DE19718199A1 - Multi-layer, stretched, heat-sealable polypropylene film - Google Patents
Multi-layer, stretched, heat-sealable polypropylene filmInfo
- Publication number
- DE19718199A1 DE19718199A1 DE19718199A DE19718199A DE19718199A1 DE 19718199 A1 DE19718199 A1 DE 19718199A1 DE 19718199 A DE19718199 A DE 19718199A DE 19718199 A DE19718199 A DE 19718199A DE 19718199 A1 DE19718199 A1 DE 19718199A1
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- ethylene
- composite film
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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
Description
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 can be because of their gas barrier properties, especially as packaging film for such goods suitable that 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-2 644 209 und EP 0 062 815 B1 wird durch Einbau einer Schicht aus verseiftem Ethylenvinylacetat die Gasdurchlässigkeit erheblich verringert. Verseiftes Ethylenvi nylacetat weist aber bezüglich seiner Verarbeitbarkeit erhebliche Nachteile auf. In folge der hohen Metallhaftung und der geringen Temperaturstabilität führt es bei der Extrusion häufig zu polymeren Ablagerungen im Extruder und der Extrusionsdüse. 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 Schlauchbeu teln Schwierigkeiten bereitet.The use of composite films made of polyolefins with a sealable layer from ethylene homo- or copolymers as packaging film has long been known. Attempts have also been made to make the gas permeability of such composite films possible to improve the installation of various polar barrier materials. In DE-A-2 644 209 and EP 0 062 815 B1 are made by incorporating a layer of saponified Ethylene vinyl acetate significantly reduces gas permeability. Saponified ethylene vi However, nylacetate has considerable disadvantages with regard to its processability. In due to the high metal adhesion and the low temperature stability it leads to the Extrusion often to polymeric deposits in the extruder and the extrusion die. In order to achieve a low gas permeability, the use of ethylene vinyl is necessary alcohol Copolymers with a relatively high content of vinyl alcohol are necessary. this has to the disadvantage that composite films made of PP and EVOH have only limited stretchability exhibit and require relatively high stretching temperatures. A major disadvantage of barrier films with ethylene vinyl alcohol copolymers as a barrier layer is their low kink resistance, particularly in the manufacture of hose bags difficulties.
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 that 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.Therefore, it turned out to be necessary to use a multilayer, heat-sealable BOPP film to manufacture that contains a barrier material that has a high oxygen barrier has, is easy to process and to a high breaking strength of the Foil composite leads.
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 Olefinpolymerisaten,
dadurch gekennzeichnet, daß die Basisfolie mindestens auf einer Oberfläche eine
gegebenenfalls wenigstens monoaxial orientierte Schichtkombination trägt, die sich
zusammensetzt aus
This object is achieved by a heat-sealable composite film made from a biaxially stretched polypropylene film as the base film, an adhesion promoter layer made from modified polyolefin, a gas barrier layer made from a copolymer of one or more olefins and carbon monoxide and a heat seal layer made from olefin polymers, characterized in that the base film is at least on one Surface carries 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), bei dem das/die Olefin(e) und Kohlenmon oxid in alternierender Abfolge eingebaut sind;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 mon oxide are installed 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 may have a layer A on at least one of its surfaces, carries a layer combination A to E, A to D or B and C.
Gegebenenfalls können 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 Poly meren vereinigt werden.Optionally, layers A and B and / or D and E or the layers B and C or C and D to form a layer by mixing the corresponding poly mer be united.
Das bevorzugte Merkmal besteht darin, daß die mittels eines sequentiellen Verfahren hergestellte biaxial gereckte und heißsiegelbare Polypropylen-Folie eine Gassperr schicht 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. Bevor zugt sind Ethylen und C3- bis C10-Alkene wie beispielsweise Propylen, 1-Buten, 2-Buten, 1-Penten, 1-Hexen, 1-Octen, 1-Nonen, 1-Decen. Besonders bevorzugt sind 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 olefinisch 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.The preferred feature is that the biaxially stretched and heat-sealable polypropylene film produced by a sequential process contains a gas barrier layer made of 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. Preference is given to ethylene and C 3 - to C 10 -alkenes such as propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-octene, 1-nonen, 1-decene. Ethylene and propylene 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 being 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- statistical propylene / ethylene / olefin terpolymers
- - Mischungen aus zwei oder drei der vorstehenden Polymere.Mixtures of two or three of the above polymers.
Besonders bevorzugt wird ein Propylen/Ethylen-Copolymerisat dadurch gekennzeich net, 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.To ensure good machinability of biaxially oriented polypropylene films guarantee, it is necessary to include at least the sealing or cover layers 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-(C1-C4)-alkyl-Gruppen substituiert sind, wo bei N,N-bis-(2-hydroxyethyl)-alkylamine mit 10 bis 20 Kohlenstoffatomen, vorzugs weise 12 bis 18 Kohlenstoffatomen, im Alkylrest besonders geeignet sind. Die wirksame Menge an Antistatikum liegt im Bereich von 0,05 bis 0,5 Gew.-%. 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 with 10 to 20 carbon atoms ω-Hydroxy- (C 1 -C 4 ) -alkyl groups are substituted, where N, N-bis (2-hydroxyethyl) alkylamines having 10 to 20 carbon atoms, preferably 12 to 18 carbon atoms, are particularly suitable in the alkyl radical are. 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, Cal cium carbonate, magnesium silicate, aluminum silicate, calcium phosphate and the like and / or incompatible organic polymers such as polyamides, polyacrylates, poly methacrylates, polyesters, polycarbonates and the like, poly are preferred methacrylates and silicon dioxide used. 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, whereby Particles with a spherical shape are particularly suitable.
Gleitmittel sind höhere aliphatische Säureamide, höhere aliphatische Säureester, Wachse und Metallseifen sowie Polydimethylsiloxane. Die wirksame Menge an Gleit mittel liegt im Bereich von 0,01 bis 3 Gew.-%, vorzugsweise 0,02 bis 1 Gew.-%.Lubricants are higher aliphatic acid amides, higher aliphatic acid esters, Waxes and metal soaps as well as polydimethylsiloxanes. The effective amount of glide medium is in the range from 0.01 to 3% by weight, preferably 0.02 to 1% by weight.
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 von 5000 bis 1 000 000 mm2/s.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 are preferred, in particular polydimethylsiloxanes with a viscosity of 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,β-einfach ungesättigten Dicarbonsäuren, wie z. B. Maleinsäure, Fumarsäure, Itaconsäure oder deren Säureanhydride, Säureester, Säureamide und Säureimide aufgepfropft enthalten, Copolymerisate von Ethylen mit α,β-einfach ungesättigten Carbonsäuren, wie Acryl säure, Methacrylsäure und/oder deren Metallsalzen (Zn, Na) und/oder deren Alkyl- (C1-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. Modified polyolefins are used to produce the adhesion promoter layer. These are preferably polyolefins with carboxyl groups, such as. B. polypropylene or polyethylene, with at least one monomer from the group of α, β-monounsaturated dicarboxylic acids, such as. B. maleic acid, fumaric acid, itaconic acid or their acid anhydrides, acid esters, acid amides and acid imides grafted, copolymers of ethylene with α, β-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 saponified copolymers already described which have been graft polymerized with a monomer of the abovementioned unsaturated acids.
Besonders bevorzugt sind Polyolefine wie Polypropylen oder Copolymerisate von Propylen und Ethylen mit maximal 1,0 Gew.-% aufgepfropften α,β-einfach unge sättigtem Dicarbonsäureanhydrid wie Maleinsäureanhydrid oder deren verseifte Mischpolymerisate.Polyolefins such as polypropylene or copolymers of are particularly preferred Propylene and ethylene with a maximum of 1.0% by weight grafted-on α, β-simple saturated 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 either in the sealable layer A or in the Gas barrier layer C incorporated, so are from the modified polyolefin 40 wt .-%, preferably 25-30 wt .-%, based on layer-forming polymers for Production of the corresponding polymers used.
Ein weiterer Gegenstand der Erfindung sind Verpackungen vorzugsweise für sauerstoffempfindliche Lebensmittel aus der erfindungsgemäßen Mehrschichtfolie.Another object of the invention is packaging for oxygen-sensitive foods from the multilayer film according to the invention.
Die erfindungsgemäßen Folien können nach den üblichen Verfahren wie Laminierung, 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 schen 8/1 und 12/1 und das Querrecken des Filmes wird bei einer Temperatur zwi schen 130°C und 170°C vorgenommen. Die nachfolgende Thermofixierung wird vor zugsweise bei 1°C-40°C unter der Querrecktemperatur durchgeführt. Um die Affini tät 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 Poly propylenfolien sind die Flamm-, Plasma- und Fluorvorbehandlung.The films according to the invention can be prepared using the customary processes such as lamination Coating or melt coextrusion can be produced. After extrusion and As the thick film solidifies on the casting roll, the film becomes in the direction of travel (longitudinal) with a draw ratio of 4/1 to 7/1 at a temperature of Stretched 120 ° C-150 ° C. The stretching 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 between 130 ° C and 170 ° C. The subsequent heat setting is done before preferably carried out at 1 ° C-40 ° C below the transverse stretching temperature. To the affini to ensure the largely non-polar film surface to the printing inks, it is necessary to subject the film to a corona (spray) pretreatment. Here atmospheric oxygen is in the form of carbonyl, epoxy, ether or alcohol groups stored on the film surface. Other methods of pretreating poly Propylene films are flame, plasma and fluorine pretreatment.
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 5 g/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 mPa.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 Maleinsäure anhydrid und einem Schmelzindex von 5 g/10 min bei 250°C/216 kp/cm2 für die Haftvermittlerschichten und einem alternierenden Kohlenmonoxid-Ethylen Copolyme risat (F. 220°C, MFI 6 ml/10 min 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 dem 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.To produce a layer combination, 98.7% by weight of a propylene-ethylene copolymer with 4.5% by weight of ethylene and a density of 0.90 g / cm 3 with a melt index of 5 g / 10 min were used for layer A at 230 ° C / 2, 16 kp / cm 2 and the crystal melting point 140 ° C 0.5 wt .-% N, N-bis (2-hydroxyethyl) - (C 12 -C 16 ) alkylamine, 0, 3% by weight of a polydimethylsiloxane with a density of 0.985 g / cm 3 at 20 ° C. and a viscosity of 106 mPa.s and 0.3% by weight of 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 copolyme risat (F. 220 ° C, MFI 6 ml / 10 min at 230 ° C / 2, 16 kg) coextruded 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 a melt index of 2 g / 10 min at 230 ° C / 2.16 kp / cm 2 and the softening range from 160 to 166 ° C 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.
Claims (11)
- A) einer heißsiegelbaren Außenschicht aus einem olefinischen Homo-, Co- oder Terpolymerisat;
- B) einer Haftvermittlerschicht aus modifiziertem Polyolefin;
- C) einer Gassperrschicht aus einem Copolymer aus einem oder mehreren Olefinen und Kohlenmonoxid (Polyketon);
- D) einer Haftvermittlerschicht aus modifiziertem Polyolefin und
- E) einer Schicht aus Polyethylen einem Ethylenpolymerisat mit wenigstens 3 Gew.-% Ethylen,
- A) a heat-sealable outer layer made of an olefinic homo-, co- or terpolymer;
- 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);
- D) an adhesion promoter layer made of modified polyolefin and
- E) a layer of polyethylene an ethylene polymer with at least 3% by weight of ethylene,
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19718199A DE19718199A1 (en) | 1997-04-30 | 1997-04-30 | Multi-layer, stretched, heat-sealable polypropylene film |
BR9809372-0A BR9809372A (en) | 1997-04-30 | 1998-04-21 | Multi-layered, heat-sealable polypropylene sheet with polyketone gas blocking layer |
PCT/EP1998/002348 WO1998049006A1 (en) | 1997-04-30 | 1998-04-21 | Multi-layered stretched hot-sealable polypropylene film with a polyketone gas barrier layer |
AU75279/98A AU7527998A (en) | 1997-04-30 | 1998-04-21 | Multi-layered stretched hot-sealable polypropylene film with a polyketone gas barrier layer |
CA002288158A CA2288158A1 (en) | 1997-04-30 | 1998-04-21 | Multi-layered stretched hot-sealable polypropylene film with a polyketone gas barrier layer |
EP98922756A EP0977665A1 (en) | 1997-04-30 | 1998-04-21 | Multi-layered stretched hot-sealable polypropylene film with a polyketone gas barrier layer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19718199A DE19718199A1 (en) | 1997-04-30 | 1997-04-30 | Multi-layer, stretched, heat-sealable polypropylene film |
Publications (1)
Publication Number | Publication Date |
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DE19718199A1 true DE19718199A1 (en) | 1998-11-05 |
Family
ID=7828172
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE19718199A Withdrawn DE19718199A1 (en) | 1997-04-30 | 1997-04-30 | Multi-layer, stretched, heat-sealable polypropylene film |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0977665A1 (en) |
AU (1) | AU7527998A (en) |
BR (1) | BR9809372A (en) |
CA (1) | CA2288158A1 (en) |
DE (1) | DE19718199A1 (en) |
WO (1) | WO1998049006A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003013852A1 (en) * | 2001-08-01 | 2003-02-20 | Trespaphan Gmbh | Transparent biaxially oriented polyolefin film with improved sealing qualities |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI405666B (en) * | 2010-12-09 | 2013-08-21 | Ind Tech Res Inst | Gas-barrier heat-seal composite films and vacuum insulation panels comprising the same |
DE102015003516A1 (en) * | 2015-03-20 | 2016-09-22 | Wihuri Packaking Oy | Thermoforming film |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5763101A (en) * | 1995-03-31 | 1998-06-09 | Kuraray Co., Ltd. | Polyalcohol film and laminated film comprising the same |
-
1997
- 1997-04-30 DE DE19718199A patent/DE19718199A1/en not_active Withdrawn
-
1998
- 1998-04-21 WO PCT/EP1998/002348 patent/WO1998049006A1/en not_active Application Discontinuation
- 1998-04-21 EP EP98922756A patent/EP0977665A1/en not_active Withdrawn
- 1998-04-21 BR BR9809372-0A patent/BR9809372A/en not_active Application Discontinuation
- 1998-04-21 AU AU75279/98A patent/AU7527998A/en not_active Abandoned
- 1998-04-21 CA CA002288158A patent/CA2288158A1/en not_active Abandoned
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003013852A1 (en) * | 2001-08-01 | 2003-02-20 | Trespaphan Gmbh | Transparent biaxially oriented polyolefin film with improved sealing qualities |
AU2002321278B2 (en) * | 2001-08-01 | 2007-09-06 | Trespaphan Gmbh | Transparent biaxially oriented polyolefin film with improved sealing qualities |
Also Published As
Publication number | Publication date |
---|---|
EP0977665A1 (en) | 2000-02-09 |
AU7527998A (en) | 1998-11-24 |
CA2288158A1 (en) | 1998-11-05 |
BR9809372A (en) | 2000-07-04 |
WO1998049006A1 (en) | 1998-11-05 |
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