EP3962736A1 - Verfahren zur herstellung einer mehrschichtigen verbundfolie, mehrschichtige verbundfolie und deren verwendung - Google Patents
Verfahren zur herstellung einer mehrschichtigen verbundfolie, mehrschichtige verbundfolie und deren verwendungInfo
- Publication number
- EP3962736A1 EP3962736A1 EP20723390.9A EP20723390A EP3962736A1 EP 3962736 A1 EP3962736 A1 EP 3962736A1 EP 20723390 A EP20723390 A EP 20723390A EP 3962736 A1 EP3962736 A1 EP 3962736A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- composite film
- mpa
- ethylene
- outside
- 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.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 149
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 230000005855 radiation Effects 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 28
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 26
- 238000004132 cross linking Methods 0.000 claims abstract description 20
- 230000002285 radioactive effect Effects 0.000 claims abstract description 7
- 239000004952 Polyamide Substances 0.000 claims description 47
- 229920002647 polyamide Polymers 0.000 claims description 47
- 229920000098 polyolefin Polymers 0.000 claims description 40
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 37
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 36
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 35
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 claims description 34
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 claims description 34
- 229920000554 ionomer Polymers 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 32
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims description 30
- -1 polyethylene terephthalate Polymers 0.000 claims description 30
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 29
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 29
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 24
- 239000004698 Polyethylene Substances 0.000 claims description 23
- 239000004743 Polypropylene Substances 0.000 claims description 23
- 229920000573 polyethylene Polymers 0.000 claims description 23
- 229920001155 polypropylene Polymers 0.000 claims description 23
- 238000007789 sealing Methods 0.000 claims description 20
- 235000013305 food Nutrition 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229920000728 polyester Polymers 0.000 claims description 15
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 14
- 238000007654 immersion Methods 0.000 claims description 12
- 239000002318 adhesion promoter Substances 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 238000004806 packaging method and process Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 8
- 239000004626 polylactic acid Substances 0.000 claims description 7
- 241000251468 Actinopterygii Species 0.000 claims description 3
- 235000013351 cheese Nutrition 0.000 claims description 3
- 235000019688 fish Nutrition 0.000 claims description 3
- 235000013372 meat Nutrition 0.000 claims description 3
- 238000000071 blow moulding Methods 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 2
- 229920000915 polyvinyl chloride Polymers 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 151
- 230000004888 barrier function Effects 0.000 description 22
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 239000002994 raw material Substances 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 230000008901 benefit Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 229920006300 shrink film Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YMOSUBJHLKNJIU-UHFFFAOYSA-N 1,1-dichloroethene Chemical compound ClC(Cl)=C.ClC(Cl)=C YMOSUBJHLKNJIU-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229920012753 Ethylene Ionomers Polymers 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229920000034 Plastomer Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- CAPAZTWTGPAFQE-UHFFFAOYSA-N ethane-1,2-diol Chemical compound OCCO.OCCO CAPAZTWTGPAFQE-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ZWPWUVNMFVVHHE-UHFFFAOYSA-N terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.OC(=O)C1=CC=C(C(O)=O)C=C1 ZWPWUVNMFVVHHE-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
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- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- B32B7/04—Interconnection of layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
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- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
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- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0012—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular thermal properties
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
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- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
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- B32B2250/05—5 or more layers
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Definitions
- the invention relates to a method for producing a multi-layer composite film according to claim 1, a multi-layer composite film according to claim 10 or 11 and the use of the composite film according to claim 20.
- Multi-layer composite films which provide a polyamide resin as the main resin and EVOH as the gas barrier layer, the properties required for the intended use, for example as a heat-shrinkable packaging film for food, exclusively by means of the
- Combinations of raw materials can be achieved.
- the use of higher percentages of the raw materials polyamide, EVOH and PET leads to relatively stiff films.
- the tendency of these raw materials to recrystallize, especially when using PA and EVOH can impair the dimensional stability of the film.
- the use of EVOH as a layer component also has the disadvantage that its barrier properties against oxygen permeation decrease over time due to the action of permeating moisture from outside and inside. Therefore, in order to maintain a sufficient oxygen barrier, the EV OH-containing layer must be protected by embedding in layers with a good water vapor barrier function, for example in the form of a sandwich arrangement, which is disadvantageous for the number of layers required and the complexity of the overall composite increase.
- composite films which use polyamide in one or more layers have the disadvantage of undesirable cold or post-shrinkage.
- the use of polyamide in the outer layer can also lead to an undesirable tendency to roll, known as curling.
- the publication DE 10 2006 046 483 A1 discloses a multilayer food casing or film for food packaging in which a central EVOH-based gas barrier layer is embedded in two polyolefin layers as a water vapor barrier and which has a PET layer for the purpose of heat resistance, puncture resistance and shrinkage .
- document EP 1 857 271 B1 disclose a 7-layer film and document DE 10 2006 036 844 B3 a food casing or film for food packaging in which the EVOH layer is embedded between two PA layers, which in turn are between two PO layers are embedded, and in which the outer layer consists of PET.
- multilayer composite films which are crosslinked by radiation and use PVdC as a barrier material. Due to the radiation crosslinking integrated in the film production process or downstream by radioactive irradiation or irradiation with electrons, essential properties such as sufficiently high shrinkage, good puncture resistance and heat resistance are achieved, which advantageously complement the oxygen, gas and aroma barrier properties that were originally present in PVdC . As the following table 1 shows, cold shrinkage compared to other conventional films can be completely avoided by using radiation-crosslinked PVdC.
- radiation crosslinked composite films often have the disadvantage that, due to the interaction of the raw materials and the radiation crosslinking, the appearance in terms of cloudiness, gloss and coloring (brown or yellowish) is not satisfactory.
- the haze in films based on radiation-crosslinked PVdC is significantly increased compared to other conventional films, as is shown below
- Table 2 Haze, measured with conventional multilayer films based on EVOH vs. radiation crosslinked PVdC (ASTM D1003)
- the further processing of the radiation-crosslinked composite films is limited to further processing machines due to the relatively low or limited number of cycles due to the non-optimal heat resistance and the sometimes too low rigidity of the film, as Table 3 below shows.
- a composite film which has at least one, preferably several of the following properties: high shrinkage, high further processability (high cycle rates), high puncture resistance, high heat resistance, good optical properties in terms of low haze and / or a low color tint, recyclability and a long-term, unaffected or stable oxygen barrier.
- the presence of a slight cloudiness of the composite film is advantageous. Disclosure of the invention
- a method for producing a multilayer composite film comprising at least the following steps:
- the layer (a) forms a surface of the composite film to the outside;
- the layer (c) forms a surface of the composite film which faces or comes into contact with an item to be packaged; and the layer (b) is arranged between the layer (a) and the layer (c);
- layer (a) contains or consists of a thermoplastic resin
- layer (b) contains or consists of a polyvinylidene chloride (PVdC) resin
- the layer (c) contains or consists of a resin, preferably a sealable, in particular heat-sealable resin;
- thermoplastic resin of layer (a) has a density of 0.94 g / cm 3 or more;
- any crosslinking of the composite film by means of radioactive radiation in particular by means of beta, gamma, X-ray and / or electron radiation, is omitted during the production of the composite film and / or afterwards.
- non-radiation crosslinked composite films with PVdC has the advantage over certain other materials used as oxygen barriers that the barrier property against water or water vapor and in particular against oxygen is constant over a long period of 3 to 6 months or more. Consequently, the barrier is stable over time in relation to use
- an ethylene-vinyl alcohol copolymer (EVOH) as a barrier material in an inner or intermediate layer is improved, which is a considerable advantage especially when the packaged goods, in particular a food, have a long shelf life.
- EVOH ethylene-vinyl alcohol copolymer
- the thermoplastic resin of layer (a) has a density of 0.94 g / cm 3 or more, preferably 0.96 g / cm 3 or more, preferably between 0.96 and 2 g / cm 3 , in particular between 0.96 and 1.5 g / cm 3 . If a resin or polymer with a high density, in particular PET, a PA or a PO with a correspondingly high density, is used as a layer component for the layer (a), a high puncture resistance of the entire composite film and a high heat resistance of the layer (a ) achieved.
- a resin from the material groups PA or PET with a high density in layer (a) brings about attractive optical properties, such as transparency and gloss, of the composite film. Furthermore, with such an outer layer (a) with a high density, improved further processing in the sense of high cycle rates can be ensured.
- the thermoplastic resin of layer (a) of the composite film according to the invention can be a polyester, preferably a polyethylene terephthalate (PET) or a polylactic acid or a polylactide (PLA), a polyamide (PA), a polyolefin (PO), an ethylene - vinyl acetate copolymer (EVA), an ethylene-methyl methacrylate copolymer (EMMA), an ethylene-methacrylic acid copolymer (EMA), an ionomer (IO), or any mixture thereof or consist thereof.
- PET polyethylene terephthalate
- PLA polylactic acid or a polylactide
- PA polyamide
- PO polyolefin
- EMMA ethylene - vinyl acetate copolymer
- EMMA ethylene-methyl methacrylate copolymer
- EMA ethylene-methacrylic acid copolymer
- IO ionomer
- polyamide in layer (a) ensures high heat resistance, high strength, in particular puncture resistance, and sufficient shrinkage. These advantages are achieved in particular if the layer (a) contains PET instead of the polyamide or consists of PET.
- PET instead of PA in layer (a)
- PET is brought into a crystallized state during bi-axial stretching as part of the manufacturing process.
- the use of PET in layer (a) effectively prevents a tendency to curl, as is usual with partially crystallized PA.
- PA in the outer layer is also characterized by an excellent printability of the composite film.
- PLA offers significantly better barrier protection, especially after stretching, especially after biaxial stretching.
- the layer (a) when using the raw materials optionally provided according to the invention for the layer (a), such as polyester, preferably a polyethylene terephthalate (PET) or a polylactic acid (PLA), a polyamide (PA), or any Mixing the same also achieves increased rigidity and thus also improved process stability during stretching, more precisely during biaxial stretching of the bubble-shaped film. And because of the sufficient rigidity of the composite film according to the invention, higher cycle rates and thus improved processability (bagging) can be achieved.
- PET polyethylene terephthalate
- PLA polylactic acid
- PA polyamide
- the improved rigidity of the film according to the invention can be seen from Table 5 below.
- the raw material-related heat resistance or the high Vicat softening temperature and the associated high rigidity even at high temperatures combined with the fundamentally higher rigidity of the raw materials used compared to those networked in jet Films used raw materials, surprisingly a significantly higher processability (cycle rates) compared to comparable radiation-crosslinked composite films, as can be seen from Table 6 below.
- the main raw material 80 to 90% layer content
- EVA the main raw material
- this raw material has an extremely low Vicat softening temperature.
- the EVA types used have a Vicat softening temperature, which is usually between 45 and 70 ° C, but not more than 85 ° C.
- raw materials are therefore used specifically in layer (a) which have a Vicat softening temperature which is at least above 100 ° C. (see Table 7 below).
- VST Vicat softening temperature
- the composite film according to the invention has a lower haze or a higher transparency and a higher gloss and thus improved optical properties compared to radiation-crosslinked composite films, as can be seen from Table 8 below.
- the composite film according to the invention can have a sealing layer which, despite or precisely because of the temperature introduced from the outside, begins to seal earlier than the outer layer in order to ensure that the film to be welded seals inside before it sticks to the outer layer on the sealing tool (sealing bar) . According to the invention by completely dispensing with a sealing layer which, despite or precisely because of the temperature introduced from the outside, begins to seal earlier than the outer layer in order to ensure that the film to be welded seals inside before it sticks to the outer layer on the sealing tool (sealing bar) . According to the invention by completely dispensing with a sealing layer which, despite or precisely because of the temperature introduced from the outside, begins to seal earlier than the outer layer in order to ensure that the film to be welded seals inside before it sticks to the outer layer on the sealing tool (sealing bar) . According to the invention by completely dispensing with a sealing tool (sealing bar) .
- the thermoplastic resin of the layer (a) may be a material having a melting temperature or a melting point of 170 ° C. or higher, preferably 175 ° C. or higher, preferably 180 ° C. or higher.
- layer (a) contains or consists of polyamide or PET, and neither the composite film nor individual layers are crosslinked by radiation, this is the case It has surprisingly been shown that the composite film has excellent transparency or low haze and excellent gloss.
- the thermoplastic resin of layer (a) of the composite film according to the invention can have a sealing temperature (measured at 1 bar, air atmosphere, 23 ° C.) which is equal to or higher than the sealing temperature of the resin of layer (c) (measured at 1 bar, air atmosphere, 23 ° C).
- the thermoplastic resin of layer (a) can in particular be one of the polymer materials mentioned above for layer (a) or a mixture of at least two of these polymer materials.
- thermoplastic resin for layer (a) with a sealing temperature that is the same or higher than the sealing temperature of the resin of layer (c), it is advantageous to avoid sticking of the film to the sealing bar or of films or film parts to one another.
- the composite film can have a haze (ASTM D1003) of at most 15%, preferably at most 12%, preferably at most 10%, preferably at most 7%, in particular at most 5%.
- a haze ASTM D1003
- the desired optical properties of the composite film according to the invention are achieved.
- the visual appearance of the resulting composite film and the recognizability / testability of the goods packed with it by the buyer of the goods are improved without the packaging having to be opened.
- the above-discussed haze of the composite film can in particular be combined with the above-discussed feature of the same or higher sealing temperature of the thermoplastic resin of layer (a) compared to the resin of layer (c).
- the choice of a thermoplastic resin for layer (a) with a sealing temperature that is equal to or higher than the sealing temperature of the resin of layer (c) is combined with the above-described, low haze values of the multilayer film.
- the composite film can have a stiffness (DIN EN ISO 527), expressed as a modulus of elasticity, measured in the machine direction, of at least 200 MPa, preferably at least 250 MPa, preferably at least 300 MPa, preferably at least 350 MPa, preferably at least 400 MPa, in particular at least 450 MPa.
- the composite film can have a stiffness (DIN EN ISO 527), expressed as the modulus of elasticity, measured in the transverse direction, ie in a direction which is perpendicular or transverse to the machine direction, of at least 200 MPa, preferably at least 250 MPa, preferably at least 300 MPa, preferably at least 350 MPa, preferably at least 400 MPa, in particular at least 450 MPa.
- a stiffness DIN EN ISO 527
- the composite film can have a rigidity (DIN EN ISO 527), expressed as the modulus of elasticity, measured in the machine direction, of at most 700 MPa, preferably at most 650 MPa, preferably at most
- the composite film can have a stiffness (DIN EN ISO 527), expressed as the modulus of elasticity, measured in the transverse direction, of at most 700 MPa, preferably at most 650 MPa, preferably at most
- 600 MPa preferably at most 550 MPa, in particular at most 500 MPa.
- the layer (a) or the composite film according to the invention containing it can in particular be characterized by one of the following features or any combination of the following features:
- thermoplastic resin of layer (a) can be a polyester, preferably PET or PLA, PA, PO, an ethylene-vinyl acetate copolymer (EVA), an ethylene-methyl methacrylate copolymer (EMMA), an ethylene-methacrylic acid copolymer (EMA contain or consist of an ionomer (IO), or any mixture thereof;
- the thermoplastic resin of layer (a) can have a sealing temperature (measured at 1 bar, air atmosphere, 23 ° C.) which is equal to or higher than the sealing temperature of the resin of layer (c);
- thermoplastic resin of layer (a) is a material with a melting temperature or a melting point of 170 ° C or higher, preferably 175 ° C or higher, preferably 180 ° C or higher, preferably between 170 and 300 ° C, preferably between 175 and 300 ° C, in particular between 180 and 300 ° C;
- the haze of the composite film can be limited to a maximum of 15%, preferably a maximum of 12%, preferably a maximum of 10%, preferably a maximum of 7%, in particular a maximum of 5%;
- Young's modulus measured in the machine or transverse direction, can be limited to at least 200 MPa, preferably at least 250 MPa, preferably at least 300 MPa, preferably at least 350 MPa, preferably at least 400 MPa, especially at least 450 MPa; and or
- the modulus of elasticity measured in the machine direction or transverse direction, can be limited to at most 700 MPa, preferably at most 650 MPa, preferably at most 600 MPa, preferably at most 550 MPa, especially at most 500 MPa.
- the resin of layer (c) can be a polyolefin (PO), preferably a polyethylene (PE) and / or a polypropylene (PP), an ethylene-vinyl acetate copolymer (EVA), an ionomer (IO) Contain or consist of ethylene-methyl methacrylate copolymer (EMMA), an ethylene-methacrylic acid copolymer (EMA), or any mixture thereof.
- PO polyolefin
- PE polyethylene
- PP polypropylene
- EVA ethylene-vinyl acetate copolymer
- IO ionomer
- EMMA ethylene-methyl methacrylate copolymer
- EMA ethylene-methacrylic acid copolymer
- a polyolefin preferably a polyethylene (PE) and / or a polypropylene (PP), or EVA
- an ionomer IO
- an ethylene-methyl methacrylate copolymer EMMA
- an ethylene-methacrylic acid copolymer EMA
- any mixture thereof for example a mixture of PO and EVA
- the omission of radiation crosslinking leads to the retention of the excellent sealability, which would otherwise be lost or at least restricted by radiation crosslinking.
- Layer (c) preferably contains a high proportion of a polyolefin or consists of a polyolefin.
- the layer (a) can have a thickness in the range from 0.5 to 20 ⁇ m, preferably 1 to 10 ⁇ m; and / or the thickness of layer (a) can be at most 30%, preferably at most 10%, in particular at most 5%, of the thickness of the entire composite film.
- the thickness of the layer (a) is limited to a value in the range from 0.5 to 20 ⁇ m, preferably 1 to 10 ⁇ m, ensures that only a small amount of the resin or resin mixture forming the layer (a) is in the composite film is inserted or applied.
- This restriction of the amount of material in layer (a) avoids compromises in terms of suppleness and the associated damage to other packaging or the shrinkage of the resulting composite film, which can otherwise occur if too much material is used in layer (a).
- the provision of a thin outer layer (a) ensures that the resulting composite film is extremely flexible.
- none of the layers of the composite film which are arranged between layer (a) and layer (c) contain a polyamide (PA). Due to this restriction, a higher dimensional stability is achieved with lower rigidity at the same time. In addition, a lower cold shrinkage is achieved.
- PA polyamide
- none of the layers of the composite film, which are arranged between layer (a) and layer (c), contain an ethylene-vinyl alcohol copolymer (EVOH).
- EVOH ethylene-vinyl alcohol copolymer
- the composite film according to the invention can advantageously completely dispense with the use of an ethylene-vinyl alcohol copolymer (EVOH) as a layer component in the inner layers by providing PVdC in layer (b).
- EVOH ethylene-vinyl alcohol copolymer
- an “inner layer” is understood to mean a layer within the composite film according to the invention which is arranged between layer (a) and layer (c).
- the composite film can have a (hot) shrinkage of at least 20%, preferably at least 25%, in particular at least 50%, in each case in the longitudinal and in the transverse direction, measured in water at 90 ° C., preferably within 1 second after immersion, but at least within 10 seconds after immersion.
- the composite film can have a total shrinkage based on the area of at least 40%, preferably at least 50%, in particular at least 100%, measured in water at 90 ° C., preferably within 1 second after immersion, but at least within of 10 seconds after immersion.
- the sample is immersed in water at 90 ° C. for a predetermined, in particular the aforementioned period of time, and immediately cooled to room temperature with water after removal.
- the length of a pre-marked section after this treatment is measured and related to the measured length of the same section of the sample before the treatment.
- the resulting length ratio (“shrunk" to "not shrunk"), given in percent, defines the shrinkage.
- the shrinkage results in the longitudinal (MD) and in the transverse direction (TD).
- the total shrinkage is calculated by adding the shrinkage in the longitudinal and in the transverse direction.
- the shrinkage and the total shrinkage can be determined in accordance with ASTM 2732 in particular.
- composite films can advantageously be produced which consequently have a high degree of shrinkage both in the longitudinal direction (Longitudinal / machine direction) as well as in the transverse direction (transverse direction). Even high demands on the resulting composite film, which are placed on a shrink film for packaging a foodstuff such as meat, fish or cheese, for example, are thus met.
- the composite film can also have the following layer structure, counted from the outside in, with at least seven layers, wherein:
- a first layer from the outside as a layer component a polyethylene terephthalate (PET), a polyamide (PA), a polylactic acid (PLA), or any mixture thereof;
- PET polyethylene terephthalate
- PA polyamide
- PLA polylactic acid
- PO polyolefin
- PP polypropylene
- PE polyethylene
- EVA ethylene-vinyl acetate copolymer
- IO ionomer
- EMMA ethylene-methyl methacrylate copolymer
- EMA ethylene methacrylic acid copolymer
- HV Adhesion promoter
- PVdC polyvinylidene chloride
- HV Adhesion promoter
- PO polyolefin
- PE polyethylene
- PP polypropylene
- EVA ethylene-vinyl acetate copolymer
- IO ionomer
- EMMA ethylene-methyl methacrylate copolymer
- EMA ethylene methacrylic acid copolymer
- the composite film may contain or consist of.
- a high heat resistance of the composite film is achieved.
- the composite film is not too stiff.
- the object according to the invention is achieved in terms of production technology by the composite film according to claim 11.
- the advantages and modifications of the method according to the invention discussed above also apply analogously to the composite film according to the invention.
- a multilayer composite film which is preferably produced by means of a blow molding process and biaxially stretched, and in particular produced by the process according to one of Claims 1 to 9.
- the composite film comprises at least three layers (a), (b) and (c), of which
- the layer (a) forms a surface of the composite film to the outside; the layer (c) forms a surface of the composite film which faces or comes into contact with an item to be packaged; and the layer (b) is arranged between the layer (a) and the layer (c).
- Layer (a) contains or consists of a thermoplastic resin.
- Layer (b) contains or consists of a polyvinylidene chloride (PVdC) resin.
- the layer (c) contains or consists of a resin, preferably a sealable, in particular heat-sealable resin.
- the thermoplastic resin of layer (a) has a density of 0.94 g / cm 3 or more. There is no crosslinking of the composite film by means of radioactive radiation, in particular by means of beta, gamma, X-ray and / or electron radiation, during the production of the composite film and / or afterwards.
- the advantages of the composite film according to the invention can ideally be used especially in the packaging of light-, oxygen-, temperature- and / or aroma-sensitive goods, such as food in particular.
- the composite film according to the invention offers ideal protection for sensitive packaged goods, in addition to the advantages described above.
- Table 10 Layer structures of exemplary composite films according to the invention with seven layers, not cross-linked by radiation: Layer components and layer thicknesses (total thickness in each case 50 ⁇ m)
- the invention is not restricted to the embodiments mentioned, in particular not to the total thickness of the layer structure and the thickness ratios of the individual layers, as indicated in Table 10.
- the invention thus also expressly includes the layer sequences of Examples 1 to 3 of Table 10, but with layer thicknesses other than those indicated in Table 10 and in each case different total thicknesses.
- the method according to the invention and the composite film according to the invention can preferably be carried out or produced using the so-called double-bubble and in particular the triple-bubble method, for which the applicant provides suitable systems, which are known to the person skilled in the art.
- the multilayer composite film can, for example, be coextruded from the respective resin melts by means of a nozzle blow head set up by the applicant for the production of composite films with three or more layers, preferably with thermal separation of the individual layers, cooled with water cooling by the applicant, reheated, biaxially by means of an enclosed compressed air bubble stretched and finally heat-set in a further step in a defined temperature regime.
- the composite film according to the invention can be a composite film which has a barrier against gas diffusion, in particular oxygen diffusion, and / or against water vapor diffusion.
- the composite film of the present invention can advantageously be achieved on a device or system from the same applicant for the production of tubular food films for food packaging, such as shrink films or shrink bags, in the jet blowing process if the patent specification DE 199 16 428 B4 by the same applicant is also disclosed Device for rapid cooling of thin thermoplastic tubes after their extrusion is used. A corresponding further development according to patent specification DE 100 48 178 B4 can also be taken into account for this purpose.
- the tubular film produced from the plastic melt in the die head is subjected to intensive cooling during which the amorphous structure of the thermoplastics from the plastic melt is retained.
- the tubular film extruded vertically from the plastic melt in the die head initially migrates into the cooling device without touching the wall, as described in detail in the publications DE 199 16 428 B4 and DE 100 48 178 B4.
- this cooling device also referred to as a calibration device, reference is made in full to the content of the documents DE 199 16 428 B4 and DE 100 48 178 B4 to avoid repetition.
- the tubular film then passes through supports in the cooling device, against which the film is supported as a result of a differential pressure between the interior of the tubular film and the coolant, a liquid film being retained between the film and the supports so that the tubular film cannot stick.
- the diameter of the supports influences the diameter of the tubular film, which is why this cooling device by the same applicant is also referred to as a calibration device.
- PVdC polyvinylidene chloride
- polyamide (PA) can be a substance selected from a group consisting of PA from e-caprolactam or poly (-caprolactam) (PA6), PA from hexamethylene diamine and adipic acid or polyhexamethylene adipamide (PA6.6), PA from e -Caprolactam and hexamethylenediamine / adipic acid (PA6.66), PA from hexamethylenediamine and dodecanedioic acid or polyhexamethylene dodecanamide (PA6.12), PA from 11-aminoundecanoic acid or polyundecanamide (PA11), PA from 12-laurolactam or poly (co-laurolactam) ) (PA 12), or a mixture of these PA or a mixture of these PAs with amorphous PAs or with other polymers.
- PAx.y is synonymous with PAx / y or PAxy.
- polyolefin can be a substance selected from a group consisting of PP, PE, LDPE, LLDPE, polyolefin plastomer (POP), ethylene-vinyl acetate copolymers (EVA), ethylene-methyl methacrylate copolymers (EMMA ), Ethylene-methacrylic acid copolymers (EMA), ethylene-acrylic acid copolymers (EAA), copolymers of cycloolefins / cycloalkenes and 1-alkenes or cycloolefin copolymers (COC), ionomers (IO) or a mixture or mixture thereof his.
- PO can be a mixture of the above POs with ionomers.
- polyester can be used as a layer component for layer (a).
- Polyesters are polymers with ester functions in their main chain and can in particular be aliphatic or aromatic polyesters. Polyesters can be obtained by polycondensation of corresponding dicarboxylic acids with diols. Any dicarboxylic acid which is suitable for forming a polyester can be used to synthesize the polyester, especially terephthalic acid and isophthalic acid, as well as dimers of unsaturated aliphatic acids.
- Diols can be used as the further component for the synthesis of the polyester, such as, for example: polyalkylene glycols, such as ethylene glycol, propylene glycol,
- Tetramethylene glycol Tetramethylene glycol, neopentyl glycol, hexamethylene glycol, diethylene glycol, polyethylene glycol and polytetramethylene oxide glycol; 1,4-Cyclohexanedimethanol, and 2-alkyl-1,3-propanediol.
- PET which stands for the polyester polyethylene terephthalate, is particularly preferred. PET can be obtained by polycondensation of terephthalic acid (1,4-benzene dicarboxylic acid) and ethylene glycol (1,2-dihydroxyethane).
- polyesters are the polylactides or polylactic acids (PLA), which can be contained as a layer component in the layers for which a polyester is provided as a layer component.
- PLA polylactides or polylactic acids
- These polymers are biocompatible / biodegradable and have a low Moisture absorption high melting temperatures or high melting points and good tensile strength.
- EVOH stands for EVOH as well as a mixture of EVOH with other polymers, ionomers, EMA or EMMA.
- EVOH also includes a mixture of EVOH and PA or of EVOH and ionomer.
- the adhesion promoters (HV) stand for adhesive layers which ensure good bond between the individual layers.
- HV can be based on a base material selected from a group consisting of PE, PP, EVA, EMA, EMMA, EAA and an ionomer, or a mixture thereof.
- EVA, EMA or EMMA each with a purity of> 99%, preferably> 99.9%, are particularly suitable as adhesion promoters (HV).
- layers which have HV as a layer component can also be a mixture of PO and HV or a mixture of EVA, EMA, EMMA and / or EAA and HV or a mixture of ionomer and HV or a mixture of a plurality of Show HV.
- further processability means the speed (units per unit of time) at which the composite film produced according to the invention can be further processed into usable packaging units, such as shrink bags for food.
- usable packaging units such as shrink bags for food.
- This can include, for example, the formation of a bag shape, the application of sealing seams and, in a broader sense, possibly also the filling with the goods to be packaged and the closing of the filled packaging.
- the designation of a material as a “layer component” means that a layer of the food film according to the invention at least partially comprises this material.
- the designation “Layer component” within the meaning of this invention include in particular that the layer consists entirely or exclusively of this material.
- the composite film according to the invention is preferably flat or tubular.
- the composite film is preferably a foodstuff film or food casing.
- the composite film is also preferably suitable for use as a heat-shrinkable packaging material.
- crosslinking by radiation means crosslinking by means of radioactive radiation, preferably “crosslinking by means of beta, gamma, x-ray and / or electron radiation”.
- dispensing with radiation crosslinking includes an integrated and a downstream radiation crosslinking in the production of the composite film.
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Clinical Laboratory Science (AREA)
- Laminated Bodies (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102019111458.6A DE102019111458A1 (de) | 2019-05-03 | 2019-05-03 | Verfahren zur Herstellung einer mehrschichtigen Verbundfolie, mehrschichtige Verbundfolie und deren Verwendung |
PCT/EP2020/062162 WO2020225136A1 (de) | 2019-05-03 | 2020-04-30 | Verfahren zur herstellung einer mehrschichtigen verbundfolie, mehrschichtige verbundfolie und deren verwendung |
Publications (1)
Publication Number | Publication Date |
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EP3962736A1 true EP3962736A1 (de) | 2022-03-09 |
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Application Number | Title | Priority Date | Filing Date |
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EP20723390.9A Pending EP3962736A1 (de) | 2019-05-03 | 2020-04-30 | Verfahren zur herstellung einer mehrschichtigen verbundfolie, mehrschichtige verbundfolie und deren verwendung |
Country Status (8)
Country | Link |
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US (1) | US20220219437A1 (de) |
EP (1) | EP3962736A1 (de) |
CN (1) | CN113677528A (de) |
AU (1) | AU2020267808B2 (de) |
BR (1) | BR112021021716A2 (de) |
CA (1) | CA3132791C (de) |
DE (1) | DE102019111458A1 (de) |
WO (1) | WO2020225136A1 (de) |
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CN114228291B (zh) * | 2021-12-31 | 2023-11-03 | 常州市华健药用包装材料有限公司 | 基于温敏技术的药用复合膜及其加工工艺 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2347031A1 (en) * | 1998-10-29 | 2000-05-11 | Cryovac, Inc. | New high resistance heat-shrinkable thermoplastic film |
DE19916428B4 (de) | 1999-04-12 | 2004-06-17 | Kuhne Anlagenbau Gmbh | Einrichtung zum raschen Abkühlen dünner thermoplastischer Schläuche nach deren Extrusion |
DE10048178B4 (de) | 2000-09-28 | 2005-12-29 | Kuhne Anlagenbau Gmbh | Verfahren zur Erhöhung der Abkühlgeschwindigkeit dünner thermoplastischer Schläuche nach deren Extrusion, und Vorrichtung zur Durchführung des Verfahrens |
DE10227580A1 (de) | 2002-06-20 | 2004-01-08 | Kuhne Anlagenbau Gmbh | Mehrschichtige flächen- oder schlauchförmige Nahrungsmittelhülle oder -folie |
DE202006020148U1 (de) | 2006-08-07 | 2007-12-06 | Kuhne Anlagenbau Gmbh | Mehrschichtige flächen- oder schlauchförmige Nahrungsmittelhülle oder -folie |
DE102006046483B4 (de) | 2006-09-29 | 2009-01-29 | Kuhne Anlagenbau Gmbh | Mehrschichtige flächen- oder schlauchförmige Nahrungsmittelhülle oder -folie |
EP2077297B1 (de) * | 2008-01-02 | 2012-04-04 | Flexopack S A | PVDC-Formulierung und wärmeschrumpfbare Folie |
EP2147783B1 (de) * | 2008-07-23 | 2018-05-09 | Flexopack S.A. | Blockversiegelbare, wärmeschrumpfende folie |
BR112016015680B8 (pt) * | 2014-01-15 | 2022-10-04 | Cryovac Inc | Película de embalagem contraível por calor de barreira biaxialmente orientada coextrudada de múltiplas camadas, artigo para embalagem na forma de um tubo sem costura, embalagem, processo para manufatura de uma película, e uso de uma película |
WO2015181333A1 (en) * | 2014-05-28 | 2015-12-03 | Cryovac, Inc. | Multilayer heat shrinkable films |
CN106794683A (zh) * | 2014-10-03 | 2017-05-31 | 纳幕尔杜邦公司 | 多层食品肠衣或食品膜 |
AU2018209677B2 (en) * | 2017-01-17 | 2022-05-12 | Cryovac, Llc | Multilayer non-cross-linked heat-shrinkable packaging films |
-
2019
- 2019-05-03 DE DE102019111458.6A patent/DE102019111458A1/de active Pending
-
2020
- 2020-04-30 BR BR112021021716A patent/BR112021021716A2/pt unknown
- 2020-04-30 CA CA3132791A patent/CA3132791C/en active Active
- 2020-04-30 CN CN202080028369.7A patent/CN113677528A/zh active Pending
- 2020-04-30 WO PCT/EP2020/062162 patent/WO2020225136A1/de unknown
- 2020-04-30 US US17/607,779 patent/US20220219437A1/en active Pending
- 2020-04-30 EP EP20723390.9A patent/EP3962736A1/de active Pending
- 2020-04-30 AU AU2020267808A patent/AU2020267808B2/en active Active
Also Published As
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CA3132791A1 (en) | 2020-11-12 |
CA3132791C (en) | 2023-12-19 |
CN113677528A (zh) | 2021-11-19 |
AU2020267808B2 (en) | 2023-05-04 |
AU2020267808A1 (en) | 2021-09-30 |
DE102019111458A1 (de) | 2020-11-05 |
US20220219437A1 (en) | 2022-07-14 |
WO2020225136A1 (de) | 2020-11-12 |
BR112021021716A2 (pt) | 2021-12-21 |
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