WO2004073978A1 - Metallisierte opake folie - Google Patents
Metallisierte opake folie Download PDFInfo
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- WO2004073978A1 WO2004073978A1 PCT/EP2004/001664 EP2004001664W WO2004073978A1 WO 2004073978 A1 WO2004073978 A1 WO 2004073978A1 EP 2004001664 W EP2004001664 W EP 2004001664W WO 2004073978 A1 WO2004073978 A1 WO 2004073978A1
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- weight
- propylene
- cover layer
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Classifications
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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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
- B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
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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
-
- 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
- B32B2038/0052—Other operations not otherwise provided for
- B32B2038/0092—Metallizing
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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
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/41—Opaque
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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
- 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
- B32B2323/04—Polyethylene
- B32B2323/043—HDPE, i.e. high density polyethylene
-
- 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
- B32B2439/40—Closed containers
- B32B2439/46—Bags
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- 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
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2813—Heat or solvent activated or sealable
- Y10T428/2817—Heat sealable
- Y10T428/2826—Synthetic resin or 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]
- Y10T428/31678—Of metal
- Y10T428/31692—Next to 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
- Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon
Definitions
- the present invention relates to a metallized opaque polypropylene film and its use in laminates, and to a method for producing pouch packaging from these laminates
- Biaxially oriented polypropylene films are used today as packaging films in a wide variety of applications.
- Polypropylene films are characterized by many advantageous usage properties such as high transparency, gloss, barrier against water vapor, good printability, rigidity, puncture resistance, etc.
- opaque polypropylene films have developed very successfully in recent years. On the one hand, the special appearance (opacity and whiteness) of these films is particularly desirable for some applications. On the other hand, opaque films offer the user a higher yield due to the reduced density of these films.
- polypropylene films have so far not been able to establish themselves as the sole packaging material, particularly for moisture and oxygen sensitive products.
- both the water vapor barrier and the oxygen barrier play a decisive role. With a water absorption of only about 3%, potato chips and other snack items become so sticky that the consumer perceives them as inedible.
- the oxygen barrier must ensure that the fats contained in the snack items do not develop a rancid taste through photo-oxidation.
- the polypropylene film alone does not meet these requirements as packaging material.
- the barrier properties of polypropylene films with a vacuole-containing base layer are even more problematic, since with these types the vacuoles in the base layer additionally impaired the water vapor barrier.
- the water vapor barrier of a transparent biaxially oriented polypropylene film of 25 ⁇ m is approximately 4.4 g / m 2 * day at 38 ° C.
- a comparable barrier value can only be achieved with an opaque film with a vacuole-containing base layer from a thickness of 35 ⁇ m.
- the oxygen barrier for both transparent and opaque polypropylene films is completely inadequate for many applications.
- boPP foils are only metallized with a view to their visual appearance.
- the consumer should get the impression of high-quality packaging without actually having a better barrier.
- the requirements for the metallized film are comparatively uncritical.
- the metallized film only has to have a uniform appearance and adequate metal adhesion.
- DE 39 33 695 describes a non-sealable film consisting of a base layer made of polypropylene and at least one cover layer, which is composed of a special ethylene-propylene copolymer.
- This copolymer is characterized by an ethylene content of 1.2 to 2.8% by weight and a distribution factor of> 10 and a melting enthalpy of> 80 J / g and a melt index of 3 to 12 g / 10min (21, 6N and 230 ° C). It is described that the properties of the copolymer must be kept within these narrow limits in order to improve the printability and the optical properties. Overall, this document refers to transparent films.
- the present invention was based on the special task of providing a bag packaging for powdered filling material which protects the filling material particularly well against moisture and oxygen supply and which at the same time has an appealing printed appearance from the outside.
- the usual usage properties of the film with regard to its use as a laminate component must also be retained. For example, the film should still be easy to process.
- a metallized, biaxially oriented opaque polypropylene multilayer film which comprises a vacuole-containing base layer and at least one first cover layer, the first cover layer containing at least 80% by weight of a propylene-ethylene copolymer which has an ethylene content of 1 , 2 to ⁇ 2.8% by weight and a propylene content of 97.2-98.8% by weight and a melting point in the range from 145 to 160 ° C. and an enthalpy of fusion from 80 to 110 J / g and wherein the first cover layer has a thickness of at least 4 ⁇ m and is metallized on its surface.
- a metallized, biaxially oriented, opaque polypropylene multilayer film which comprises a vacuole-containing base layer and at least a first intermediate layer and a first cover layer on the outer side of the first intermediate layer, the first cover layer and the first intermediate layer each having at least 80% by weight.
- the object is further achieved by laminates which are produced from these films.
- the base layer is that layer of the film which makes up more than 50%, preferably more than 65% of the total thickness of the film.
- Intermediate layers are layers that lie between the base layer and another polyolefin layer.
- Cover layers form the outer layers of the unmetallized coextruded film. Cover layers can be applied directly to the base layer. Furthermore, there are embodiments in which the cover layers are applied to the intermediate layer or layers of the film.
- the present invention is based on the known metallized transparent coextruded films which are known to have the required good barrier properties. It has been found that these known metallized films with transparent polyolefin layers cannot be used advantageously for pouch packaging since the sealing properties are inadequate, in particular impurities due to the powdery filling material significantly impair the quality of the sealing seam.
- Various modifications of the coextruded sealing layer were investigated in the context of the present invention. However, this did not solve the problem satisfactorily. Surprisingly, it was found that the sealing properties could be improved by using an opaque base layer with vacuoles (instead of a transparent base). With a vacuole-containing base layer, the quality of the sealed seam was significantly less affected by powder contamination.
- the barrier impaired by a vacuole-containing base layer could be compensated for by modifying the layer of the film to be metallized. It was found that the film with an opaque base layer, after metallization, has an excellent barrier if the layer to be metallized has a thickness of at least 4 ⁇ m and from the propylene-ethylene copolymer with a low ethylene content, as defined in claims 1 and 2 is constructed.
- This thick layer to be metallized can be realized by a single cover layer of appropriate thickness on the opaque base layer.
- An intermediate layer can advantageously also be combined with a cover layer, the total thickness of the intermediate and cover layers likewise being intended to have a minimum thickness of 4 ⁇ m and of course both layers must be made of the said copolymer.
- This embodiment is particularly favorable with regard to additives because the respective additives for the cover layer and for the intermediate layer can be selected independently. For example, antiblocking agents can be added to the top layer where they effectively prevent blocking in small amounts.
- this measure considerably improves the barrier of the opaque film after metallization, although no special barrier properties can be detected on the unmetallized opaque films.
- the metallized opaque films according to the invention offer improved sealing properties compared to transparent metallized films and, at the same time — despite the vacuole-containing base layer — a very good barrier after metallization both against water vapor and against oxygen.
- This film can therefore be used particularly advantageously for the production of pouch packaging for water-vapor and oxygen-sensitive powdery filling goods.
- the propylene copolymers with a low ethylene content and a high melting point used in the layer to be metallized according to the invention are known per se and are also called "minicopo" in the context of the present invention because of their comparatively low ethylene content.
- minicopo in the context of the present invention because of their comparatively low ethylene content.
- propylene-ethylene copolymers with an ethylene content of 1.2 to 2.8% by weight, in particular 1.2 to 2.3% by weight, preferably 1.5 to ⁇ 2% by weight. -% particularly preferred.
- the melting point is preferably in a range from 150 to 155 ° C and the enthalpy of fusion is preferably in a range from 90 to 100J / g.
- the melt flow index is generally 3 to 15 g / 10 min, preferably 3 to 9 g / 10 min (230 ° C, 21, 6N DIN 53 735). Furthermore, it is particularly advantageous if a high proportion of the
- Ethylene units are built into the propylene chain in isolation between two propylene units. This characteristic can be described using a so-called distribution factor, which should generally be more than 5, preferably more than 10, in particular> 15. The determination of the distribution factor is described, for example, in DE 39 33 695 (page 2), which is hereby expressly stated
- the first cover layer contains at least 80% by weight, preferably
- the top layer can be customary
- small amounts of a second different polyolefin, preferably propylene polymer can be present if its proportion is below 20% by weight, preferably below 5% by weight, and the metallizability of the layer is not impaired.
- antiblocking agents are incorporated via concentrates based on another polymer, such as, for example, propylene homopolymer or other propylene copolymers.
- additives that impair the metallizability should not be contained in the top layer. This applies, for example, to migrating lubricants or antistatic agents.
- the metallizable layer is a combination of a first cover layer D and a first intermediate layer Z, which is applied between said first cover layer and the base layer B, i.e. one surface of this intermediate layer is connected to the base layer and the second opposite surface is connected to the cover layer, according to a structure BZD
- both layers, first cover layer and first intermediate layer are constructed from the same minicopo described above.
- Both layers each contain at least 80% by weight, preferably 95 to 100
- composition of the individual layers need not be identical.
- These embodiments with a combination of intermediate layer and cover layer are advantageous with regard to possible different additives of the individual layers.
- antiblocking agents it is only possible to use.
- Stabilizers and neutralizing agents included are preferred which do not contain any vacuole-containing fillers.
- TiO 2 can be added without significant technical disadvantages, although the this achieved a higher degree of whiteness in the application, if at all, would only be recognizable as a whiter look on the inside after opening the bag.
- the thickness of the first cover layer is generally at least 4 ⁇ m, preferably 5 to 10 ⁇ m.
- this information applies correspondingly to the total thickness of the intermediate layer and the cover layer, the thickness of the intermediate layer generally being at least 3.5 ⁇ m, preferably 4.5-8 ⁇ m, and the thickness of the cover layer generally 0.5 to 4 ⁇ m, is preferably 0.5 to 2 ⁇ m.
- the surface of the first cover layer is generally subjected to a process for increasing the surface tension in a manner known per se by means of corona, flame or plasma.
- the surface tension of the as yet unmetallized top layer treated in this way then typically lies in a range from 35 to 45 mN / m.
- the film according to the invention is further characterized by vacuoles in the base layer, which give the film an opaque appearance.
- “opaque film” means an opaque film whose light transmission (ASTM-D 1003-77) is at most 70%, preferably at most 50%.
- the vacuole-containing base layer of the multilayer film contains polyolefin, preferably a propylene polymer and vacuole-initiating fillers and, if appropriate, further conventional additives in effective amounts in each case.
- the base layer contains at least 70% by weight, preferably 75 to 98% by weight, in particular 85 to 95% by weight, of the polyolefin, in each case based on the weight of the layer.
- the base layer can additionally contain pigments, in particular TiO 2 .
- Propylene polymers are preferred as polyolefins of the base layer.
- propylene polymers contain 90 to 100% by weight, preferably 95 to 100% by weight, in particular 98 to 100% by weight, of propylene units and have a melting point of 120 ° C. or higher, preferably 150 to 170 ° C., and in generally a melt flow index of 1 to 10 g / 10 min, preferably 2 to 8 g / 10 min, at 230 ° C and a force of 21.6 N (DIN 53735).
- the percentages by weight refer to the respective polymer.
- Suitable other polyolefins in the polymer mixture are polyethylenes, in particular HDPE, MDPE, LDPE, VLDPE and LLDPE, the proportion of these polyolefins in each case not exceeding 15% by weight, based on the polymer mixture.
- the opaque base layer of the film generally contains vacuole-initiating fillers in an amount of at most 30% by weight, preferably 2 to 25% by weight, in particular 2 to 15% by weight, based on the weight of the opaque base layer.
- vacuole-initiating fillers are solid particles which are incompatible with the polymer matrix and when the
- vacuole-like cavities size, type and The number of vacuoles depends on the amount and size of the solid particles and the stretching conditions, such as stretching ratio and stretching temperature.
- the vacuoles reduce the density and give the films a characteristic pearlescent, opaque appearance, which is caused by light scattering at the "vacuole / polymer matrix" interfaces.
- the light scattering on the solid particles themselves generally contributes comparatively little to the opacity of the film.
- 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 to 4 ⁇ m.
- the chemical character of the particles plays a 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, of 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, of 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 copolymers of cyclic olefins (COC) as described in EP-AO 623 463, polyesters, polystyrenes, polyamides, halogenated organic polymers, polyesters such as polybutylene terephthalates and cycloolefin copolymers are preferred.
- COC cyclic olefins
- polyesters, polystyrenes, polyamides, halogenated organic polymers, polyesters such as polybutylene terephthalates and cycloolefin copolymers 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 base layer can additionally contain pigments, for example in an amount of 0.5 to 10% by weight, preferably 1 to 8% by weight, in particular 1 to 5% by weight.
- 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 caused by the particles themselves.
- pigments is generally linked to an average particle diameter in the range from 0.01 to a maximum of 1 ⁇ m and includes both so-called “white pigments”, which color the films white, and “colored pigments”, which give the film a colored or black color
- the average particle diameter of the pigments is in the range from 0.01 to 1 ⁇ m, preferably 0.01 to 0.7 ⁇ m, in particular 0.01 to 0.4 ⁇ m.
- Common 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, among which white pigments such as calcium carbonate, silicon dioxide, titanium dioxide and barium sulfate are preferably used. Titanium dioxide is particularly preferred. Various modifications and coatings of TiO 2 are known per se in the prior art.
- the density of the film is essentially determined by the density of the base layer.
- the density of the vacuole-containing base layer will generally be reduced by the vacuoles, unless larger amounts of TiO2 compensate for the density-reducing effect of the vacuoles.
- the density of the opaque base layer is in a range of 0.45-0.85 g / cm 3 .
- the density of the film can vary within a wide range for the white-opaque embodiments described and is generally in a range from 0.5 to 0.95 g / cm 3 , preferably 0.6 to 0.9 g / cm 3 .
- the density is fundamentally increased by adding TiO 2 , but at the same time reduced by the vacuole-initiating fillers in the base layer.
- the density of the opaque base layer is preferably in a range from 0.45 to 0.75 g / cm 3 , whereas for the white-opaque base layer the range is from 0.6 to 0.9 g / cm 3 . cm 3 is preferred
- the total thickness of the film is generally in a range from 20 to 100 ⁇ m, preferably 25 to 60 ⁇ m, in particular 30 to 50 ⁇ m.
- the thickness of the base layer is accordingly 10 to 50 ⁇ m, preferably 10 to 40 ⁇ m.
- the film comprises further layers which are applied to the opposite side of the base layer.
- a second cover layer results in three- or four-layer films.
- Embodiments which additionally have a second intermediate layer and a second cover layer applied thereon lead to four- or five-layer films.
- the thickness of the second cover layer is generally 0.5-3 ⁇ m
- intermediate layers are in the range from 1 to 8 ⁇ m.
- Combinations of intermediate layer and cover layer preferably have a total thickness of 2 to 8 ⁇ m.
- Sealable layers are preferred as further layers, which are understood to mean both heat-sealable and cold-sealable layers. Cold seal coatings can also be applied directly to the surface of the base layer. In general, however, it is preferred to first cover the base layer with a polymer cover layer and to apply the cold seal coating to this polymer cover layer.
- the additional layer or layers generally contain at least 80% by weight, preferably 90 to ⁇ 100% by weight, of olefinic polymers or mixtures thereof.
- Suitable polyolefins are, for example, polyethylenes, propylene copolymers and / or propylene terpolymers, and also the propylene homopolymers already described in connection with the base layer.
- Suitable propylene copolymers or terpolymers are generally composed of at least 50% by weight of propylene and ethylene and / or butylene units as comonomers.
- Preferred copolymers are statistical ethylene-propylene copolymers with an ethylene content of 2 to 10% by weight, preferably 5 to 8% by weight, or statistical propylene-butylene-1 copolymers with a butylene content of 4 to 25 % By weight, preferably 10 to 20% by weight, in each case based on the total weight of the copolymer, or statistical ethylene-propylene-butylene-1 terpolymers with an ethylene content of 1 to 10% by weight, preferably 2 to 6% by weight .-%, and a butylene 1 content of 3 to 20 wt .-%, preferably 8 to 10 wt .-%, each based on the total weight of the terpolymer.
- copolymers and terpolymers generally have a melt flow index of 3 to 15 g / 10min, preferably 3 to 9 g / 10min (230 ° C, 21, 6N DIN 53735) and a melting point of 70 to 145 ° C, preferably 90 to 140 ° C (DSC).
- Suitable polyethylenes are, for example, HDPE, MDPE, LDPE, LLDPE, VLDPE, of which HDPE and MDPE types are particularly preferred.
- the HDPE generally has an MFI (50 N / 190 ° C.) of greater than 0.1 to 50 g / 10 min, preferably 0.6 to 20 g / 10 min, measured according to DIN 53 735 and a viscosity number, measured according to DIN 53 728, Part 4, or ISO 1191, in the range from 100 to 450 cm 3 / g, preferably 120 to 280 cm 3 / g.
- the crystallinity is 35 to 80%, preferably 50 to 80%.
- the density, measured at 23 ° C according to DIN 53479, method A, or ISO 1183, is in the range of> 0.94 to 0.96 g / cm 3 .
- the melting point, measured with DSC (maximum of the melting curve, heating rate 20 ° C / min), is between 120 and 140 ° C.
- Suitable MDPE generally has an MFI (50 N / 190 ° C.) of greater than 0.1 to 50 g / 10 min, preferably 0.6 to 20 g / 10 min, measured according to DIN 53 735.
- the density, measured at 23 ° C according to DIN 53 479, method A, or ISO 1183, is in the range from> 0.925 to 0.94 g / cm 3 .
- the melting point, measured with DSC (maximum of the melting curve, heating rate 20 ° C / min), is between 115 and 130 ° C.
- the film As a bag packaging for powdered filling goods, a mixture of the described propylene copolymers and / or terpolymers and the mentioned polyethylenes is particularly preferred for the second cover layer and optionally for the second intermediate layer.
- these cover layer mixtures are particularly advantageous if the bag is used for packaging powdered contents.
- a Contamination of the sealing areas cannot be prevented effectively. These contaminants often lead to problems with sealing.
- the sealed seams have a reduced or no strength in the contaminated areas, the tightness of the sealed seam is also impaired.
- the impurities do not interfere with the sealing, or only slightly, if the sealing layers are made up of a mixture of propylene polymers and polyethylenes.
- HDPE and / or MDPE-containing cover layer mixtures with an HDPE or MDPE content of 10 to 50% by weight, in particular 15 to 40% by weight, are particularly advantageous for this.
- the layer thickness of the second cover layer, or the total thickness of the second intermediate layer and the second cover layer should be at least 4 ⁇ m, preferably 4 to 8 ⁇ m, in particular 4 to 6 ⁇ m.
- all layers of the film preferably contain neutralizing agents and stabilizers in effective amounts.
- 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 stabilizers, alkali / alkaline earth stearates and / or alkali / alkaline earth carbonates are particularly suitable. Phenolic stabilizers are preferred in an amount of 0.1 to 0.6% by weight, in particular 0.15 to 0.3% by weight, and with a molar mass of more than 500 g / mol.
- Neutralizing agents are preferably calcium stearate and / or calcium carbonate and / or synthetic dihydrotalcite (SHYT) 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. In general, neutralizing agents are used in an amount of 50 to 1000 ppm, based on the layer.
- antiblocking agents are added to the top layer to be metallized and to the opposite top 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 polymers such as polymethyl methacrylate (PMMA), polyamides, polyesters, polycarbonates and the like; preference is given to polymethyl methacrylate (PMMA), silicon dioxide and calcium carbonate.
- the effective amount of antiblocking agent is in the range from 0.1 to 2% by weight, preferably 0.1 to 0.5% by weight, based on the respective top layer.
- the average particle size is between 1 and 6 ⁇ m, in particular 2 and 5 ⁇ m, particles with a spherical shape, as described in EP-A-0 236 945 and DE-A-38 01 535, being particularly suitable.
- the invention further relates to a method for producing the multilayer film according to the invention by the coextrusion method known per se, the stenter method being particularly preferred.
- the melts corresponding to the individual layers of the film are coextruded through a flat die, the film obtained in this way is pulled 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.
- the polymer or the polymer mixture of the individual layers is compressed and liquefied in an extruder, it being possible for the vacuole-initiating fillers and other optionally added additives to be contained in the polymer or in the polymer mixture. Alternatively, these additives can also be incorporated using a masterbatch.
- melts are then pressed together and 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 5 to 100 ° C., preferably 10 to 50 ° C., while cooling and cooling solidified.
- 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 80 to 150 ° C., expediently with the aid of two rollers running at different speeds according to the desired stretching ratio, and the transverse stretching is preferably carried out at a temperature of 120 to 170 ° C. with the aid of an appropriate tenter frame.
- the longitudinal stretching ratios are in the range from 4 to 8, preferably 4.5 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, in particular 39 to 40 mN / m.
- the film is passed between two conductor elements serving as electrodes, such a high voltage, usually AC voltage (approximately 10,000 V and 10,000 Hz), being applied between the electrodes that spray or corona discharges can take place.
- the air above the film surface is ionized by the spray or corona discharge and reacts with the molecules of the film surface, so that polar inclusions arise in the essentially non-polar polymer matrix.
- the treatment intensities are in the usual range, with 37 to 45 mN / m being preferred.
- the co-extruded multilayer film is provided with a metal layer, preferably made of aluminum, on the outer surface of the first cover layer by the methods known per se.
- This metallization takes place in a vacuum chamber in which aluminum is evaporated and deposited on the film surface.
- the surface to be metallized is subjected to a plasma treatment immediately before the metallization.
- the thickness of the metal layer generally correlates with the optical density of the metallized film, i.e. the thicker the metal layer, the higher the optical density of the metallized film.
- the optical density of the metallized film according to the invention should be at least 2, in particular 2.5 to 4.
- the foil metallized in this way can be used directly for the production of pouch packaging, for example for packaging potato flakes, coffee powder, etc.
- the opaque film according to the invention is distinguished by excellent barrier values which have not yet been implemented for opaque films.
- the water vapor permeability of the opaque metallized film according to the invention is generally ⁇ 0.5 g / m 2 * day at 38 ° C. and 90% relative atmospheric humidity, preferably in a range from 0.05 to 0.3 g / m 2 * day.
- the oxygen permeability is preferably ⁇ _ 50 cm 3 / m 2 * day * bar, preferably 5 to 30 cm 3 / m 2 * day * bar, in particular 5 to 25 cm 3 / m 2 * day * bar.
- the metallized film according to the invention is laminated with a further biaxially oriented film, the lamination taking place against the metallized side of the metallized film.
- the other boPP film is preferably printed so that the bag packaging has an attractive appearance.
- transparent or opaque boPP films can be used for the additional film.
- the metallized film is preferably laminated against an opaque multi-layer boPP film which has a vacuole-containing base layer and a printable cover layer.
- Suitable are, for example, four-layer film with a cover layer on one surface of the base layer which is suitable for lamination against the metal layer and a combination of homopolymer intermediate layer, which may have been modified with TiO2, and a printable cover layer applied thereon on the opposite surface of the base layer.
- These laminates are characterized by a particularly attractive surface gloss of the finished printed laminate.
- the melt flow index was measured according to DIN 53 735 at 21.6 N load and 230 ° C.
- the water vapor permeability is determined in accordance with DIN 53 122 part 2.
- the oxygen barrier effect is determined in accordance with draft DIN 53 380 part 3 at an air humidity of 50%. Determination of the ethylene content
- the ethylene content of the copolymers is determined by means of 13 C-NMR spectroscopy. The measurements were carried out using a Bruker Avance 360 nuclear magnetic resonance spectrometer. The copolymer to be characterized is dissolved in tetrachloroethane so that a 10% mixture is formed. Octamethyl tetrasiloxane (OTMS) was added as a reference standard. The nuclear magnetic resonance spectrum was measured at 120 ° C. The spectra were evaluated as described in JC Randall Polymer Sequence Distribution (Academic Press, New York, 1977).
- the melting point and the enthalpy of fusion are determined by means of DSC (differential scanning calometry) measurement (DIN 51 007 and DIN 53 765). A few milligrams (3 to 5 mg) of the raw material to be characterized are heated in a differential calorimeter at a heating rate of 20 ° C per minute. The heat flow rate is plotted against the temperature and the melting point is determined as the maximum of the melting curve and the enthalpy of melting as the area of the respective melting peak.
- DSC differential scanning calometry
- Density The density is determined according to DIN 53 479, method A.
- the surface tension was determined using the ink method according to DIN 53 364.
- the optical density is the measurement of the transmission of a defined light beam.
- the measurement is carried out using a TCX densitometer from Tobias Associates Ine.
- the optical density is a relative value that is given dimensionless.
- Example 1 The invention is now illustrated by the following examples.
- Example 1 The invention is now illustrated by the following examples.
- a three-layer prefilm was extruded from a slot die at an extrusion temperature of 240 to 270 ° C. This pre-film was first removed on a chill roll and cooled. The pre-film was then oriented in the longitudinal and transverse directions and finally fixed. The surface of the first cover layer was pretreated with corona to increase the surface tension.
- the three-layer film had a layer structure of the first cover layer / base layer / second cover layer.
- the individual layers of the film had the following composition:
- Second top layer (2.0 ⁇ m):
- Cooling roll temperature 30 ° C
- the film was surface-treated by means of corona on the surface of the first cover layer and had a surface tension of 38 mN / m.
- the film had a thickness of 40 ⁇ m and an opaque appearance.
- Example 1 An opaque film according to Example 1 was produced. In contrast to Example 1, the composition of the second top layer was changed and a second intermediate layer was added:
- Example 2 An opaque film according to Example 2 was produced.
- a first intermediate layer with a thickness of 4 ⁇ m was inserted between the base layer and the first cover layer.
- the thickness of the first cover layer was reduced from 5 ⁇ m to 1.5 ⁇ m, so that the overall thickness of the first cover layer and the first intermediate layer was 5.5 ⁇ m:
- Example 1 An opaque film according to Example 1 was produced. In contrast to Example 1, the thickness of the first cover layer was only 0.5 ⁇ m. The total thickness of the film was 40 ⁇ m.
- Example 1 An opaque film according to Example 1 was produced.
- the thickness of the first cover layer was reduced from 5 ⁇ m to 1 ⁇ m and a first intermediate layer of 4 ⁇ m made of propylene homopolymer was inserted:
- a film was produced as described in Comparative Example 2. in the The difference to Comparative Example 2 was the composition of the first
- PMMA polymethyl methacrylate
- a film was produced according to Example 1, in contrast to Example 1, the thickness of the first cover layer was only 0.5 ⁇ m.
- the thickness of the first cover layer was only 0.5 ⁇ m.
- the film was a total of 35 microns thick. In contrast to Comparative Example 2, this film was transparent.
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Thermal Sciences (AREA)
- Laminated Bodies (AREA)
- Wrappers (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE200450001343 DE502004001343D1 (de) | 2003-02-20 | 2004-02-20 | Metallisierte opake folie |
EP04713042A EP1597073B1 (de) | 2003-02-20 | 2004-02-20 | Metallisierte opake folie |
CA 2516584 CA2516584A1 (en) | 2003-02-20 | 2004-02-20 | Metallized opaque film |
MXPA05008927A MXPA05008927A (es) | 2003-02-20 | 2004-02-20 | Pelicula opaca metalizada. |
US10/545,118 US20060093812A1 (en) | 2003-02-20 | 2004-02-20 | Metallized opaque film |
AU2004213151A AU2004213151B2 (en) | 2003-02-20 | 2004-02-20 | Metallized opaque film |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10307133.4 | 2003-02-20 | ||
DE2003107133 DE10307133B4 (de) | 2003-02-20 | 2003-02-20 | Metallisierte opake Folie |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004073978A1 true WO2004073978A1 (de) | 2004-09-02 |
Family
ID=32841729
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2004/001664 WO2004073978A1 (de) | 2003-02-20 | 2004-02-20 | Metallisierte opake folie |
Country Status (11)
Country | Link |
---|---|
US (1) | US20060093812A1 (de) |
EP (1) | EP1597073B1 (de) |
CN (1) | CN1750931A (de) |
AT (1) | ATE337910T1 (de) |
AU (1) | AU2004213151B2 (de) |
CA (1) | CA2516584A1 (de) |
DE (2) | DE10307133B4 (de) |
ES (2) | ES2350882T3 (de) |
MX (1) | MXPA05008927A (de) |
WO (1) | WO2004073978A1 (de) |
ZA (3) | ZA200506052B (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006021472A1 (de) * | 2004-08-25 | 2006-03-02 | Treofan Germany Gmbh & Co. Kg | Metallisierte folie mit guten barriereeigenschaften |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1634699A1 (de) * | 2004-09-10 | 2006-03-15 | Syrom 90 S.P.A. | Metallisierter Mehrschichtfilm und Verfahren zur Herstellung |
US8617717B2 (en) * | 2006-06-09 | 2013-12-31 | Exxonmobil Chemical Patents Inc. | Heat sealable films from propylene and α-olefin units |
US8048532B2 (en) | 2006-09-15 | 2011-11-01 | Exxonmobil Oil Corporation | Metallized polymeric films |
US20120145304A1 (en) * | 2009-08-19 | 2012-06-14 | Upm Raflatac Oy | Removable label for containers |
EP3003708A1 (de) | 2013-06-04 | 2016-04-13 | Treofan Germany GmbH & Co. KG | Siegelfähige polypropylenfolie |
Citations (1)
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EP0361280A2 (de) * | 1988-09-28 | 1990-04-04 | Hoechst Aktiengesellschaft | Biaxial orientierte Polypropylenfolie für die Metallisieranwendung |
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US5236680A (en) * | 1987-01-20 | 1993-08-17 | Mizusawa Industrial Chemicals, Ltd. | Preparation of amorphous silica-alumina particles by acid-treating spherical P-type zeolite particles crystallized from a sodium aluminosilicate gel |
US5236683A (en) * | 1987-01-20 | 1993-08-17 | Mizusawa Industrial Chemicals, Ltd. | Amorphous silica spherical particles |
US4897305A (en) * | 1987-03-12 | 1990-01-30 | Hercules Incorporated | Plasma treatment with organic vapors to promote a meal adhesion of polypropylene film |
DE3933695C2 (de) * | 1989-10-09 | 2001-02-08 | Hoechst Trespaphan Gmbh | Polypropylenfolie mit guten Hafteigenschaften |
DE4202982A1 (de) * | 1992-02-03 | 1993-08-05 | Hoechst Ag | Siegelbare, opake, biaxial orientierte polypropylen-mehrschichtfolie, verfahren zu ihrer herstellung und ihre verwendung |
DE4315006A1 (de) * | 1993-05-06 | 1994-11-10 | Hoechst Ag | Siegelbare, opake, biaxial orientierte Polypropylen-Mehrschichtfolie, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE4402689A1 (de) * | 1994-01-29 | 1995-08-03 | Hoechst Ag | Mehrschichtige biaxial orientierte Polypropylenfolie, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE4443411A1 (de) * | 1994-12-07 | 1996-06-13 | Hoechst Ag | Siegelbare, weiß-opake, biaxial orientierte Polypropylen-Mehrschichtfolie, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE4443458A1 (de) * | 1994-12-07 | 1996-06-13 | Wolff Walsrode Ag | Mehrschichtige, gereckte, heißsiegelbare Polypropylenfolie |
EP0874734A1 (de) * | 1995-09-27 | 1998-11-04 | Applied Extrusion Technologies, Inc. | Metallisierte folien |
US6013353A (en) * | 1996-05-07 | 2000-01-11 | Mobil Oil Corporation | Metallized multilayer packaging film |
US5981079A (en) * | 1997-01-29 | 1999-11-09 | Mobil Oil Corporation | Enhanced barrier vacuum metallized films |
US5958566A (en) * | 1997-10-17 | 1999-09-28 | Fina Technology, Inc. | Metal bond strength in polyolefin films |
GB2332390A (en) * | 1997-12-19 | 1999-06-23 | Hoechst Trespaphan Gmbh | Polymeric films |
US6190760B1 (en) * | 1997-12-26 | 2001-02-20 | Toray Industries, Inc. | Biaxially oriented polypropylene film to be metallized a metallized biaxially oriented polypropylene film and a laminate formed by using it |
DE19842376A1 (de) * | 1998-09-16 | 2000-03-23 | Hoechst Diafoil Gmbh | Biaxial orientierte Polypropylenfolie, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE19949898C2 (de) * | 1999-10-15 | 2003-01-30 | Trespaphan Gmbh | Verwendung einer Polyolefinfolie als In-Mould-Etikett |
US20030211298A1 (en) * | 1999-12-30 | 2003-11-13 | Migliorini Robert A. | Multi-layer oriented polypropylene films with modified core |
DE10022306A1 (de) * | 2000-05-09 | 2001-11-29 | Trespaphan Gmbh | Transparente biaxial orientierte Polyolefinfolie mit verbesserten Hafteigenschaften |
US6916526B1 (en) * | 2000-07-19 | 2005-07-12 | Toray Plastics (America), Inc. | Biaxially oriented polypropylene metallized film for packaging |
WO2002045956A1 (de) * | 2000-12-06 | 2002-06-13 | Trespaphan Gmbh | Etikettenfolie mit verbesserter haftfähigkeit |
DE10121150A1 (de) * | 2001-04-30 | 2002-11-07 | Trespaphan Gmbh | Opake Folie aus PLA |
AU2002316938B2 (en) * | 2001-06-02 | 2007-06-21 | Trespaphan Gmbh | Film having an improved sealability and adherence |
DE10235557B4 (de) * | 2002-08-03 | 2004-08-26 | Trespaphan Gmbh | Etikettenfolie für In-Mould-Verfahren |
US6773818B2 (en) * | 2002-09-06 | 2004-08-10 | Exxonmobil Oil Corporation | Metallized, metallocene-catalyzed, polypropylene films |
-
2003
- 2003-02-20 DE DE2003107133 patent/DE10307133B4/de not_active Expired - Fee Related
-
2004
- 2004-02-20 ES ES04713057T patent/ES2350882T3/es not_active Expired - Lifetime
- 2004-02-20 DE DE200450001343 patent/DE502004001343D1/de not_active Expired - Lifetime
- 2004-02-20 CN CNA2004800047110A patent/CN1750931A/zh active Pending
- 2004-02-20 MX MXPA05008927A patent/MXPA05008927A/es active IP Right Grant
- 2004-02-20 EP EP04713042A patent/EP1597073B1/de not_active Expired - Lifetime
- 2004-02-20 CA CA 2516584 patent/CA2516584A1/en not_active Abandoned
- 2004-02-20 AU AU2004213151A patent/AU2004213151B2/en not_active Expired
- 2004-02-20 AT AT04713042T patent/ATE337910T1/de not_active IP Right Cessation
- 2004-02-20 ES ES04713042T patent/ES2275210T3/es not_active Expired - Lifetime
- 2004-02-20 US US10/545,118 patent/US20060093812A1/en not_active Abandoned
- 2004-02-20 WO PCT/EP2004/001664 patent/WO2004073978A1/de active IP Right Grant
-
2005
- 2005-07-28 ZA ZA200506052A patent/ZA200506052B/en unknown
- 2005-07-28 ZA ZA200506050A patent/ZA200506050B/en unknown
- 2005-07-28 ZA ZA200506051A patent/ZA200506051B/en unknown
Patent Citations (1)
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EP0361280A2 (de) * | 1988-09-28 | 1990-04-04 | Hoechst Aktiengesellschaft | Biaxial orientierte Polypropylenfolie für die Metallisieranwendung |
Cited By (1)
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---|---|---|---|---|
WO2006021472A1 (de) * | 2004-08-25 | 2006-03-02 | Treofan Germany Gmbh & Co. Kg | Metallisierte folie mit guten barriereeigenschaften |
Also Published As
Publication number | Publication date |
---|---|
ES2275210T3 (es) | 2007-06-01 |
MXPA05008927A (es) | 2005-10-05 |
DE10307133B4 (de) | 2007-05-16 |
EP1597073A1 (de) | 2005-11-23 |
DE10307133A1 (de) | 2004-09-09 |
AU2004213151B2 (en) | 2009-03-12 |
US20060093812A1 (en) | 2006-05-04 |
EP1597073B1 (de) | 2006-08-30 |
ATE337910T1 (de) | 2006-09-15 |
AU2004213151A1 (en) | 2004-09-02 |
ZA200506051B (en) | 2006-06-28 |
CN1750931A (zh) | 2006-03-22 |
DE502004001343D1 (de) | 2006-10-12 |
ES2350882T3 (es) | 2011-01-27 |
ZA200506050B (en) | 2006-07-26 |
CA2516584A1 (en) | 2004-09-02 |
ZA200506052B (en) | 2006-06-28 |
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