WO2019020687A1 - Bobine de film barrière irradié, facultativement mono-orienté, pour la production de tubes malléables - Google Patents

Bobine de film barrière irradié, facultativement mono-orienté, pour la production de tubes malléables Download PDF

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Publication number
WO2019020687A1
WO2019020687A1 PCT/EP2018/070156 EP2018070156W WO2019020687A1 WO 2019020687 A1 WO2019020687 A1 WO 2019020687A1 EP 2018070156 W EP2018070156 W EP 2018070156W WO 2019020687 A1 WO2019020687 A1 WO 2019020687A1
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WO
WIPO (PCT)
Prior art keywords
film
ethylene
polymers
layers
copolymer
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.)
Ceased
Application number
PCT/EP2018/070156
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English (en)
Inventor
Massimo CENTONZE
Simonetta LANATI
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.)
INDUSTRIA TERMOPLASTICA PAVESE SpA
Original Assignee
INDUSTRIA TERMOPLASTICA PAVESE SpA
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Priority to EP18742520.2A priority Critical patent/EP3658370A1/fr
Publication of WO2019020687A1 publication Critical patent/WO2019020687A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

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    • 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
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    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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Definitions

  • the present invention relates to a coil of multilayered barrier film (hereinafter also referred to as flat sheet), also with high thickness, intended for the subsequent production of flexible packagings in the form of tubes, where said film is a co- extruded film, blown or cast, with a base of polyolefins and irradiated, which comprises at least three layers whereof one barrier.
  • flat sheet multilayered barrier film
  • the present invention relates to a coil of multilayered flat sheet, mainly a polyolefins-based sheet, with barrier properties and non-heat-shrinkable, preferably treated on the surface with a corona discharge treatment, intended for the subsequent production of tubes, where said flat sheet is blown or cast co-extruded and subsequently irradiated.
  • the present invention relates to a process for producing the aforesaid coil of barrier film comprising a phase of irradiation and optionally a preceding phase of machine orientation (mono-oriented) and/or annealing.
  • the aluminium tube has been almost completely replaced by tubes in plastic material with various degrees of rigidity, barrier, colouring/printing, because plastic materials are able to ensure the same performances and function as metal, and to also add some further benefits including, for example, the lower environmental impact, the better aesthetic quality also during use and emptying of the same by the consumer (e.g. the plastic tube during pressing has always reversible deformations).
  • the solution gained ground of the tube made from a flat sheet which, cut adequately, can be bent/rolled on itself so as to be shaped into a tube and subsequently heat- welded vertically and horizontally for the closure of the tube.
  • This technique certainly offers a greater flexibility in the design of the dimensions of the tube which can be varied if needed without any investment in production technologies, yet requires an exceptionally seal of the weld (high welding force) also under stress and under the effect of pressure.
  • an essential requirement is a good overall rigidity of the tube which must not appear too soft during handling and use by the consumer. Moreover the tube must ensure a perfect barrier to steam, gases and aromas, and to the component chemical products of the cream contained, and must be aesthetically shiny and with an attractive appearance and printable.
  • Another limit of the laminated structure is represented by the fact that these tubes, when they contain aggressive ingredients (e.g. surfactants, alcoholic components), may come up against processes of delamination.
  • aggressive ingredients e.g. surfactants, alcoholic components
  • the presence of aggressive components in the products contained in these tubes is in effect a problem greatly felt in the packagings sector, in light of the fact that the times of exposure to these substances are normally very long (because the packaged products have conservation times lasting years) and that there is a considerable variability of chemical substances inserted in the product contained, which cannot be absolutely controlled by those who make the container tube.
  • the tube moreover has to demonstrate excellent resistance to these chemical agents also at the welds since small leaks in this zone would cause a serious loss of product.
  • Irradiated barrier films are also known which are however made to be heat-shrinkable so as to adhere to fresh food products such as meat, when said food products are packaged under vacuum.
  • this type of films are made with double or triple bubble extrusion technologies that are able to give very high shrinking properties both in terms of size (% of shrinkage) and in terms of compactness of the food, once it has been vacuum packed (retraction force);
  • said films which also normally have low thickness, are generally characterized by a softness and flaccidity which does not render them suitable for making dispenser tubes with a certain rigidity, and a proper shape and consistency also when empty, which are required to be collapsible and sometime also squeezable, such as for example tubes dispensing cosmetic products.
  • the object of the present invention is that of overcoming, at least in part, the disadvantages of the prior art by providing a co-extruded film with a base of polyolefins apt to produce flexible tube containers, having an improved chemical resistance to the aggression of the components of the product contained in the flexible tube.
  • Another object is that of making such a film using a simple and economical process.
  • An object of the present invention relates to a coil of barrier film, more particularly non-heat-shrinkable, co-extruded, blown or cast, surface irradiated, intended for the production of flexible containers in the form of tubes (e.g. collapsible tube containers), which generally have their own shape even when empty, where said co-extruded and irradiated barrier film is a film comprising two outer layers with a base of olefin (co)polymers, at least one intermediate barrier layer and optionally at least two intermediate binding layers.
  • At least the outer layer of the present film which is intended to be the inner surface of the tube is irradiated/radiated, and preferably also treated on the surface with corona discharge treatment.
  • the object of the present invention is a coil of multilayered flat polyolefin-based sheet, preferably polyolefins of high molecular weight, with barrier properties and non-heat-shrinkable, preferably treated on the surface with a corona discharge treatment, where said flat sheet is blown or cast co-extruded and also preferably treated on the surface with corona discharge treatment.
  • the aforesaid flat sheet is particularly suitable for making flexible and soft tubes which dispense products in cream, paste or the like, which are required to be collapsible and at times also squeezable, as well as printable on the outside such as for example tubes dispensing cosmetic products.
  • the corona discharge treatment is particularly advantageous in order to promote the adhesion of the printing inks on the sheet which will then be transformed into a tube.
  • the film and sheet that are the object of the present invention are not to be considered heat-shrinkable in that when they are subjected to the test of Unrestrained Linear Thermal Shrinkage of Plastic Film and sheeting in accordance with ASTM D 2732, they show a quite null linear swelling in both direction (longitudinal and transversal) that it is to be considered non measurable with respect to the effectively heat- shrinkable films of the prior art which in the case of primary packaging show percentage of shrinkage even in the order of 80-90%.
  • heat-shrinkable generally refers to a film which, when it is subjected to a source of heat, shrinks up to approximately 50% of the initial size, at least in one of the directions, adhering to the object around which it has been wound, thus compacting the packaging. After cooling, the film maintains its new shape.
  • carrier here is intended to identify those materials which, thanks to their chemical structure, (normally containing polar functional groups for the different electrical negativity of the atoms constituting the bond) are able to form hydrogen bridge bonding, generating in this way a sort of net which hinders the passage of molecules, even small ones, such as those of the gases (whether 0 2 , N 2 , CO2, and others) where the properties of impermeability to aeriform substances are measured according to measurement methods of the coulometric type, for example that provided by ASTM D3985 and ASTM F1927.
  • This barrier can be a "high barrier” or a “low barrier”, as defined, for example, by the standard UNI 10534.
  • the term "co-extruded” here is intended to identify a film obtained from the process of extrusion of two or more materials, in the molten state, through one or more orifices arranged in a way that the extruded parts fuse and weld together in a laminar structure before cooling, without the aid of any type of glue. Co-extrusion can be performed according to the prior art with blowing in a bubble, flat head, extrusion coating or the like.
  • the present film is preferably co-extruded using screw extruders and bubble blowing or flat head extrusion.
  • machine direction orientation (MDO) (uniaxial orientation) here is intended to identify a process of orientation which stretches the film mainly in a single direction.
  • annealing here is intended to identify a process of heating and subsequent cooling of a film for reducing and/or cancelling out the tensions which may have been generated during the previous processing phases, in particular during the co-extrusion of different layers of different thicknesses and composition.
  • irradiation here the intent is to identify a treatment of irradiation of at least one surface of a film with ionizing radiations, for example by means of bombarding with accelerated electrons (electron beam) having energy comprised between 0.05 and 10 Mev, where this irradiation can also penetrate the thickness (and the layers) of the film according to the depth at which it is intended to arrive with crosslinking of the polymer.
  • ionizing radiations for example by means of bombarding with accelerated electrons (electron beam) having energy comprised between 0.05 and 10 Mev
  • the ionizing rays produced by beams of accelerated electrons are used for different purposes such as the decontamination and sterilisation of material, or the drying of inks and paints.
  • the Applicant has found that the process of electronic irradiation of the film is able to determine such a crosslinking of the polymer chains as to give high chemical resistance to the film.
  • Figure 1 is a schematic view of a system of blown extrusion and stretching by annealing of the present coil
  • Figure 2 is a schematic view of the appliance used for the irradiation
  • Figure 3 is a schematic view of the steps of production of a tube starting from a coil in accordance with the present invention.
  • Figure 4 illustrates schematically the tube obtained from the steps illustrated in Fig. 3;
  • Figure 5 illustrates schematically the layers forming a first embodiment of the film of the present invention (5-layers);
  • Figure 6 illustrates schematically the layers forming a first embodiment of the film of the present invention (7-layers);
  • the first step of the present process is represented by blown co-extrusion of a multilayered film 3 which takes place in "n" extruders where "n” corresponds to the number of layers of the co-extruded film of which Figure 1 shows only an extruder for simplicity of illustration, denoted in Fig. 1 by reference numeral 1.
  • the blown extruder 1 is an apparatus in itself known which is generally composed of an endless screw which conveys the molten material in an annular extrusion head 15, fed simultaneously by a series of extruders (not shown in the drawing), each one fed with a respective polymer material chosen to form the relative layer of the multilayered film 3,
  • the overall thickness of the film 3 intended for the production of collapsible tubes varies from 100 to 400 ⁇ , preferably from 200 to 350 ⁇ .
  • the overall thickness is at least 100 ⁇ .
  • the multilayered structure of the present extruded film 3 is with five layers composed as follows (Fig. 5):
  • - outer layer 10 with a base of olefin (co)polymers, (detailed here below), e.g. PE;
  • barrier layer (detailed here below);
  • - outer layer 50 with a base of olefin (co)polymers, (detailed here below), e.g. PE, where the two outer layers 10 and 50, which are opposite one to the other, define the outer face and the inner one of the co-extruded bubble.
  • olefin (co)polymers e.g. PE
  • olefin (co)polymers suitable for forming the outer layers 10 and 50 are understood to be both olefin homopolymers (olefin polymers) and copolymers among olefin and other types of comonomers.
  • olefin polymers suitable for forming the outer layer 10 which is to be the outer layer of the tube mention can be made, for example, of: polyethylenes such as LD-PE (low-density polyethylene), MD-PE (medium-density polyethylene), HD-PE (high-density polyethylene), LLD-PE (linear low-density polyethylene) mLLD-PE (metallocene linear low-density polyethylene), in all of the various commercially available densities or mixtures thereof.
  • polyethylenes such as LD-PE (low-density polyethylene), MD-PE (medium-density polyethylene), HD-PE (high-density polyethylene), LLD-PE (linear low-density polyethylene) mLLD-PE (metallocene linear low-density polyethylene), in all of the various commercially available densities or mixtures thereof.
  • Said outer layer 10 can also be made in PP (polypropylene), PP-PE copolymers and optional terpolymers, elastomers and plastomers copolymers propylene-ethylene and the like, or said outer layer 10 can be made with the materials mentioned above, but in a mixture with other polymers, such as for example EVA (ethylene-vinylacetate copolymer), ethylene-acrylic esters copolymers such as for example EMA (ethylene- methylacrylate copolymer), EBA (ethylene-butylacrylate copolymer), EEHA (ethylene-2-ethylhexylacrylate copolymer), EEA (ethylene-ethylacrylate copolymer), ethylene-acrylic acid copolymers, such as EAA (ethylene-acrylic acid copolymer) EMAA (ethylene-methacrylic acid copolymer), and relative ionomers where the polar comonomer content (VA, MA, BA, EHA, EA
  • This outer layer 10 is that normally intended to be subsequently printed on the surface, at least in some parts thereof, so that it could undergo corona discharge treatment, in a special apparatus 500 (Fig. 1).
  • Said corona discharge treatment apparatus 500 which very often is placed immediately downstream of the extrusion system 1 and upstream of the winding section 4 (Fig. 1) can be placed downstream of the stretching and/or annealing section 300 (Fig. 1) so as to subject the film to corona discharge treatment before being irradiated.
  • said corona discharge treatment apparatus can be placed in the irradiation system (before or after the phase of irradiation) and in all cases has the purpose of increasing the wettability of the surface which is treated and promoting adhesion of the ink and, in some cases, promoting the subsequent coupling of the outer layer 10 by means of lamination to other films normally thinner which have various functions (protection of the outer surface 10 from scratches and abrasions arising from handling, thermal resistance, increase in shine or conferring of a different surface appearance: more opaque, "silky", soft touch).
  • the binding layers 20 and 40 have the purpose of binding one to the other the layers 10 and 30, or the layers 50 and 30, respectively, which, being normally poorly compatible one with the other, given the different polymeric nature, risk separating easily during the operations of preparation, filling and use of the future tube.
  • binding layers 20 and 40 are constituted by any polymer of the layer 10 or 50 provided it is grafted, or copolymerised, with maleic anhydride.
  • the barrier layer 30 can be constituted by EVOH (ethylene vinyl alcohol), PVOH (polyvinyl alcohol), PA (polyamide, in all its forms of PA6 homopolymer, of copolyamide, terpolyamide, and the like, and aromatic polyamides) and also any other polymer capable of providing a barrier to gases and aromas, such as polyvinylidene chloride, Barex (polyacrylonitrile methyl acrylate), polyketones, or any polyolefin added with nanofillers capable of improving the barrier to gases of the base polyolefin in which they are dispersed.
  • EVOH ethylene vinyl alcohol
  • PVOH polyvinyl alcohol
  • PA polyamide, in all its forms of PA6 homopolymer, of copolyamide, terpolyamide, and the like, and aromatic polyamides
  • any other polymer capable of providing a barrier to gases and aromas such as polyvinylidene chloride, Barex (polyacrylonitrile methyl acrylate), polyketone
  • the polymers which form the outer layer 50, which is intended to be the inner side of the tube 200 can be for example polyethylenes such as LD-PE (low-density polyethylene), MD-PE (medium-density polyethylene), HD-PE (high-density polyethylene), LLD-PE (linear low-density polyethylene) mLLD-PE (metallocene linear low-density polyethylene), VLD-PE (very low-density polyethylene), elastomers and plastomers, propylene-ethylene copolymers and the like, possibly grafted or copolymerized with maleic anhydride (MA), or mixtures thereof to ensure good welding capacity.
  • polyethylenes such as LD-PE (low-density polyethylene), MD-PE (medium-density polyethylene), HD-PE (high-density polyethylene), LLD-PE (linear low-density polyethylene) mLLD-PE (metallocene linear low-density polyethylene), V
  • EVA ethylene-vinylacetate copolymer
  • ethylene-acrylic esters copolymers such as for example EMA (ethylene-methylacrylate copolymer), EBA (ethylene-butylacrylate copolymer), EEHA (ethylene-2- ethylhexylacrylate copolymer), EEA (ethylene-ethylacrylate copolymer), ethylene- acrylic acid copolymers such as EAA (ethylene-acrylic acid copolymer), EMAA (ethylene-methacrylic acid copolymer), which are normally used also to improve the seal of welding or even ionomers, these polymers can also be mixed with polyethylenes.
  • EVA ethylene-vinylacetate copolymer
  • EMA ethylene-methylacrylate copolymer
  • EBA ethylene-butylacrylate copolymer
  • EEHA ethylene-2- ethylhexylacrylate copolymer
  • EEA ethylene-ethylacrylate copo
  • the extruded film 3 is a multilayered film with seven layers comprising also one or more intermediate functional layers, with various technological functions in order to increase some properties such as mechanical strength and rigidity of the structure, defined as follows (Fig. 6): - outer layer 10 with a base of polyolefins
  • intermediate barrier layer 30 e.g. EVOH
  • These functional layers 10A and 50A can for example be constituted by LD-PE, HD- PE (to confer rigidity), or MD-PE or also LLD or also other polymers present in the other layers but their function is that of incorporating components which it is preferable not to place in the outer layers.
  • the layer 10A and/or 50A can be advantageously filled with white master with a base of titanium dioxide, useful for conferring a white colouring to the tube but which, if added in the outer layer 10 or 50, would jeopardise the surface shine.
  • polymers such as HD-PE, useful for achieving the necessary rigidity of the tube (necessary to the extent that the thicknesses of the film are reduced according to a tendency towards lightening of the packaging which involves also this type of containers), yet which confer typically opacity to the surface of the tube.
  • co-extruded films 3 can be provided with a structure with nine layers or more, without thereby departing from the scope of the present invention. Moreover, even if not explicitly described, films 3 can also be provided which provide in their structure more than one barrier layer (using different polymers included in the list given above for the barrier layer 30, possibly positioned in different layers) and/or a number of functional layers greater than two, without thereby departing from the scope of the present invention.
  • each of the layers 10, 20, 30, 40, 50 of the extruded film 3 in accordance with the present invention including the functional layers 10A, 50A
  • one or more functionalising additives including, typically, coloured masters (white, but also other colours), antiblock (e.g. silica), slip, antistatic, anti- condensation, antimicrobial, anti-UV, antioxidant, process aids, nanofiller additives, and others known in the art.
  • additives are not explicitly included in the formulas mentioned but can be added in one or more of the layers of the co-extruded item.
  • the multilayered extruded film 3 is subjected to a phase of irradiation, downstream of the blown extruder 1.
  • Irradiation can take place in line with the production of the film 3 or off line at a later time.
  • the film 3 exiting from the rollers 2 of the blown extruder 1 is wound in coils in a winding section 4 in order to be stored and treated off line.
  • the co-extruded film 3 is sent into a special irradiation station which, as mentioned, can be downstream of the blown extruder 1 or in a separate line where the film 3 is subjected to ionizing rays (Fig. 2) for example by means of bombardment with high-energy electrons, in particular accelerated electrons with energy from 0.05 to 10 Mev. More particularly the co-extruded film 3 is subjected to the abovementioned irradiation treatment by passing into a special chamber in which the irradiating apparatus is placed.
  • the film 3 is made therefore to pass inside a vacuum chamber 60 in such a way as to wind the outer layer 50, intended to be the inner layer of the tube 200, towards the emitter of the electron beam 61 which is then focused towards the material to be treated, so as to make said beam 61 penetrate at least in the outer layer 50, generating radicals and creating a series of chain reactions of the radical type which lead to the formation of new bonds (e.g. crosslinking).
  • the electron beam 61 is generated through the thermionic effect by filaments of tungsten 62 heated to very high temperatures (above 2000°C) and accelerated by a high-voltage electrical field in a vacuum chamber.
  • the electron beams 61 with high dosages are therefore used here to modify the molecular structure in that it was found by the Applicant that the crosslinking that can be obtained with these electron beams entails a substantial modification of the molecular structure, with respect to the film not subjected to this irradiation, so that the film itself, after irradiation as described above, has at least two distinctive features:
  • the fluidity of the polymer understood as melt flow index measured according to ASTM D1238, passes from values of some units, e.g. 1 or 2 (expressed in g/lOmin), to such low fraction values, so as not to be measurable with conventional methods and instruments (the molten polymer subjected to irradiation does not exit the nozzle of the special instrumentation);
  • said coil 100 of irradiated film 3" can be sent to a phase of further processing such as printing on the surface and/or lamination of other functional films on the surface of the outer layer 10, of the film 3, for example to protect the print, and then sent to a section for the making of the tube 200 (Fig. 4). It is specified that the coil 100 of Figure 3 is already represented in the printed version for greater diagram clarity.
  • the co-extruded film 3, directly exiting from the extruder 1, as in the more typical case (or unwound from a coil produced in the winding section 4), can also be subjected to a treatment of stretching and/or of annealing before being irradiated.
  • the co-extruded film 3 is sent into a special treatment section 300 (Fig. 1) constituted by an MDO (machine direction orientation) section and/or by an annealing section as will be described here below in detail.
  • a special treatment section 300 constituted by an MDO (machine direction orientation) section and/or by an annealing section as will be described here below in detail.
  • the passage into the stretching and/or annealing section 300 can be performed on line at the extrusion phase by operating on the extruded film 3 exiting from the blown extruder 1, or it can take place at a later time off line by operating on the film 3 unwound from a coil prepared in the winding section 4.
  • the film 3 is brought to the temperature of softening by making it pass through the first heating rollers 5;
  • the film 3 is toughened by annealing rollers 7 and subjected to voltage; the heat blocks the physical features achieved by the film in the previous steps;
  • Cooling the film 3 is brought to ambient temperature by passing through a series of cold rollers 8, and then exiting from the section 300.
  • the film exiting the treatment section 300 which is a stretched and/or annealed film 3', will then be sent to the phase of irradiation (if the irradiation is to be performed in line) or of winding in a coil in the winding station 11 (if the irradiation is to be performed off line) .
  • rollers 5, 6, 7, 8 of the various phases which take place in the treatment section 300 are independent and rotate at different speeds in that designed to perform different operations.
  • the operating conditions of said rollers and of said phases of stretching and/or annealing depend on the type of film to be treated and the relative multilayered structure of the co-extruded film 3. It is to be noted however that the aforesaid operation of stretching which takes place in the treatment section 300 must not be confused with the light physiological stretching which the film 3 undergoes during the formation of the bubble of film during the extrusion in the extruder 1, thanks to the fact that in the treatment section 300 the stretching conditions can be set to obtain a certain degree of stretch.
  • the Applicant has found that the abovementioned stretching and annealing treatment is particularly advantageous, especially in the case of co-extruded film 3 with high thickness, e.g. greater than 250 ⁇ , in that this treatment confers improved planarity to the film 3 and an alignment of the edges of a quality which is difficult to obtain with simple blown extrusion. It is therefore understood that the treatment of stretching and/or annealing in the station 300 is optional, even if it is preferred in that advantageous in terms of final properties of the film. In a particularly preferred embodiment, the co-extruded film 3 is subjected both to stretching and to annealing before being irradiated.
  • the step of annealing is particularly advantageous for extruded films with high thickness (such as those that are the object of the present invention) in that, in addition to conferring features of improved transparency and shine, greater elastic modulus and improved mechanical properties in general, allow the thickness to be uniformed enormously to the extent of leading to the production of coils with alignment of the edges of quality unachievable with a traditional extrusion without annealing station, with consequent reduction in the waste through scrap arising from the subsequent phase of printing.
  • the tube 200 illustrated in Fig. 4 can be made from a coil 100 of co- extruded and irradiated film 3", optionally machine oriented and/or annealed previously.
  • the irradiated film 3" flat sheet
  • the irradiated film 3" is cut adequately and folded/wound on itself so as to be shaped into a tube and subsequently heat-welded vertically and horizontally for the closure of the tube.
  • the application of the rigid part allows the closure at one end and therefore the filling of the tube 200 and finally the successive horizontal welding allows the closure from the other end.
  • barrier film in the form of a sheet or flat sheet intended for the production of flexible containers in the form of tubes, where said barrier film is co- extruded, subsequently cut to size, and comprises two opposite outer layers with a base of olefin (co)polymers, an intermediate barrier layer and optionally at least two intermediate binding layers wherein at least one of the two opposite outer layers of said film cut to size is irradiated at least on the surface.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une bobine (100) de film barrière (3") soufflé ou moulé coextrudé, destiné à la production de récipients souples (200) sous la forme de tubes, caractérisé en ce que ledit film barrière coextrudé est également irradié en surface sur au moins l'une des deux couches externes opposées (10; 50) avec une base de (co)polymères d'oléfine, ledit film comprenant en outre une couche barrière intermédiaire (30) et, en option, au moins deux couches de liaison intermédiaires (20; 40).
PCT/EP2018/070156 2017-07-26 2018-07-25 Bobine de film barrière irradié, facultativement mono-orienté, pour la production de tubes malléables Ceased WO2019020687A1 (fr)

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IT102017000085388A IT201700085388A1 (it) 2017-07-26 2017-07-26 Bobina di film barriera irradiato, opzionalmente mono-orientato, per la realizzazione di tubetti collassabili e relativo metodo di produzione
IT102017000085388 2017-07-26

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Publication number Priority date Publication date Assignee Title
CN111319216A (zh) * 2020-03-03 2020-06-23 武汉惠强新能源材料科技有限公司 一种三层共挤锂离子电池隔膜的制备方法
EP4166317A1 (fr) * 2021-10-12 2023-04-19 Albea Services Récipient tubulaire flexible pour pcr
CN117580706A (zh) * 2021-07-29 2024-02-20 阿贝尔服务 柔性管容器

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Publication number Priority date Publication date Assignee Title
IT201800006996A1 (it) 2018-07-06 2020-01-06 Accoppiato termolaminato in “monomateriale” a base di polietilene per imballaggi flessibili riciclabili
IT202200013846A1 (it) 2022-06-30 2023-12-30 Ind Termoplastica Pavese S P A Film polimerico per la copertura di autoveicoli

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WO1999050064A1 (fr) * 1998-03-31 1999-10-07 American National Can Company Sacs a volaille retractables
WO2000000392A1 (fr) * 1998-06-26 2000-01-06 American National Can Company Sachets protecteurs thermoretractables
WO2002055386A2 (fr) * 2001-01-11 2002-07-18 Pechiney Emballage Flexible Eu Sachets protecteurs thermoretractables avec additifs antiadherents
WO2012151679A1 (fr) * 2011-05-12 2012-11-15 Macro Engineering & Technology Inc. Tube en plastique multicouches

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WO1995000333A1 (fr) * 1993-06-24 1995-01-05 American National Can Company Structures ameliorees de polymeres produits a l'aide de catalyseurs a site unique
WO1999050064A1 (fr) * 1998-03-31 1999-10-07 American National Can Company Sacs a volaille retractables
WO2000000392A1 (fr) * 1998-06-26 2000-01-06 American National Can Company Sachets protecteurs thermoretractables
WO2002055386A2 (fr) * 2001-01-11 2002-07-18 Pechiney Emballage Flexible Eu Sachets protecteurs thermoretractables avec additifs antiadherents
WO2012151679A1 (fr) * 2011-05-12 2012-11-15 Macro Engineering & Technology Inc. Tube en plastique multicouches

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111319216A (zh) * 2020-03-03 2020-06-23 武汉惠强新能源材料科技有限公司 一种三层共挤锂离子电池隔膜的制备方法
CN117580706A (zh) * 2021-07-29 2024-02-20 阿贝尔服务 柔性管容器
EP4166317A1 (fr) * 2021-10-12 2023-04-19 Albea Services Récipient tubulaire flexible pour pcr
EP4166316A1 (fr) * 2021-10-12 2023-04-19 Albea Services Récipient de tube flexible contenant des résines recyclées

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EP3658370A1 (fr) 2020-06-03

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