (lengthways) with a stretching ratio of 4/1 to 7/1 at a temperature of 120 ° C - 150 ° C. The stretch ratio in the transverse direction is preferably between 8/1 and 12/1 and the transverse stretching of the film is carried out at a temperature between 130 ° C. and 170 ° C. The subsequent heat setting is preferably carried out at 1 ° C - 40 ° C below the transverse stretching temperature. In order to ensure the affinity of the largely non-polar film surface for the printing inks, it is necessary to subject the film to a corona (spray) pretreatment. The atmospheric oxygen is stored in the form of carbonyl, epoxy, ether or alcohol groups on the film surface. Other methods of pretreating polypropylene films are flame, plasma and fluorine pretreatment. example
Zur Herstellung einer Schichtkombination wurden für die Schicht A in 98,7 Gew.-% eines Propylen-Ethylen-Copolymerisates mit 4,5 Gew.-% Ethylen, der Dichte 0,90 g/cm3 mit dem Schmelzindex 5g/10 min bei 230 °C/2,16 kp/cm2 und dem Kristal- litschmelzpunkt 140 °C 0,5 Gew.-% N,N-Bis-(2-hydroxyethyl)-(C12-C16)-alkylamin, 0,3 Gew.-% eines Polydimethylsiloxans der Dichte von 0,985 g/cm3 bei 20°C und einer Viskosität von 106 m Pa s und 0,3 Gew.-% Siliciumdioxid mit einer mittleren Teilchengröße von 2,5 μm eingearbeitet und mit einem modifizierten Polypropylen wie einem verseiften Mischpolymerisat mit 0,7 Gew.-% aufgepfropften Maleinsäureanhydrid und einem Schmelzindex von 5 g/10 min bei 250 °C/216 kp/cm2 für die Haftvermittlerschichten und einem alternierenden Kohlenmonoxid-Ethylen Copoiyme- risat (F. 220°C, MFI 6ml/10min bei 230°C/2,16 kg) für die Gassperrschicht coextrudiert, nach üblichen Verfahren mit der Basisfolie aus Polypropylen der Dichte 0,905 g/cm3, mit dem Schmelzindex von 2 g/10 min bei 230°C/2,16 kp/cm2 und demTo produce a layer combination, 98.7% by weight of a propylene-ethylene copolymer with 4.5% by weight of ethylene had a density of 0.90 g / cm 3 with a melt index of 5 g / 10 min for layer A 230 ° C / 2.16 kp / cm 2 and the crystalline melting point 140 ° C 0.5 wt .-% N, N-bis (2-hydroxyethyl) - (C 12 -C 16 ) alkylamine, 0, 3 wt .-% of a polydimethylsiloxane with a density of 0.985 g / cm 3 at 20 ° C. and a viscosity of 10 6 m Pa s and 0.3 wt .-% silicon dioxide with an average particle size of 2.5 μm and incorporated with a modified polypropylene such as a saponified copolymer with 0.7% by weight of grafted maleic anhydride and a melt index of 5 g / 10 min at 250 ° C / 216 kp / cm 2 for the adhesion promoter layers and an alternating carbon monoxide-ethylene copolymer (F. 220 ° C, MFI 6ml / 10min at 230 ° C / 2.16 kg) co-extruded for the gas barrier layer, according to conventional methods with the base film made of polypropylene with a density of 0.905 g / cm 3 , with which Melt index of 2 g / 10 min at 230 ° C / 2.16 kp / cm 2 and that
Erweichungsbereich von 160 bis 166 °C verbunden und verstreckt, so daß eine Verbundfolie mit einer Längsreckung im Verhältnis 5:1 und einer Querreckung im Verhältnis 10: 1 erhalten wurde. Der Schichtaufbau und die Schichtdicken sind in Tabelle 1 zusammengefaßt. Die Sauerstoffbarriere der Verbundfolie beträgt 15 cm3/m2 d bar.Softening range of 160 to 166 ° C connected and stretched so that a composite film with a longitudinal stretching in the ratio 5: 1 and a transverse stretching in the ratio 10: 1 was obtained. The layer structure and the layer thicknesses are summarized in Table 1. The oxygen barrier of the composite film is 15 cm 3 / m 2 d bar.
Tabelle 1Table 1
Schichtaufbau und Schichtdicke:Layer structure and layer thickness:
P E-Copo 1 μmP E-Copo 1 μm
HV 0,5 μmHV 0.5 μm
Polyketon 1 μm1 µm polyketone
HV 0,5 μmHV 0.5 μm
PP 24 μmPP 24 μm
HV 0,5 μmHV 0.5 μm
Polyketon 1 μm1 µm polyketone
HV 0,5 μmHV 0.5 μm
P/E-Copo 1 μm P / E-Copo 1 μm

Claims

Patentansprücheclaims
1) Heißsiegelbare Verbundfolie aus einer biaxial gereckten Polypropylenfolie als Basisfolie, einer Haftvermittlerschicht aus modifiziertem Polyolefin, einer Gas- Sperrschicht aus einem Copolymer aus Ethylen und Kohlenmonoxid und einer1) Heat-sealable composite film made of a biaxially stretched polypropylene film as the base film, an adhesion promoter layer made of modified polyolefin, a gas barrier layer made of a copolymer of ethylene and carbon monoxide and one
Heißsiegelschicht aus Olefinpolymerisaten, dadurch gekennzeichnet, daß die Basisfolie mindestens auf einer Oberfläche eine gegebenenfalls wenigstens monoaxial orientierte Schichtkombination trägt, die sich zusammensetzt ausHeat seal layer made of olefin polymers, characterized in that the base film carries at least on one surface an optionally at least monoaxially oriented layer combination, which is composed of
A) einer heißsiegelbaren Außenschicht aus einem olefinischen Homo-, Co- oder Terpolymerisat;A) a heat-sealable outer layer made of an olefinic homo-, co- or terpolymer;
B) einer Haftvermittlerschicht aus modifiziertem Polyolefin;B) an adhesion promoter layer made of modified polyolefin;
C) einer Gassperrschicht aus einem Copolymer aus einem oder mehreren Olefinen und Kohlenmonoxid (Polyketon); D) einer Haftvermittlerschicht aus modifiziertem Polyolefin undC) a gas barrier layer made of a copolymer of one or more olefins and carbon monoxide (polyketone); D) an adhesion promoter layer made of modified polyolefin and
E) einer Schicht aus Polyethylen einem Ethylenpolymerisat mit wenigstens 3 Gew.-% Ethylen,E) a layer of polyethylene an ethylene polymer with at least 3% by weight of ethylene,
die Basisfolie auf mindestens einer ihrer Oberflächen gegebenenfalls eine Schicht A, eine Schichtkombination A bis E, A bis D oder B und C trägt.the base film optionally carries a layer A, a layer combination A to E, A to D or B and C on at least one of its surfaces.
2) Verbundfolie nach Anspruch 1, dadurch gekennzeichnet, daß die Gassperrschicht aus einem Terpolymer aus Kohlenmonoxid, Ethylen und Propylen besteht.2) composite film according to claim 1, characterized in that the gas barrier layer consists of a terpolymer of carbon monoxide, ethylene and propylene.
3) Verbundfolie nach Anspruch 1, dadurch gekennzeichnet, daß Kohlenmonoxid und das/die Olefine in alternierender Abfolge in das Terpolymer der Gassperrschicht eingebaut sind.3) composite film according to claim 1, characterized in that carbon monoxide and the / the olefins are installed in an alternating sequence in the terpolymer of the gas barrier layer.
4) Verbundfolie nach Anspruch 3, dadurch gekennzeichnet, daß das Terpolymer aus 50 Mol-% Kohlenmonoxid, 25-24 Mol-% Ethylen und 5-25 Mol-% Propylen besteht. 5) Verbundfolie nach Anspruch 1, dadurch gekennzeichnet, daß die Schichten A und B und/oder D und E oder die Schichten B und C bzw. C und D zu einer Schicht durch Vermischen der entsprechenden Polymeren vereinigt sind.4) composite film according to claim 3, characterized in that the terpolymer consists of 50 mol% carbon monoxide, 25-24 mol% ethylene and 5-25 mol% propylene. 5) Composite film according to claim 1, characterized in that the layers A and B and / or D and E or the layers B and C or C and D are combined to form a layer by mixing the corresponding polymers.
6) Verbundfolie nach mindestens einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß mindestens die Siegel- bzw. Deckschichten mit Additiven, wie Gleitmittel, Antiblockmittel und Antistatika ausgestattet sind.6) Composite film according to at least one of the preceding claims, characterized in that at least the sealing or cover layers are equipped with additives such as lubricants, antiblocking agents and antistatic agents.
7) Verbundfolie nach Anspruch 1, dadurch gekennzeichnet, daß die Schicht B aus Polypropylen oder Polyethylen mit aufgepfropften Einheiten von Maleinsäure, Fumarsäure, Itaconsäure oder deren Säureanhydride, Säureester, Säureamide und Säureimide oder Copolymerisaten von Ethylen mit Acrylsäure, Methacrylsäure, und/oder deren Metallsalzen und/oder deren Alky^d -ehestem oder entsprechenden Pfropfpolymeren besteht.7) Composite film according to claim 1, characterized in that the layer B made of polypropylene or polyethylene with grafted units of maleic acid, fumaric acid, itaconic acid or their acid anhydrides, acid esters, acid amides and acid imides or copolymers of ethylene with acrylic acid, methacrylic acid, and / or their metal salts and / or their alky ^ d -estem or corresponding graft polymers.
8) Verbundfolie nach Anspruch 1 , dadurch gekennzeichnet, daß die Schichtpolymeren A und E und/oder B und D identisch sind.8) Composite film according to claim 1, characterized in that the layer polymers A and E and / or B and D are identical.
9) Verbundfolie nach mindestens einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß die Schichtkombination durch Laminieren oder9) composite film according to at least one of the preceding claims, characterized in that the layer combination by lamination or
Schmelzextrudieren hergestellt wird.Melt extruding is produced.
10) Verbundfolie nach mindestens einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß sie auf den äußeren Deckschichten flamm-, plasma- oder coronavorbehandelt ist.10) composite film according to at least one of the preceding claims, characterized in that it is flame, plasma or corona pretreated on the outer cover layers.
11) Verpackungen, vorzugsweise für Lebensmittel, hergestellt aus Verbundfolien nach einem der vorstehenden Ansprüche. 11) Packaging, preferably for food, made from composite films according to one of the preceding claims.
EP98922756A 1997-04-30 1998-04-21 Multi-layered stretched hot-sealable polypropylene film with a polyketone gas barrier layer Withdrawn EP0977665A1 (en)

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