EP3962740A1 - Procédé pour fabriquer un film composite multicouche, film composite multicouche et son utilisation - Google Patents

Procédé pour fabriquer un film composite multicouche, film composite multicouche et son utilisation

Info

Publication number
EP3962740A1
EP3962740A1 EP20723394.1A EP20723394A EP3962740A1 EP 3962740 A1 EP3962740 A1 EP 3962740A1 EP 20723394 A EP20723394 A EP 20723394A EP 3962740 A1 EP3962740 A1 EP 3962740A1
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
Application number
EP20723394.1A
Other languages
German (de)
English (en)
Inventor
Jürgen Michael Schiffmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kuhne Anlagenbau GmbH
Original Assignee
Kuhne Anlagenbau GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kuhne Anlagenbau GmbH filed Critical Kuhne Anlagenbau GmbH
Publication of EP3962740A1 publication Critical patent/EP3962740A1/fr
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—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
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • 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
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/08—PVDC, i.e. polyvinylidene chloride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/003—PET, i.e. poylethylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0082—Flexural strength; Flexion stiffness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0094—Geometrical properties
    • B29K2995/0097—Thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B29L2007/008—Wide strips, e.g. films, webs
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/05—5 or more layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • 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
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    • B32B2307/54—Yield strength; Tensile strength
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    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging

Definitions

  • the invention relates to a method for producing a multilayer composite film according to claim 1, a multilayer 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 a gas barrier layer, the properties required for the intended use, for example as heat-shrinkable packaging film for food, being achieved exclusively by means of the raw material combinations used.
  • the use of higher percentages of the raw materials polyamide, EVOH and PET leads to relatively stiff films.
  • PA and EVOH the tendency of these raw materials to recrystallize 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 permeable moisture from the outside and inside.
  • 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 disadvantageously increases the number of layers required and the complexity of the overall composite .
  • composite films that 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 multi-layer 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 embedded between two PO layers, and in which the outer layer consists of PET.
  • multilayer composite films which are crosslinked by radiation and use PVdC as a barrier material.
  • the radiation crosslinking integrated or downstream in the film production process through radioactive irradiation or irradiation with electrons achieves essential properties such as sufficiently high shrinkage, good puncture resistance and heat resistance, which prevent the oxygen, gas and aroma properties originally already present in PVdC - best supplement.
  • the use of radiation-crosslinked PVdC can result in cold shrinkage compared to other conventional ones
  • radiation crosslinked composite films often have the disadvantage that, due to the interaction of the raw materials and the radiation crosslinking, the appearance is not satisfactory in terms of cloudiness, gloss and coloring (brown or yellowish tint).
  • the haze in films based on radiation-crosslinked PVdC is significantly increased compared to other conventional films, as Table 2 below shows.
  • Table 2 Haze, measured with conventional multilayer films based on EVOH vs. radiation crosslinked PVdC (ASTM D1003)
  • 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 cast, recyclability and a long-term, un influenceable or stable oxygen barrier.
  • the presence of a slight cloudiness of the composite film is advantageous.
  • 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) contains or consists of a polyester, preferably a polyethylene terephalate (PET), a polylactic acid (PLA), a polyamide (PA), or any mixture thereof; and wherein 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.
  • PET polyethylene terephalate
  • PLA polylactic acid
  • PA polyamide
  • non-radiation cross-linked 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 especially against oxygen is constant over a long period of 3 to 6 months or more.
  • the stability of the barrier over time is improved compared to the use of an ethylene-vinyl alcohol copolymer (EVOH) in particular as a barrier material in an inner or intermediate layer, which is a considerable advantage especially when the packaged goods, in particular a food, have a long shelf life.
  • EVOH ethylene-vinyl alcohol copolymer
  • thermoplastic resin of layer (a) of the composite film according to the invention contains or consists of a polyester, preferably a polyethylene terephthalate (PET) or a polylactic acid or a polylactide (PLA), a polyamide (PA), or any mixture thereof.
  • PET polyethylene terephthalate
  • PLA polylactic acid or a polylactide
  • PA polyamide
  • 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)
  • the cold shrinkage or post-shrinkage that can occur when using PA as a layer component due to post-crystallization is effectively reduced or even avoided (see table below 9).
  • 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. Furthermore, PA and PLA are far superior to polyolefin-based raw materials in terms of processability and recyclability.
  • polyester preferably a polyethylene terephthalate (PET), a polylactic acid (PLA), a polyamide (PA), or any mixture thereof, is also used increased rigidity and thus also improved process stability during stretching, more precisely in the biaxial stretching of the bubble-shaped film.
  • PET polyethylene terephthalate
  • PLA polylactic acid
  • PA polyamide
  • the improved rigidity of the film according to the invention is from the following
  • 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 the in Radiation-crosslinked 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
  • this raw material has an extremely low Vicat softening temperature.
  • the EVA types used have a V icat 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) .
  • the risk of incorrect or poorly dosed radiation cross-linking is excluded. This avoids the risk of a radiation-related deterioration in the sealability of the composite film.
  • the fact that there is no radiation crosslinking means that the composite film remains recyclable.
  • the thermoplastic resin of layer (a) of the composite film according to the invention can be 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.
  • layer (a) contains or consists of polyamide or PET, and neither the composite film nor individual layers are radiantly crosslinked, it has surprisingly been found that the composite film has excellent transparency or low haze and excellent gloss.
  • the thermoplastic resin of layer (a) can have 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 or a PA with a correspondingly high density, is used as layer component for layer (a), a high puncture resistance of the entire composite film and high heat resistance of layer (a) are advantageously achieved. In addition, a resin from the material groups PA or PET with a high density in layer (a) brings about appealing optical properties, such as transparency and gloss, of the composite film.
  • 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) (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 realized.
  • 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).
  • thermoplastic resin for layer (a) with a sealing temperature equal to or higher than the sealing temperature of the resin in layer (c) is combined with the low haze values of the multilayer film described above.
  • 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.
  • a stiffness DIN EN ISO 527
  • 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 stiffness (DIN EN ISO 527), expressed as a modulus of elasticity, measured in the machine 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 composite film can have a rigidity (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:
  • 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);
  • the thermoplastic resin of layer (a) can have 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 ;
  • 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 (ASTM D1003) 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%;
  • the rigidity of the composite film (DIN EN ISO 527), expressed as the modulus of elasticity, measured in the machine direction or transverse direction, can be 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; and or
  • the stiffness of the composite film (DIN EN ISO 527), expressed as the modulus of elasticity, measured in the machine direction or transverse direction, can be limited to a maximum of 700 MPa, preferably a maximum of 650 MPa, preferably a maximum of 600 MPa, preferably a maximum of 550 MPa, especially a maximum of 500 MPa his.
  • 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) Ethylene-methyl methacrylate copolymer (EMMA), an ethylene-methacrylic acid copolymer (EMA), or any mixture of the same or consist 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 -Copolymers EMA
  • 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).
  • 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). This prevents the decrease in the barrier function due to the external influence of moisture on the composite film, which occurs as a barrier material with EVOH. In this way, a sufficient barrier function with long-term stability can be ensured despite or precisely because of the waiver of EVOH.
  • 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 additional "protective layers" can be applied according to the invention. be waived. This simplifies the overall structure and the production method of the composite film. In addition, the manufacturing costs decrease.
  • 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. Additionally or alternatively, 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, at least but within 10 seconds of being immersed.
  • 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.
  • the composite film can furthermore 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
  • HV adhesion promoter
  • 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
  • a seventh layer from the outside as a layer component a polyolefin (PO), preferably a polyethylene (PE) or a polypropylene (PP), an ethylene-vinyl acetate copolymer (EVA), an ionomer (IO), an 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 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) contains or consists of a polyester, preferably a polyethylene terephalate (PET), a polylactic acid (PLA), a polyamide (PA), or any mixture.
  • 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.
  • a composite film according to one of Claims 10 to 19 or a casing produced therefrom for packaging an object, preferably a food or luxury food, in particular a food containing meat, fish or cheese, is claimed.
  • 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 packaging 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 50 ⁇ m each)
  • the invention is not limited to the embodiments mentioned, in particular not to the total thickness of the layer structure and the thickness ratios of the individual layers, as are given in Table 10.
  • the invention thus also expressly encompasses 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. Further disclosure and alternatives
  • 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, for example, shrink films or shrink bags, in the jet blowing process, if one also uses the same as described in patent DE 199 16 428 B4 Applicant disclosed device for rapid cooling of thin thermoplastic tubes after their extrusion. 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.
  • the full content of the contents of the documents DE 199 16 428 B4 and DE 100 48 178 B4 is referred to in full to avoid repetition of the procedures, the structure and the mode of operation of this cooling device, also referred to as calibration device.
  • 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 (s-caprolactam) (PA6), PA from hexamethylene diamine and adipic acid or polyhexamethylene adipamide (PA6.6), PA from e-Ca- prolactam and hexamethylenediamine / adipic acid (PA6.66), PA made from hexamethylenediamine and dodecanedioic acid or polyhexamethylene dodecanamide (PA6.12), PA made from 11-aminoundecanoic acid or polyundecanamide (PA11), PA made from 12-laurolactam or poly ( co-laurin lactam) (PA 12), or a mixture of these PA or a mixture of these PA with amorphous PA 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 a mixture thereof.
  • 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, for example: polyalkylene glycols, such as ethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, hexamethylene glycol, diethylene glycol, polyethylene glycol and polytetra methylene oxide glycol; 1,4-cyclohexanedimethanol, and 2-alkyl-1,3-propanediol.
  • polyalkylene glycols such as ethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, hexamethylene glycol, diethylene glycol, polyethylene glycol and polytetra methylene oxide glycol
  • 1,4-cyclohexanedimethanol 1,4-cyclohexanedimethanol
  • 2-alkyl-1,3-propanediol 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, in addition to low moisture absorption, have 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 that 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 that 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) with 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.
  • a material for the purposes of this invention, 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 term “layer component” in the context of this invention can in particular include the fact 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” or “radiation crosslinking” means crosslinking by means of radioactive radiation, preferably “crosslinking by means of beta, gamma, x-ray and / or electron radiation”.
  • the omission of 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)
  • Laminated Bodies (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

La présente invention concerne un procédé pour fabriquer un film composite multicouche, ce procédé comprenant une étape de coextrusion d'au moins trois couches (a), (b) et (c), la couche (a) formant une surface extérieure du film composite ; la couche (c) formant une surface du film composite qui fait face à un produit à emballer ou vient en contact avec celui-ci ; et la couche (b) étant disposée entre la couche (a) et la couche (c). Ce procédé comprend en outre une étape d'étirage biaxial du film composite ainsi coextrudé. La couche (a) contient une résine thermoplastique ou est constituée d'une telle résine. La couche (b) contient une résine de polychlorure de vinylidène (PVDC) ou est constituée d'une telle résine. La couche (c) contient une résine, de préférence soudable, en particulier thermosoudable, ou est constituée d'une telle résine. Par ce procédé, aucune réticulation du film composite ne se produit sous l'effet d'un rayonnement radioactif, en particulier d'une exposition à un rayonnement bêta, gamma, X et/ou à des électrons, pendant et après la fabrication du film composite.
EP20723394.1A 2019-05-03 2020-04-30 Procédé pour fabriquer un film composite multicouche, film composite multicouche et son utilisation Pending EP3962740A1 (fr)

Applications Claiming Priority (2)

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DE102019111460.8A DE102019111460A1 (de) 2019-05-03 2019-05-03 Verfahren zur Herstellung einer mehrschichtigen Verbundfolie, mehrschichtige Verbundfolie und deren Verwendung
PCT/EP2020/062166 WO2020225140A1 (fr) 2019-05-03 2020-04-30 Procédé pour fabriquer un film composite multicouche, film composite multicouche et son utilisation

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US (1) US20220203658A1 (fr)
EP (1) EP3962740A1 (fr)
BR (1) BR112021021757A2 (fr)
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WO (1) WO2020225140A1 (fr)

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1131205B1 (fr) * 1998-10-29 2004-12-15 Cryovac, Inc. Nouveau film thermoplastique thermoretractable a haute resistance
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
DE102006036844B3 (de) 2006-08-07 2008-01-03 Kuhne Anlagenbau Gmbh Mehrschichtige flächen- oder schlauchförmige Nahrungsmittelhülle oder -folie
DE102006062787B4 (de) 2006-09-29 2009-12-31 Kuhne Anlagenbau Gmbh Mehrschichtige flächen- oder schlauchförmige Nahrungsmittelhülle oder -folie
EP2030784B1 (fr) * 2007-08-27 2016-04-13 Cryovac, Inc. Films rétractables à barrière contre les gaz pour une utilisation dans des applications à formage profond
ATE552304T1 (de) * 2008-01-02 2012-04-15 Flexopack Sa Pvdc-formulierung und wärmeschrumpfbare folie
EP2147783B1 (fr) * 2008-07-23 2018-05-09 Flexopack S.A. Film thermorétrécissable scellable en superposition
EP3094494B2 (fr) * 2014-01-15 2023-11-22 Cryovac, Inc. Films thermorétractables multicouches
EP3149078B1 (fr) * 2014-05-28 2018-07-25 Cryovac, Inc. Films thermorétractables multicouches
CN105437686A (zh) * 2014-08-26 2016-03-30 丹东全德高科技包装有限公司 Pa/tie/pe/eva/pvdc/eva/pe7层共挤深拉伸膜
CA3014699C (fr) * 2016-02-15 2023-01-17 Macro Technology Inc. Film barriere multicouche
RU2749311C2 (ru) * 2017-01-17 2021-06-08 Криовак, Ллк Многослойные несшитые термоусадочные упаковочные пленки

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US20220203658A1 (en) 2022-06-30
WO2020225140A1 (fr) 2020-11-12
BR112021021757A2 (pt) 2021-12-28

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