EP3707195A1 - Film barrière à base de polyéthylène utilisé dans la production d'ensilage - Google Patents

Film barrière à base de polyéthylène utilisé dans la production d'ensilage

Info

Publication number
EP3707195A1
EP3707195A1 EP18800134.1A EP18800134A EP3707195A1 EP 3707195 A1 EP3707195 A1 EP 3707195A1 EP 18800134 A EP18800134 A EP 18800134A EP 3707195 A1 EP3707195 A1 EP 3707195A1
Authority
EP
European Patent Office
Prior art keywords
film
polyethylene
film according
based film
hydrocarbon resin
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.)
Withdrawn
Application number
EP18800134.1A
Other languages
German (de)
English (en)
Inventor
Marc DERVYN
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.)
Trioworld Ombree dAnjou SAS
Original Assignee
Trioplast France SAS
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 Trioplast France SAS filed Critical Trioplast France SAS
Publication of EP3707195A1 publication Critical patent/EP3707195A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01F—PROCESSING OF HARVESTED PRODUCE; HAY OR STRAW PRESSES; DEVICES FOR STORING AGRICULTURAL OR HORTICULTURAL PRODUCE
    • A01F25/00—Storing agricultural or horticultural produce; Hanging-up harvested fruit
    • A01F25/13—Coverings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01F—PROCESSING OF HARVESTED PRODUCE; HAY OR STRAW PRESSES; DEVICES FOR STORING AGRICULTURAL OR HORTICULTURAL PRODUCE
    • A01F15/00—Baling presses for straw, hay or the like
    • A01F15/07—Rotobalers, i.e. machines for forming cylindrical bales by winding and pressing
    • A01F15/071—Wrapping devices
    • A01F2015/0745—Special features of the wrapping material for wrapping the bale
    • 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
    • B32B2250/24—All layers being polymeric
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
    • 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
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/58—Cuttability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/582—Tearability
    • B32B2307/5825—Tear resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/71—Resistive to light or to UV
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional 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
    • B32B2410/00—Agriculture-related articles
    • 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
    • B32B2571/00—Protective equipment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons

Definitions

  • the present invention relates to protective films for use in agriculture, in particular silage production.
  • Plastic film is used for many different purposes.
  • plastic stretch film is frequently used in different fields of application, in particular for wrapping various products, for example wrapping goods for shipping or storing, or for wrapping agricultural bulk products, such as grass, straw, various crops, etc.
  • stretch film may for instance be used as fodder protection and silage film.
  • silage anaerobic conditions are desirable, and so the film should provide a barrier against moisture and oxygen.
  • Silage can be produced and stored in the form of bales or in a bunker silo or a pit silo.
  • a baler is first used to form a compact bale of the crop/vegetable product intended to be ensiled, and the bale is subsequently wrapped tightly with net, twine or film to retain the shape of the bale. Once the net, twine or film is lying around the bale, the formed bale is ejected from the baling chamber. The bale is then wrapped with an agricultural stretch wrap film using a bale wrapper.
  • the agricultural stretch wrap film is stretched, typically in the range of 50-75% and the stretched agricultural stretch wrap film is wrapped multiple turns around the bale to form an airtight and waterproof bale suitable for silage production.
  • a large volume of crop e.g. grass
  • a protective silage film to provide an airtight cover.
  • the crop may be compacted prior to covering with the protective film.
  • the film is often secured by placing heavy objects, such as tyres, on top of the film.
  • agricultural silage films are made primarily of one or more polymers, in particular polyolefins (e.g. polyethylene).
  • the polyolefin is extruded and blown to form a tubular film.
  • various additives such as pigments, tackifiers, UV stabilizers, etc, are added to the film composition in order to meet the requirements of the intended use.
  • Silage films typically contain UV stabilizers, and often pigments to reflect sunlight and/or to reduce transmission of sunlight into the bale or silo.
  • Stretch film for baled silage also requires high cling, and high mechanical performance in terms of good resistance to puncturing and tearing. Also for use in bunker or pit silos the mechanical properties of the film are of importance.
  • silage films have consisted of a single layer, although in recent years multilayer films for silage applications have emerged.
  • oxygen barrier films are available, containing a core layer of an oxygen barrier material such as ethylene-vinyl alcohol or polyamide.
  • an oxygen barrier material such as ethylene-vinyl alcohol or polyamide.
  • such films are relatively expensive and may be difficult to produce, process and/or recycle due to the content of ethylene-vinyl alcohol or polyamide.
  • a polyethylene-based film useful in the production of silage comprising polyethylene at a content of 60-90 % by weight of the film, wherein the polyethylene is selected from linear low density polyethylene (LLDPE) and low density polyethylene (LDPE) and combinations thereof, and a dicyclopentadiene hydrocarbon resin at a content of 3-20 % by weight of the film.
  • LLDPE linear low density polyethylene
  • LDPE low density polyethylene
  • the present inventors surprisingly found that by including dicyclopentadiene hydrocarbon resin in a film based on linear low density polyethylene (LLDPE) and optionally low density polyethylene (LDPE), considerably improved oxygen barrier property was obtained, while preserving the excellent mechanical properties of polyethylene of low density making the film useful as a silage film. It was found that the oxygen transmission rate was reduced by up to 35-40 % compared to films that did not contain the dicyclopentadiene hydrocarbon resin. Meanwhile, the strength at break (MD and TD,
  • low density when referring to polyethylene typically refers to a density of 0.930 g/cm 3 or less, such as 0.925 g/cm 3 or less.
  • the films according to the invention may further be free of conventional barrier materials such as, for instance, ethylene vinyl alcohol (EVOH) or polyamide, which are not easily recyclable and/or obstructs recycling of the polyethylene content of such conventional barrier films.
  • EVOH ethylene vinyl alcohol
  • polyamide polyamide
  • At least part of the polyethylene content of the film may originate from regranulated polyethylene, that is, recycled polyethylene.
  • the regranulated polyethylene may contain a combination of linear low density polyethylene (LLDPE) and low density polyethylene (LDPE), and may have a density of up to 930 g/cm 3 s, such as in the range of from 0.860 to 0.930 g/cm 3 .
  • the dicyclopentadiene hydrocarbon resin has a softening point in the range of 100-145 °C, preferably 130- 145 °C.
  • a dicyclopentadiene hydrocarbon resin having a softening point above 130 °C, such as between 130-145 °C, may have increased barrier properties.
  • the film comprises a dicyclopentadiene hydrocarbon resin at a content of 4.5-15 % by weight of the film, such as 5-15 % by weight of the film, such as 6-13 % by weight of the film.
  • the dicyclopentadiene hydrocarbon resin is at least 90 % hydrogenated.
  • the dicyclopentadiene hydrocarbon resin originates from thermal cracking of hydrocarbons, such as naphtha.
  • the film comprises at least one layer containing a mixture of linear low density polyethylene and dicyclopentadiene.
  • the dicyclopentadiene hydrocarbon resin is present at a content of 5-13 % by weight of the film.
  • the film has an oxygen gas transmission rate (OTR) of 250 cm 3 /m 2 /24h or less, as measured according DIN 53380-3 using air instead of oxygen gas.
  • OTR oxygen gas transmission rate
  • the film may have an OTR of 200 cm 3 /m 2 /24h or less, such as an OTR of 160 cm 3 /m 2 /24h or less.
  • a film having such OTR levels may have a thickness of about 90-150 ⁇ , such as about 100-120 ⁇ , such as about 1 10 ⁇ .
  • the film is a multilayer film, preferably comprising at least a first outer layer, a second outer layer, and a core layer arranged between said first outer layer and said second outer layer.
  • the film has a thickness in the range of from 15 to 180 ⁇ .
  • the film may have a thickness that is more than 70 ⁇ , such as more than 80 ⁇ .
  • the film may further comprise pigments.
  • the film may further comprise dyes.
  • the film may further comprise fillers.
  • the film may further comprise UV stabilizers.
  • the film may further comprise tackifiers.
  • the film may further comprise slip agents.
  • the film may further comprise nucleating agents.
  • the film may further comprise processing aids.
  • the film further comprises one or more additives selected from pigments, dyes, fillers, UV stabilizers, tackifiers, slip agents, nucleating agents, and processing aids.
  • the film comprises one or more pigments at a content of from 3 to 10 % by weight of the film, such as from 5 to 7 % by weight of the film.
  • the film has a density in the range of from 0.920 to 1 .00 kg/m 3 .
  • the film has a thickness in the range of from 80 to 180 ⁇ , preferably from 90 to 125 ⁇ and optionally a width in the range of 5-20 m, preferably 6-18 m.
  • the film is cut to a length of 400 m or less, preferably 100 m or less.
  • the film has a thickness in the range of from 15 to 30 ⁇ and optionally a width in the range of from 500 to 1500 mm, preferably 500- 750 mm or 1 100 to 1500 mm.
  • the film may be cut to a length of 1500-2500 m, preferably 1800-2200 m.
  • the film is prestretched. In embodiments, the film is a stretch film.
  • the film according to embodiments of the present invention allows an anaerobic environment to be formed and thereby nutrients and energy content of the silage to be preserved during storage.
  • a silage film should form a gas barrier, in particular an oxygen barrier.
  • the oxygen barrier properties can be measured according to known standards, such as ASTM D3985 or DIN 53380-3.
  • a silage film as disclosed herein may have an oxygen transmission rate (OTR) of 10 000 cm 3 /m 2 /24h or less as determined according to DIN 53380-3.
  • a silage film according to embodiments of the present invention suitable for use as a stretch wrap silage film for baling may have an oxygen permeability of less than 10 000 cm 3 /m 2 /day, such as within the range of from 1 000 to 10 000 cm 3 /m 2 /24 h measured according to DIN 53380-3 Stretch wrap films are thin, but are wrapped multiple turns around a bale.
  • Silage films for bunker or pit silos are typically thicker than stretch wrap silage films, and as such may have an OTR which is
  • Silage films according to the invention suitable for use in such applications may have an OTR of
  • the film may be a monolayer film or a multilayer film, and may be produced by conventional means, such as cast extrusion or blow extrusion.
  • the polyethylene film is a coextruded multi-layer blown film comprising at least two layers.
  • the polyethylene film is a multilayer film comprising at least three layers: at least one core layer arranged between two exterior layers.
  • the multilayer film may comprise at least a first outer layer, a second outer layer, and a core layer arranged between said first outer layer and said second outer layer.
  • the core layer may comprise low density polyethylene (LDPE), such as LDPE originating from regranulated polyethylene.
  • LDPE low density polyethylene
  • At least two layers of the multilayer film may comprise the dicydopentadiene hydrocarbon resin.
  • all layers of the film may comprise the dicydopentadiene hydrocarbon resin. It has been found that it is advantageous to put dicydopentadiene in all layers since too much dicydopentadiene in the same layer may decrease the tear resistance of the film.
  • no single layer of the multilayer film comprises more than 20 % of the dicydopentadiene hydrocarbon resin.
  • all layers of the film comprise the dicydopentadiene hydrocarbon resin and no single layer of the multilayer film may comprise more than 20 % of the dicydopentadiene hydrocarbon resin.
  • the dicyclopentadiene hydrocarbon resin is present in an amount that is less than 20% such as less than 15%, in all layers of the film.
  • dicyclopentadiene may be present in all layers but to an amount that is less than 20%, such as less than 15%, in each layer. Having an amount of dicyclopentadiene hydrocarbon resin in an amount that is above 20 % in a single layer may lead to a decrease in tear resistance of the film.
  • the dicyclopentadiene hydrocarbon resin may be present at a content of 5-13 % by weight of a multilayer film.
  • the multilayer film may be polyethylene-based film consisting of a first outer layer, a second outer layer, and a core layer arranged between said first outer layer and said second outer layer; wherein said outer layers comprises linear low density polyethylene (LLDPE) and said
  • the LLDPE may give the film desired mechanical properties and bubble stability.
  • the core layer arranged between said first outer layer and said second outer layer may comprise low density polyethylene (LDPE). Further, the core layer may also comprise the dicyclopentadiene hydrocarbon resin.
  • LDPE low density polyethylene
  • the low density polyethylene (LDPE) of the core layer may originate from regranulated polyethylene. Furthermore, when using LDPE that originates from
  • dicyclopentadiene in all layers since too much dicyclopentadiene in the same layer may decrease the tear resistance of a film with regranulates.
  • the polyethylene-based film may be a multilayer film having a three-layer structure, in which the first and second outer layers comprises LLDPE and the dicyclopentadiene hydrocarbon resin and wherein the core layer comprises the dicyclopentadiene hydrocarbon resin and LDPE that originates from regranulated polyethylene.
  • mechanical properties or “mechanical performance” is herein mainly meant the mechanical strength of the material, measured in terms of at least one of tensile strength, tear strength and puncture resistance. Tensile strength, measured as force per unit area, is defined as the maximum stress that a material can withstand while being stretched or pulled before failing or breaking.
  • Tear strength typically measured as force per unit length
  • Elongation at break is defined as the ultimate elongation (given as percentage of the initial length) of a material before it breaks under tension.
  • Puncture resistance typically measured as mass per unit length, is defined as the relative ability of a material to withstand a falling dart without breaking.
  • the prestretched polyethylene film is a silage film, such as an agricultural bale wrap film or a silage cover film for use in a bunker silo or a pit silo.
  • the invention provides use of a film as defined herein as a protective film for the production of silage.
  • a film as defined herein as a protective film for the production of silage.
  • the use of the film is for covering a pit silo or a bunker silo.
  • the use of the film is for wrapping of silage bales.
  • Fig. 1 is a schematically illustrates, in cross-section, a multilayer film according to embodiments of the present invention.
  • Fig. 2 is a schematic illustration of a production line for producing a film according to embodiments of the invention.
  • Fig. 1 schematically illustrates, in cross-section, a film, for instance a silage film, according to embodiments of the present invention
  • the film 100 is a multilayer film comprising three layers: a first outer layer 101 , a middle layer or core layer 102, and a second outer layer 103.
  • the first and second outer layers are arranged on opposing sides of the core layer, and in this
  • outer layers 101 , 102 are in contact with the core layer while each outer layers forms an exterior surface of the film.
  • the outer layers 101 , 102 may be referred to as outermost layers or skin layers.
  • additional skin layers may be provided outwardly of the outer layers 101 , 103 in relation to the core layer.
  • additional layers may be provided in the form of additional core layers, e.g. on opposing sides of the core layer 102 but in between the outer layers 101 , 103.
  • the layers 101 , 102, 103 may have the same or different composition.
  • Each of the layers 101 , 102, 103 may comprise, as a base material, a polyethylene or a blend of polyethylenes, having a density of up to 0.930 g/cm 3 , such as from 0.860 to 0.930 g/cm 3 or to 0.925 g/cm 3 .
  • the polyethylene or blend of polyethylenes may include virgin polyethylene material such as metallocene catalyzed LLDPE (mLLDPE) or Ziegler-Natta catalyzed LLDPE (znLLDPE), or recycled polyethylene material, which may comprise a blend of LLDPE and LDPE.
  • the outer layers 101 , 103 may contain mLLDPE as base material.
  • the core layer(s) may contain as base material a blend of LLDPE and LDPE obtained from recycled polyethylene.
  • Linear low density polyethylene (“LLDPE”) comprises, in polymerized form, a majority weight percent of ethylene based on the total weight of the LLDPE.
  • LLDPE can be an interpolymer of ethylene and at least one ethylenically unsaturated comonomer.
  • the comonomer can be a C3-C20 a-olefin.
  • the comonomer can be a C3-C8 a-olefin.
  • the C3-C8 a-olefin can be selected from propylene, 1 - butene, 1 -hexene, or 1 -octene.
  • the LLDPE used in the present invention may be selected from the following copolymers: ethylene/propylene copolymer, ethylene/butene copolymer, ethylene/hexene copolymer, and ethylene/octene copolymer.
  • the LLDPE is an ethylene/octene copolymer.
  • LLDPE typically has a density in the range from about 0.890 g/cm 3 to about 0.940 g/cm 3 , or from about 0.91 g/cm 3 to about 0.94 g/cm 3 .
  • LLDPE may have a melt index (Ml) from about 0.1 g/10 min to about 10 g/10 min, or about 0.5g/10 min to about 5g/10 min.
  • LLDPE can be produced with Ziegler-Natta catalysts, or single-site catalysts, such as vanadium catalysts and metallocene catalysts (mLLDPE). In an embodiment, the LLDPE is produced with a Ziegler-Natta type catalyst.
  • LLDPE is linear and is different than low density polyethylene ("LDPE") which is branched or heterogeneously branched polyethylene.
  • LDPE has a relatively large number of long chain branches extending from the main polymer backbone.
  • LDPE can be prepared at high pressure using free radical initiators, and typically has a density from 0.915 g/cc to 0.940 g/cc.
  • the film may contain, as a whole, polyethylene a content of 60-95 % by weight of the film, for instance from 70 to 90 %, or from 75 to 88 %.
  • any one layer 101 , 102 or 103 may contain from 40 to 99 % of polyethylene base material having a density of 0.930 g/cm 3 or less, such as 0.860-0.930 g/cm 3 .
  • the film may contain mLLDPE at a content of from 20 to 90 % by weight of the film.
  • the film may contain mLLDPE at a content of from 20 to 40 % by weight of the film, and regranulated polyethylene material at a content of from 20 to 75 % by weight of the film.
  • At least one layer of the film 100 contains a dicyclopentadiene hydrocarbon resin.
  • the core layer 102 contains a dicyclopentadiene hydrocarbon resin.
  • each of the layers 101 , 102, 103 contains a dicyclopentadiene hydrocarbon resin.
  • the total content of the dicyclopentadiene hydrocarbon resin is typically from 3 to 15 % by weight of the film.
  • dicyclopentadiene hydrocarbon resin is present in more than one layer, the content of the dicyclopentadiene hydrocarbon resin may be the same in each layer, or the content may be different in the different layers.
  • the outer layers 101 , 103 may be free of dicyclopentadiene hydrocarbon resin.
  • any skin layer may be free of dicyclopentadiene hydrocarbon resin.
  • Dicyclopentadiene hydrocarbon resins are known and may be obtained e.g. by from thermal polymerization of olefin feeds rich in dicyclopentadiene (DCPD), or by other means e.g. as described in WO 98/55537 A1 .
  • the dicyclopentadiene hydrocarbon resin may be provided in the form of a masterbatch mixed with polyethylene, such as LLDPE. Preparation of a masterbatch is known and is described e.g. in WO 98/55537 A1 .
  • the dicyclopentadiene hydrocarbon resin may originate from thermal cracking of hydrocarbons, such as naphtha.
  • the hydrocarbon may be a higher hydrocarbon, such as a hydrocarbon having 5-12 carbon atoms, such as 6-12 carbon atoms.
  • the dicyclopentadiene hydrocarbon resin may be produced by fractionating C6-C12 products produced in the process of ethylene
  • the dicyclopentadienes of the dicydopentadiene hydrocarbon resin may comprise less than 50 %, such as less than 20 %, such as less than 10 %, such as less than 5 %, of polydicyclopentadienes (PDCPD).
  • PDCPD polydicyclopentadienes
  • the dicydopentadiene hydrocarbon resin may be free of poly- dicyclopentadienes (PDCPD)
  • the dicydopentadiene hydrocarbon resin for use in the present invention may have a softening point in the range of from 100 to 140 °C, or about 140 °C.
  • the dicydopentadiene hydrocarbon resin may be at least partially
  • the dicydopentadiene hydrocarbon resin may be at least 95 %, 99 %, or fully hydrogenated.
  • the dicydopentadiene hydrocarbon resin may be provided in the form a masterbatch e.g. blended with polyethylene.
  • One or more of the layers of the film may comprise a pigment.
  • Suitable pigments for use in polyethylene films e.g. for silage making are known to persons of skill in the art and include, for instance, titanium dioxide and carbon black.
  • Different layers of the film may contain different pigments and/or amounts of pigment.
  • silage films may include a pigment providing a light colour, such as white, light blue or light green, to the side of the film intended to face outwards, such that sunlight is reflected.
  • at least an outer layer, e.g. layer 101 may contain a pigment providing a light color.
  • silage films in particular film intented for use in bunker or pit silos, may have a dark colored second side intended to face the crop, in order to prevent light transmission into the silo.
  • a layer such as the layer 103, may contain a dark pigment, such as a black pigment.
  • the film may optionally contain a UV stabilizer, present in one or more of the layers, e.g. in outer layer 101 , and optionally in each of the layers 101 , 102, 103.
  • UV stabilization is meant protection of a material from the long-term degradation effects from light, most frequently ultraviolet radiation (UV).
  • a UV stabilizer may be advantageous for preventing chain reactions caused by e.g. radicals within the polyolefin layer(s) of the prestretched polyethylene film e.g. during storage outdoors of the prestretched
  • the film may optionally contain other conventional additives, such as fillers, slip agents, tackifiers, processing aids, nucleating agents, and the like.
  • the film 100 may be a silage film, e.g. intended as a cover for a bunker silo or a pit silo.
  • the film may have one or more of the following properties: an Elmendorf tear strength (machine direction, MD) of at least 400 cN, preferably at least 500 cN; an Elmendorf tear strength (transverse direction, TD) of at least 1500 cN, preferably at least 2000 cN; a strength at break (MD and/or TD) of at least 17 MPa, preferably at least 23 MPa; an elongation at break (MD) of at least 250 %, preferably at least 500 %; an elongation at break (TD) of at least 250 %, preferably at least 500 %; and a dart resistance of at least 200 g, preferably at least 400 g.
  • Bunker silo films and pit silo films typically have a thickness in the range of from 80 to 180 ⁇ , such as from 90 to 130 ⁇ , or from 100 to 120 ⁇ , or about 1 10 ⁇ .
  • the film may have a width in the range of from 5 to 20 meters, such as from 10 to 18 meters or from 12 to 18 meters.
  • the film weight per meter of film may be in the range of from 1 .0 to 1 .5 kg/m, or from 1 .2 to 1 .4 kg/m.
  • the film may be supplied at a film length up to 400 m, e.g. from 50 to 400 m.
  • the bunker silo film may be a multilayer film, such as a multilayer film comprising two outer layers sandwiching at least one core layer.
  • the multilayer film may consist of a single core layer sandwiched between two outer layers (skin layers).
  • the at least one core layer of a silage film may have a thickness that is between 40-60% of the whole film thickness.
  • the at least one core layer may have a thickness that is between 40-80 ⁇ , such as between 50-70 ⁇ , such as about 60 ⁇
  • the outer layers each may have a thickness that is between 15-35 ⁇ , such as between 15-25 ⁇ or between 25-35 ⁇ .
  • the outer layers may have the same thickness or have different thicknesses.
  • a silage film of the present disclosure since a silage film of the present disclosure has a lower oxygen permeability, i.e. better barrier properties, than conventional silage films, the silage film of the present disclosure may be thinner than conventional silage films for the same application, but still have the same barrier properties as a conventional film. It may be advantageous to have a thinner silage film since such a film may be of lower weight, and therefore easier to handle and use. Therefore, a bunker or pit silo film of the present disclosure may have a thickness that is less than 100 ⁇ , such as between 60-100 ⁇ , such as between 70-90 ⁇ . In other embodiments, the film may be a stretch wrap film intended for wrapping of silage bales, also referred to as a bale wrap film.
  • bale wrap films are typically provided in the form of rolls, having a film width to match the operating width of the wrapper, often from 500 to 750 mm.
  • the length of the film on a single roll may be at least 1000 m, or at least 1500 m and up to 2500 m, or up to 2200 m.
  • the film may be prestretched.
  • prestretched film means that the film is stretched in the longitudinal direction during the film production process before being wound to a roll. Stretching is typically performed in a prestretch unit of the production line and involves passing the film between two or more stretching rollers rotating at different speeds.
  • the prestretching may preferably be performed directly after the extrusion or film blowing steps, while the film is still hot.
  • the degree of prestretching is intended to mean the difference in speed, in percent, between the stretching rollers in the prestretch unit. The difference in speed corresponds to the elongation of the prestretched film between the stretching rollers in the prestretch unit.
  • a prestretched polyethylene film may have a longitudinal degree of prestretching above 70%.
  • the longitudinal degree of prestretching of the prestretched polyethylene film may for example be between 70% and 150%, such as between 70% and 125%, between or 70% and 100%.
  • a prestretched polyethylene film may have a longitudinal degree of prestretching between 70% and 85%, preferably between 71 % and 79%, preferably between 73% and 77%, preferably about 75%.
  • the prestretched polyethylene film has a remaining longitudinal elongation capability of at least 320%, preferably at least 340%, as determined according to ASTM D882.
  • elongation capability means the elongation percentage at break, as measured in accordance with the ASTM D882 standard, wherein a strip of film with a width of 20 mm, clamped between two clamps at a distance of 50 mm from each other is stretched at a rate of 500 mm/min until the film breaks. At least five strips of the film must be measured, and the elongation capability corresponds to the mean value of the
  • the stress required in order to stretch the prestretched polyethylene film by 70% in the longitudinal direction is less than 19 MPa, preferably less than 18 MPa, as determined according to ASTM D882.
  • the stress required in order to stretch the prestretched film by 70% in the longitudinal direction can be read from the tensile strength graph obtained when measuring the elongation percentage at break in accordance with the ASTM D882 standard as described herein. At least five strips of the film must be measured, and the stress at 70% elongation corresponds to the mean value of the measurements.
  • At least one outer layer, or if present, a skin layer, of the film 100 may comprise a soft polymer.
  • a soft polymer may provide a relatively soft surface to the outer surface of the film which may increase friction and reduce slip in a direction substantially parallel to the film surface.
  • a soft polymer may particularly be advantageous in a stretch wrap film, which in use is wrapped with an overlap such that the film may adhere, or cling, to itself.
  • cling is meant the ability of a material to adhere to itself or an adjacent object.
  • the adjacent object may be a layer of the same or a different film.
  • the film may comprise a tackifier.
  • tackifier is herein meant an agent that provides cling to a film. Such an agent may be added to a layer of the polyethylene film in order to increase the cling of the layer.
  • a tackifier may be a soft polymer, or a migrating tackifier.
  • a tackifier thus serves to increase the cling of the polyethylene film, in particular, one or both of the outer layers or skin layers.
  • the tackifier is a migrating tackifier.
  • migrating tackifier is herein meant a tackifier which is soluble in the film material, e.g. in polyethylene. If a migrating tackifier is added to a film (or film layer) in an amount exceeding the solubility level of the film (or film layer), the excess can migrate within the film material to the film surface (including also migrating from a first layer to and through another layer, when the first layer has been saturated with the migrating tackifier).
  • a migrating tackifier may thus provide an adhesive surface which increases the friction in a direction substantially perpendicular to the film surface.
  • a migrating tackifier may be advantageous when the film is e.g. wrapped, such that an exterior layer of a first portion of the polyethylene film adhere, or cling, to an exterior layer of a second portion of the same, or a different, polyethylene film.
  • the migrating tackifier is present at a content of from 1 to 15% by weight based on the total weight of the core layer.
  • the content of migrating tackifier added to the at least one core layer typically exceeds the content of migrating tackifier required to saturate the at least one core layer with regard to the migrating tackifier.
  • the content required to saturate the at least one core layer may depend on the content of
  • the film is produced by a blown film process, known to persons of skill in the art.
  • the film may be a coextruded blown film comprising at least two layers, and typically at least three layers.
  • a monolayer or multilayer polyethylene film according to embodiments of the invention may be produced by a manufacturing process involving the following steps:
  • step f) extruding the first composition obtained in step c) to form at least one first layer;
  • step g) optionally extruding the at least one additional extrudible composition of step d) or step e) to form at least one outer layer on adjacent the first layer.
  • the first layer may be a core layer, and the at least one additional extrudible composition, optionally mixed with dicyclopentadiene hydrocarbon resin, may form one or more additional layers, such as two outer layers sandwiching the core layer.
  • a second extrudible composition optionally mixed with dicyclopentadiene hydrocarbon resin masterbatch, may form an outer layer 101 as described above.
  • a third extrudible composition, optionally mixed with dicyclopentadiene hydrocarbon resin may form a second outer layer 103 as described above.
  • the steps of extruding the first extrudible composition to form a first layer (e.g. core layer) and the one or more additional extrudible compositions to at least one outer layer, respectively, may be performed separately from each other e.g. by monoextrusion, or simultaneously e.g. by coextrusion.
  • the multilayer film is prepared by co-extrusion, using one extruder per layer simultaneously.
  • Monoextrusion and coextrusion are techniques generally known to the person skilled in the art.
  • extrudible compositions may be provided to form a plurality of core layers, at least one of which is mixed with the
  • step of extruding the first composition obtained in step a) to form at least one core layer may imply that the first composition is extruded to a single core layer or to multiple core layers.
  • the multiple core layers are extruded simultaneously by coextrusion and adhere to each other due to substantially identical chemical properties.
  • the dicyclopentadiene hydrocarbon resin may be provided in the form of a masterbatch mixed with polyethylene, such as LLDPE.
  • the masterbatch may be mixed with the first extrudible composition and optionally with one or more additional extrudible composition(s) as described above.
  • a blown film production line such as prestretched balewrap, is schematically depicted in Fig. 2.
  • a film composition as described above is extruded from a blow extruder 1 to form a blown film bubble that is advanced through primary nip rollers 1 a. The nip roller nips together the blown film.
  • the tubular film 2 is passed via guide rollers to a stretch unit 3, where stretching is performed between two rollers, first draw roller 4 and second draw roller 5, having different speeds.
  • the stretch unit 3 may be omitted, in which case the film is not prestretched.
  • Silage films intended for use in bunker silos or pit silos are typically not prestretched.
  • the tubular film is passed to a dividing station 6 where the edges of the film 2 may be cut to provide two individual sheets of film.
  • the film 2 is passed to the secondary nip rollers 7 where the individual sheets of film 8 may be separated.
  • Each film sheet 8 may optionally pass through a second dividing station (not shown) where the sheet may be divided longitudinally into two or more parallel sections of desired width.
  • the film sheets, or film sheet sections are wound onto the winders 9.
  • the tubular film is typically wound onto one of the winders 9.
  • the film may be a prestretched stretch wrap film having a degree of prestretching above 70 %, for instance in the range from 75 to 100 %.
  • the film according to the invention may be used in the production of silage.
  • the film is used in a method producing silage using a bunker silo or a pit silo, comprising the step of
  • the film is arranged over the crop to provide an airtight protective barrier.
  • the film is used in a method of wrapping a bale of crop for the production of silage bales, comprising the steps of:
  • Silage can be produced from grasses as well as numerous other crops, including grains (barley, oats, rice, wheat, rye, millet), corn, cornstalk, legumes, beans, soybeans, and vegetables.
  • Test films were produced polyethylene base material (mLLDPE or LDPE or medium density polyethylene, MDPE) of various suppliers as presented in Table 1 , mixed, at different loading contents with a
  • dicyclopentadiene hydrocarbon resin The "A" sample of each series represented a reference, without dicyclopentadiene hydrocarbon resin.
  • the films were extruded using a lab extruder LABTECH LF 250.
  • Series 1 was made using medium density polyethylene.
  • the films were subjected to the following test: oxygen transmission rate (DIN 53380-3 using air instead of oxygen gas for testing), strength at break (ASTM D882 or ISO 527-3), elongation at break (ASTM D882 or ISO 527-3), Elmendorf tear strength (ASTM D1922 or ISO 6383-2). Additionally, the pressure before and after the extruder filter was recorded as well as engine intensity. Table 2a. Polyethylene base material: HF 513 (Total), density 0.934 g/cm 3 . Film characteristics and ox en transmission data.
  • Table 2b Polyethylene base material: HF 513 (Total). Mechanical properties.
  • Table 3a Polyethylene base material: FE 3000 (Qapco). Film characteristics and ox en transmission data.
  • Polyethylene base material Regranulated PE (Trioplast) with MFI:
  • Polyethylene base material Regranulated PE (Trioplast).
  • Exemplary films and reference films were produced using a full scale blown film co-extrusion process.
  • the exemplary films had three layers, formed from first, second and third extrudible compositions having the content as shown in Table 7.
  • the extrudible compositions were each mixed separately using blending devices or mixing devices generally known to a person skilled in the art.
  • a film having an ABC layer structure was formed, wherein a core layer (B) was formed of the first extrudible composition and two exterior layers (A and C, respectively) sandwiching the core layer were formed of the second extrudible composition (A) and the third extrudible composition (C), respectively.
  • the bubble stability was excellent. 55 rolls were produced.
  • the total film composition was as shown in Table 8.
  • the film had a width of 12 m, a length of 50 m, a thickness of 1 10 ⁇ and an overall density of 0.970 g/cm 3 .
  • a reference film was produced in the same manner as described above for the exemplary film, except that instead of dicyclopentadiene hydrocarbon resin the film contained a blend of mLLDPE and regranulated polyethylene.
  • the film had a width of 12 m, a length of 50 m, a thickness of 1 10 ⁇ and an overall density of 0.958 g/cm 3 .

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental Sciences (AREA)
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Abstract

L'invention concerne un film à base de polyéthylène utile dans la production d'ensilage, ledit film comprenant du polyéthylène à hauteur de 60 à 90 % en poids du film, le polyéthylène étant choisi parmi du polyéthylène linéaire basse densité (LLDPE) et du polyéthylène basse densité (LDPE) et des combinaisons de ceux-ci, et une résine hydrocarbonée dicyclopentadiène à hauteur de 3 à 20 % en poids du film. Le film présente de bonnes propriétés de barrière à l'oxygène et est utile dans la production d'ensilage.
EP18800134.1A 2017-11-10 2018-11-08 Film barrière à base de polyéthylène utilisé dans la production d'ensilage Withdrawn EP3707195A1 (fr)

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EP17201169.4A EP3483206B1 (fr) 2017-11-10 2017-11-10 Film barrière à base de polyéthylène utile pour la production d'ensilage
PCT/EP2018/080604 WO2019092100A1 (fr) 2017-11-10 2018-11-08 Film barrière à base de polyéthylène utilisé dans la production d'ensilage

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US20220227977A1 (en) * 2019-05-13 2022-07-21 Nova Chemicals (International) S.A. Films from recycled polyethylene
US20220371308A1 (en) * 2019-10-15 2022-11-24 Braskem S.A. Shrink films incorporating post-consumer resin and methods thereof
DE202020100703U1 (de) 2020-01-31 2021-02-02 Kbg Kunststoff Beteiligungen Gmbh Verpackungsfolien aus Recycling-Kunststoffen
AR121711A1 (es) * 2020-03-31 2022-06-29 Tama group Envoltura de fardo multicapa
US20230264449A1 (en) * 2020-06-24 2023-08-24 Trioworld Nyborg A/S Tubular film for stretch hoods comprising recycled material
EP4119345A1 (fr) * 2021-07-13 2023-01-18 Trioworld Ombrée d'Anjou SAS Film multicouche comprenant du polyéthylène recyclé utile comme film d'ensilage

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DE3520944A1 (de) * 1985-06-12 1986-12-18 Wolff Walsrode Ag, 3030 Walsrode Siegelbare mehrschichtenfolien mit geringer gasdurchlaessigkeit und ihre verwendung als verpackungsmaterial
US5145728A (en) * 1987-11-30 1992-09-08 Toa Nenryo Kogyo Kabushiki Kaisha Oriented polyethylene film
US5075156A (en) * 1988-03-15 1991-12-24 Asahi Kasei Kogyo Kabushiki Kaisha Multi-layered crosslinked ethylenic resin film, a process for production thereof and a method of applying said film
WO1998055537A1 (fr) * 1997-06-06 1998-12-10 Hercules Incorporated Pellicules de polyethylene de densite elevee possedant de meilleures caracteristiques de barriere
EP1373400A2 (fr) * 2001-03-16 2004-01-02 Chevron Phillips Chemical Company LP Melanges de resines de polyethylene et de resines aliphatiques hydrogenees de faible poids moleculaire
US6824864B2 (en) * 2001-10-23 2004-11-30 Exxonmobil Oil Corporation Multi-layer, white cavitated bioriented polyethylene film with a high water vapor transmission rate
BE1017770A3 (nl) * 2007-09-28 2009-06-02 Combipac Bv Voorgerokken rekwikkelfolie.
KR101395274B1 (ko) * 2012-09-26 2014-05-15 롯데케미칼 주식회사 다층 필름용 접착성 수지 조성물
EP3009263A1 (fr) * 2014-10-15 2016-04-20 Trioplast AB Film barrière

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EP3483206A1 (fr) 2019-05-15
WO2019092100A1 (fr) 2019-05-16
ES2833848T3 (es) 2021-06-15

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