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
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
  • A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
  • A01G9/14—Greenhouses
  • A01G9/1438—Covering materials therefor; Materials for protective coverings used for soil and plants, e.g. films, canopies, tunnels or cloches
• • 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
  • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
  • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
  • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
  • Y02A40/25—Greenhouse technology, e.g. cooling systems therefor

Definitions

• the present invention relates to a multilayer film structure suitable for agricultural use, which may be prepared by co-extrusion or lamination processes.
• Plastic films are used extensively in agriculture in order to improve plant yield.
• ethylene-based polymer films are employed for this purpose, in particular for greenhouses, tunnels as well as mulching.
• Typical examples of known ethylene polymer films employed in this application are LDPE (low density polyethylene) films as well as EVA (ethylene-vinyl acetate) films. These materials typically are employed in the form of single layer films of varying thickness, typically from 100 to 250 ⁇ m. The requirements for such films are various and not all types of films are able to satisfy the needs with respect to all required properties.
• Typical requirements for agricultural films are as follows:
• They should provide a suitably high scattering of the light transmission, i.e., they should provide a rather diffusive effect in order to decrease direct light impact on young plants while avoiding at the same time sharp shadows excluding certain areas under the film from light transmission. 6. They should provide protection against harmful UV radiation, i.e., they should absorb at least a portion of the natural UV radiation.
• direct sunlight through greenhouse coverage i.e., non-scattered light
• direct sunlight also produces sharp shadows preventing light from reaching all parts of the growing crop within a greenhouse.
• a film showing a higher haze accordingly is advantageous in view of the fact that such a film diffuses the incoming light, however at the same time, it is of course important that light transmission is enabled in the p_hoto active range (PAR) of radiation which is a wavelength of from 400 to 700 nm in order to improve the growth rate of the crop within the greenhouse.
• PAR p_hoto active range
• Prior art film materials have i.a. a drawback that they show low degree of scattering, i.e. they have low or no diffusive effect.
• EVA furthermore is a relatively expensive material limiting its use in agricultural films.
• mineral fillers have been widely employed, as well as the coating of the film with a paint. This, however, disadvantageously lowers the light transmission of the light in the PAR and, at the same time, also reduces the mechanical strength of the films.
• An optimal film for agricultural and horticultural accordingly should combine as much of the advantageous properties indicated above and such a film at least should combine high light scattering, i.e. diffusive, effect, and high transmission of both direct light and diffuse light, in the photoactive range (PAR) while, at the same time, providing a sufficient mechanical strength.
• PAR photoactive range
• an alternative multilayer film structure exhibiting an excellent balance of i.a. light transmission properties, whereby the films of the invention are particularly suitable for use in agriculture.
• Another object of the present invention is to provide an alternative monolayer film structure exhibiting high scattering effect expressed as haze suitable for use in agriculture or aquaculture.
• a further object is to provide a material suitable for the use in a film layer of a monolayer or multilayer film structure for use in agriculture or aquaculture.
• a further object is to provide film structures, such as monolayer or multilayer film structures, suitable as a coverage for growing plants in agriculture or as a coverage of a fish pool in aquaculture.
• multilayer film of the invention is referred herein as "film of the invention” or "Film”.
• the less matt surface property of layer (B) of Film can be defined in two alternative ways, i.e. by an end property of the less matt layer (B) or, respectively, by the polymer composition properties of the less matt layer (B). Both alternatives, i.e. technical features, define equally applicable product parameters for describing the present invention, which parameters are well known, generally accepted parameters.
• the invention is directed to a multilayer film which comprises at least two layers (A) and (B), wherein - layer (A) comprises a linear low density polyethylene (LLDPE) composition with molecular weight distribution MWD (Mw/Mn) of 8 or more, and
• LLDPE linear low density polyethylene
• -layer (B) comprises a polymer composition selected from a group comprising a low density polyethylene composition (referred herein as LDPE), a copolymer of ethylene with one or more of comonomers selected from vinyl acetate and acrylate, linear low density polyethylene (LLDPE) composition with molecular weight distribution MWD (Mw/Mn) of less than 8 or a polypropylene polymer.
• LDPE low density polyethylene composition
• LLDPE linear low density polyethylene
• the invention is directed to a multilayer film which comprises at least two layers (A) and (B), wherein
• -layer (A) comprises a linear low density polyethylene (LLDPE) composition with molecular weight distribution MWD (Mw/Mn) of 8 or more, and
• -layer (B) comprises a polymer composition which, when produced to a blown film consisting of said polymer composition and having a film thickness of 50 ⁇ m, has a gloss value of 60 % or more when determined according to ASTM D 2457 measured at angle 60°.
• the film sample of said polymer composition of layer (B) used for the gloss measurement was prepared as described below under "Film Sample Preparation”.
• the unifying feature is the combination of a matt layer (A) with a less matt layer (B) as defined in the two alternatives, which combination provides the unexpected technical effect discussed above and below.
• the Film is a film according to the first alternative.
• the polymer composition present in layer (B) of said first alternative has, when measured from a blown film consisting of said polymer composition, as defined for the second alternative, a gloss as defined in the second alternative invention.
• the skilled person can readily choose the polymer composition for layer (B) accordingly.
• the LLDPE composition present in layer (A) as defined above or below has a broad molecular weight distribution.
• the LLDPE composition when produced to a blown film consisting of said polymer composition has typically a high haze value, as measured according to ASTM D 1003.
• Preferably said LLDPE composition of layer (A) has also low gloss value measured according to ASTM D 2457 at an angle of 60° using a film sample consisting of said LLDPE.
• said polymer composition comprised by layer (B) has preferably also a lower haze value than said LLDPE composition of layer (A).
• the specific layer combination of (A)/(B) of the invention provides a high scattering effect, i.e. high haze property. Also unexpectedly the film of the invention shows high scattering effect (haze) irrespective of which side of Film, matt layer (A) or less matt layer (B), is turned to the light.
• Film possesses said high light scattering effect and at the same time high light transmission property for both diffuses and direct light.
• This unique balance of properties can be achieved irrespective of which side, (A)-layer side or (B)-layer side of the film structure is turned towards a light source.
• the Film has additionally excellent mechanical properties, i.e. high film strength as described in details below under film properties.
• the films of the invention are particularly suitable for use in agriculture, overcoming drawbacks indicated above in connection with the prior art.
• the preferable embodiment wherein the Film has an excellent property balance between light transmission in the photoactive wavelength range (PAR) of from 400 to 700 nm and mechanical properties is highly advantageous for use as coverage for growing plants.
• PAR photoactive wavelength range
• the invention further provides, in addition to the multilayer structure mentioned above, a monolayer film having a layer thickness of 50 ⁇ m or more and comprising a linear low density polyethylene (LLDPE) composition with a MWD of 8 or more.
• LLDPE linear low density polyethylene
• the monolayer film of the invention as described above is referred herein as "Monolayer film” to differentiate it from terms “Film” and “Film of the invention” which refer to above multilayer film structure. Unless otherwise stated preferred embodiments as described for the multilayer film structure also apply for the monolayer film of the present invention.
• the thickness, i.e. the layer thickness, of said Monolayer film is preferably of 400 ⁇ m or less, more preferably of from 100 to 300 ⁇ m, more preferably of from 100 to 250 ⁇ m, and in embodiments from 50 to 300 ⁇ m, preferably 75 to 250 ⁇ m, more preferably 100 to 200 ⁇ m
• said Monolayer film has typically a haze of 40% or more, preferably of 50% or more, more preferably of 60% or more, even more preferably 65 to 80%, when produced as a blown film and measured according to ASTM D 1003. More preferably the Monolayer film has such haze values, including the preferable ranges as defined above, in combination with the preferred thickness as defined above.
• the invention further provides the use of a linear low density polyethylene (LLDPE) composition with MWD of 8 or more for preparing a monolayer film suitable for use in agriculture or aquaculture, preferably as a coverage for a fish pool.
• LLDPE linear low density polyethylene
• the invention still further provides the use of a linear low density polyethylene (LLDPE) composition with MWD of 8 or more in a film layer of a multilayer film structure as described herein, suitable for use in agriculture or aquaculture, preferably as a coverage for a fish pool.
• LLDPE linear low density polyethylene
• Film can be used in any shape and size in a form of a coverage which has a surface area e.g. of more than 10 m 2 , even more than 100 m 2 , e.g. in a form of a cover element, e.g. a wall and/or a roof material in greenhouses and tunnels, or in mulching, for plants and that it can be exposed to sunlight, preferably to the outdoor light and weather conditions.
• a cover element e.g. a wall and/or a roof material in greenhouses and tunnels, or in mulching, for plants and that it can be exposed to sunlight, preferably to the outdoor light and weather conditions.
• the upper limit of surface area is not critical and depends on the needed coverage.
• the Monolayer film or the Film of the present invention is also very suitable for use in aquaculture, preferably as a coverage for a fish pool.
• the shape and size of such coverage in aquaculture may be similar to or same as described in relation to such coverage in agriculture.
• the invention further provides the use of the monolayer or multilayer film structure of the invention in agriculture or aquaculture, preferably and particularly as a coverage for growing plants in agriculture or as a coverage of a fish pool in aquaculture.
• layers and specifically for layer (A) as to layer property or the LLDPE material thereof applies in particular also for the Monolayer film of the present invention.
• Figure 1 display the results of measurements of the light transmission in the PAR for various films tested in the examples.
• additives e.g. conventional film additives, i.e. each layer independently may contain conventional film additives in conventional amounts, such as antioxidants, UV stabilizers, anti-fogging agents, UV absorbers, IR reflectors used in agricultural films and optionally other conventional additives acid scavengers, nucleating agents, anti-blocking agents, slip agents etc., as well as polymer processing agent (PPA).
• PPA polymer processing agent
• the amount of optional additives is typically less than 5 wt%, e.g. between 0.0001- 3 wt% calculated from the sum (wt%) of additives and polymer components present in a layer.
• the Film preferably does not comprise fillers used in the prior art. If fillers or pigments, such as kaolin, are present they may be used in conventional amounts, e.g. up to 10 wt%, such as 5 to 8 wt%.
• the present invention relates to a multilayer film structure comprising at least layer (A) and layer (B).
• the film of the invention may also comprise further layers e.g. for optimising the light transmission and/or mechanical properties or for providing additional beneficial properties to Film, depending on the needs of a desired end application. Any optional layer is selected so that it has no adverse effect on the light scattering effect achieved with the invention.
• Film comprises one or more further layers (A 1 ) which may comprise, preferably consist of, a LLDPE composition which can be same or different compared to the LLDPE composition of layer (A). If one or more optional layers (Ai) are present, then the LLDPE of layer(s) (A 1 ) is preferably same as the LLDPE of layer (A). More preferably layer (A) and optional layer(s) (A 1 ) consist of a LLDPE composition, preferably again the LLDPE in these layers is the same in all of the layers.
• Film comprises one or more further layers (B 1 ) which may comprises a polymer composition selected from a group as defined above and below for layer (B) (both alternatives of the present invention).
• Layer (B 1 ) and (B) may comprise the same or different polymer composition.
• the film of the invention may also contain an adhesive layer or any of the layers may be subjected to a surface treatment in a manner well known in the art.
• the layer (A) and layer (B), and optional layers (A 1 ) and/or (B 1 ), when present, are in direct contact with each other, i.e. without any adhesive layer or surface treatment of one or more of the layers.
• Film of a (A)/(B)-layered structure comprises further layers, then preferably, layers (A) and (B) as defined above or below form the outermost layers of the multilayer Film.
• Preferred films of the invention can be selected from any of the following independent embodiments, wherein the layers are in given order:
• both layer sides (A) and (B) provide high light scattering effect and preferably high light transmission effect for diffuse and direct light and, moreover, e.g. in greenhouse applications, both layer (A) side and layer (B) side of Film can be used as an outer layer turned towards to a light source, such as sun light.
• layer (B) has a gloss value of 60 % or more when determined according to ASTM D 2457 measured at angle 60° using a blown film sample. Although for the gloss determination herein a blown Film Sample consisting of a polymer composition of layer (B) and having a film thickness of 50 ⁇ m was used, said gloss value applies for other layer thicknesses, preferably for thicknesses expressed as thickness distribution below under "Film properties".
• Layer (A) as indicated above comprises a LLDPE providing a matt surface, i.e. a lower gloss, compared with the layer (B).
• the gloss value of layer (A), determined as defined above for layer (B) is at least 10 percentage points lower than the gloss value for layer (B), e.g. layer (A) has a gloss of 50% or less, when determined as described for layer (B) above.
• layer (A) has a haze value of more than 40%, preferably more than 50%, when determined according to ASTM D 1003 using a blown film sample.
• a blown Film Sample consisting of a polymer composition of layer (A) and having a film thickness of 50 ⁇ m was used, however said haze value applies for other layer thicknesses, preferably for thicknesses expressed as thickness distribution below under "Film properties".
• said layer (A) is used as an outer layer towards a light source
• said layer (B) is used as an interior side, i.e. faces towards the growing plants.
• the light coming from the film to plants is "soft" and well utilized due to light reflection from layer (B) inside the greenhouse.
• the invention is also directed to an article comprising a multilayer film of the invention, wherein said multilayer film has a surface area of at least 10 m 2 .
• Such articles are e.g. greenhouses or tunnels having said Film coverage.
• Invention further provides a construction for agricultural use comprising a rigid framework for defining and retaining the shape of the construction and a coverage covering the framework and being supported by said framework, wherein said coverage comprises the multilayer film of the invention.
• the construct is preferably a greenhouse or a tunnel for growing plants.
• Said article or construction can also be a shelter or coverage arranged over a fish pool, wherein the roof and, if present, the walls are formed by the multilayer or monolayer film of the present invention.
• LLDPE linear low-density polyethylene which is obtainable by polymerization in a low-pressure process using a conventional coordination catalyst.
• LLDPE used alone means “LLDPE composition”.
• Said layer (A) comprises at least a LLDPE composition as defined above and below and may comprise also other polymers, such as a second, different LLDPE composition or a high density polyethylene (HDPE) composition.
• LLDPE composition as defined above and below and may comprise also other polymers, such as a second, different LLDPE composition or a high density polyethylene (HDPE) composition.
• HDPE high density polyethylene
• Layer (A) comprises said LLDPE composition in an amount of at least 50 wt%, preferably at least 70 wt%, more preferably at least 80 wt%.
• layer (A) consists of one or more, preferably one LLDPE as defined above or below.
• Said LLDPE composition may be polymerised by any conventional coordination catalysis including Ziegler Natta catalysis (referred herein as znLLDPE), single site, including metallocene and non-metallocene, catalysis (referred herein as mLLDPE) or chromium catalysis.
• LLDPE can be unimodal or multimodal with respect to molecular weight distribution as further explained below.
• LLDPE with a broad MWD present in layer (A) as defined above, below or in claims is preferably a multimodal LLDPE. More preferably, said multimodal LLDPE is a multimodal znLLDPE.
• multimodal means herein, if not otherwise stated multimodality with respect to molecular weight distribution and includes also bimodal polymer.
• a polyethylene e.g. LLDPE composition
• multimodal a polyethylene, e.g. LLDPE composition
• multimodal polymer includes so-called “bimodal” polymer consisting of two fractions.
• LLDPE will show two or more maxima or is typically distinctly broadened in comparison with the curves for the individual fractions.
• the polymer fractions produced in the different reactors will each have their own molecular weight distribution and weight average molecular weight.
• the individual curves from these fractions form typically together a broadened molecular weight distribution curve for the total resulting polymer product.
• the multimodal LLDPE comprises a lower weight average molecular weight component (LMW) and a higher weight average molecular weight component (HMW).
• LMW lower weight average molecular weight component
• HMW higher weight average molecular weight component
• the LMW component has a lower molecular weight than the higher molecular weight component.
• said multimodal LLDPE is an ethylene copolymer, whereby at least one of the LMW and HMW components is a copolymer of ethylene. It is preferred that at least HMW component is an ethylene copolymer.
• the lower molecular weight (LMW) component is also preferably an ethylene copolymer. Alternatively, if one of the components is a homopolymer, then LMW is the preferably the homopolymer.
• the multimodal LLDPE may comprise further polymer components, e.g. three components being a trimodal LLDPE.
• multimodal LLDPE may also comprise e.g. up to 10 % by weight of a well known polyethylene prepolymer which is obtainable from a prepolymerisation step as well known in the art, e.g. as described in WO9618662.
• the prepolymer component is comprised in one of LMW and HMW components, preferably LMW component, as defined above.
• said multimodal LLDPE suitable for use in said Monolayer film or layer (A) in said Multilayer film of the invention comprises at least said LMW polymer component and said HMW polymer component.
• said multimodal LLDPE is a bimodal LLDPE comprising said LMW and HMW components and optionally a prepolymerised fraction as defined above.
• LLDPE of layer (A) provides, in combination with layer (B) 1 the effect of the invention, i.a. light scattering, i.e. haze property.
• the other properties of LLDPE of layer (A) of the invention are not critical and can be varied within the scope of the invention depending on the desired end use application. Accordingly, said LLDPE composition usable in the layer(s) of the present invention may have any of the preferred properties given generally below.
• Said LLDPE composition may have a density of no more than 940 kg/m 3 , e.g. a density of 905 to 940 kg/m 3 , preferably of more than 915 kg/m 3 , more preferably between 915 to 935 kg/m 3 .
• the melt flow rate, MFR 2 , of said LLDPE is preferably in the range of 0.01 to 20 g/10min, e.g. of 0.05 to 10 g/10min, preferably of 0.1 to 6.0 g/10min, more preferably in the range of 0.1 to 5 g/10min.
• MFR 2 of LLDPE may be even less than 3 g/10 min, e.g 0.1 to 2.5 g/10min.
• the MFR2 1 of LLDPE may be in the range 5 to 500 g/10 min, preferably 10 to 200 g/10min.
• the Mw of LLDPE may be in the range 100,000 to 300,000, preferably 150,000 to 270,000.
• the molecular weight distribution (MWD), Mw/Mn, of LLDPE is 8 or more, preferably at least 10, e.g. 10 to 30, more preferably 10 to 25.
• LLDPE has preferably a flow rate ratio FRR21/2 of at least 10, preferably at least 15.
• Upper limit of said FRR 21 / 2 is not limited and can be e.g. up to 200, particularly in case of multimodal LLDPE.
• LLDPE copolymer is used in this context to encompass polymers comprising repeat units deriving from ethylene and at least one other C3-20 alpha olefin monomer.
• LLDPE copolymer as defined above and below may be formed from ethylene along with at least one C3-12 alpha-olefin comonomer, e.g. 1-butene, 1-hexene or 1-octene.
• LLDPE is a binary copolymer, i.e. the polymer contains ethylene and one comonomer, or a terpolymer, i.e. the polymer contains ethylene and two or three comonomers.
• LLDPE comprises an ethylene hexene copolymer, ethylene octene copolymer or ethylene butene copolymer.
• the amount of comonomer present in LLDPE is at least 0.25 mol-%, preferably at least 0.5 mol-%, such as preferably 0.5 to 12 mol%, e.g. 2 to 10 mol-% relative to ethylene. In some embodiments a comonomer range of 4 to 8 mol-% may be desired. Alternatively, comonomer contents present in said LLDPE may be 1.5 to 10 wt%, especially 2 to 8 wt% relative to ethylene.
• Both the LMW and HMW components of a multimodal LLDPE as defined above or below are preferably copolymers of ethylene as defined above.
• any copolymeric HMW component at least 0.5 mol-%, e.g. at least 1-mol%, such as up to 10 mol-%, of repeat units present in HMW are preferably derived from the comonomer.
• the LMW component of said LLDPE may have a MFR 2 of at least 50, typically 50 to 3000 g/10 min, preferably at least 100 g/10 min, more preferably 110 to 500 g/10 min.
• the molecular weight of the low molecular weight component should preferably range from 15,000 to 50,000, e.g. 20,000 to 40,000.
• the density of said LMW component may range from 930 to 980 kg/m 3 , e.g. 940 to 970 kg/m 3 , more preferably 945 to 955 kg/m 3 in the case of copolymer and 960 to 980 kg/m 3 , preferably 965 to 977 kg/m 3 in the case of homopolymer.
• Said LMW component has preferably from 30 to 70 wt%, e.g. 40 to 60% by weight of LLDPE with said HMW component forming 70 to 30 wt%, e.g. 40 to 60% by weight.
• the HMW component comprises 50 wt% or more of said multimodal LLDPE as defined above or below.
• Said HMW component has a lower MFR 2 and a lower density than the LMW component.
• Said HMW component has preferably an MFR 2 of less than 1 g/10 min, preferably less than 0.5 g/10 min, especially less than 0.2 g/10min.
• the density of HMW is typically less than 915 kg/m 3 , e.g. less than 910 kg/m 3 , preferably less than 905 kg/m 3 .
• the Mw of the higher molecular weight component may range from 100,000 to 1 ,000,000, preferably 250,000 to 500,000.
• Multimodal LLDPE compositions that are suitable in said layer (A), when produced to a blown film consisting of said LLDPE composition and having a film thickness of 50 ⁇ m, provide preferably a haze value of more than 40%, preferably more than 50%, or, if desired, even more than 60%, when determined according to ASTM D 1003.
• a haze value is up to 80%.
• the multimodal LLDPE composition which is present in said Monolayer film, has typically, when produced to a blown film consisting of said LLDPE composition and having a film thickness of 50 ⁇ m, a haze value of 40% or more, preferably of 50% or more, more preferably of 60% or more, even more preferably 65 to 80%, when measured according to ASTM D 1003.
• Said LLDPE for layer (A) is preferably a multimodal znLLDPE copolymer composition as defined above or below.
• LLDPE's are available i.a. from Borealis and other PE producers/suppliers.
• the following commercial multimodal znLLDPE grades are given only as examples without limiting thereto: I.a. grades available from Borealis, such as Borstar® FBXXX grades, e.g. Borstar® FB2310 or Borstar® FB2230 etc., can be mentioned as feasible multimodal LLDPE materials for layer (A) and, if present, for other layer(s).
• LLDPE compositions and the optional other polymers usable in layer (A) or in any other layer are known and can be any conventional, e.g. commercially available.
• suitable polymer compositions can be produced in a known manner according to or analogously to conventional polymerisation processes including solution, slurry and gas phase processes, described in the literature of polymer chemistry.
• Said LLDPE compositions with broad MWD, preferably multimodal (e.g. bimodal) polymers can be made by mechanical blending two or more, separately prepared polymer components or, preferably, by in-situ blending in a multistage polymerisation process during the preparation process of the polymer components. Both mechanical and in-situ blending is well known in the field. Accordingly, preferred multimodal LLDPE polymers are obtainable by in-situ blending in a multistage, i.e. two or more stage, polymerization process. Alternatively, multimodal LLDPE may be obtainable by using two or more different polymerization catalysts, including multi- or dual site catalysts, in a one-stage polymerization.
• multimodal LLDPE may be obtainable by using two or more different polymerization catalysts, including multi- or dual site catalysts, in a one-stage polymerization.
• said multimodal LLDPE is produced in at least two-stage polymerization using the same catalyst, e.g. a single site or Ziegler-Natta catalyst.
• a catalyst e.g. a single site or Ziegler-Natta catalyst.
• the multimodal LLDPE is made using a slurry polymerization in a loop reactor followed by a gas phase polymerization in a gas phase reactor.
• a loop reactor - gas phase reactor system is well known as Borealis technology, i.e. as a BORSTAR® reactor system.
• Any multimodal LLDPE polymer present in layers of the invention is thus preferably formed in a two-stage process comprising a first slurry loop polymerisation followed by gas phase polymerisation.
• Such multistage process is disclosed e.g. in EP517868.
• the reaction temperature will generally be in the range 60 to 110 0 C (e.g. 85-110 0 C)
• the reactor pressure will generally be in the range 5 to 80 bar (e.g. 50-65 bar)
• the residence time will generally be in the range 0.3 to 5 hours (e.g. 0.5 to 2 hours).
• the diluent used will generally be an aliphatic hydrocarbon having a boiling point in the range -70 to +100 0 C.
• polymerization may if desired be effected under supercritical conditions.
• Slurry polymerisation may also be carried out in bulk where the reaction medium is formed from the monomer being polymerised.
• the reaction temperature used will generally be in the range 60 to 115°C (e.g. 70 to 110°C)
• the reactor pressure will generally be in the range 10 to 25 bar
• the residence time will generally be 1 to 8 hours.
• the gas used will commonly be a non-reactive gas such as nitrogen or low boiling point hydrocarbons such as propane together with monomer (e.g. ethylene).
• a chain-transfer agent preferably hydrogen
• at least 100 to preferably at least 200, and up to 1500, preferably up to 800 moles of H 2 /kmoles of ethylene are added to the loop reactor, when the LMW fraction is produced in this reactor, and 0 to 60 or 0 to 50, and, again depending on the desired end application, in certain embodiments even up to 100, or up to 500 moles of H 2 /kmoles of ethylene are added to the gas phase reactor when this reactor is producing the HMW fraction.
• the lower molecular weight polymer fraction is produced in a continuously operating loop reactor where ethylene is polymerised in the presence of a polymerization catalyst as stated above and a chain transfer agent such as hydrogen.
• the diluent is typically an inert aliphatic hydrocarbon, preferably isobutane or propane.
• the higher molecular weight component can then be formed in a gas phase reactor using the same catalyst.
• Prepolymerisation step may precede the actual polymerisation.
• the density, MFR 2 etc of the HMW component can be calculated using Kim McAuley's equations.
• both density and MFR 2 can be found using K. K. McAuley and J. F. McGregor: On-line Inference of Polymer Properties in an Industrial Polyethylene Reactor, AIChE Journal, June 1991 , Vol. 37, No, 6, pages 825-835.
• the density is calculated from McAuley's equation 37, where final density and density after the first reactor is known.
• MFR 2 is calculated from McAuley's equation 25, where final MFR 2 and MFR 2 after the first reactor are calculated.
• LLDPE as defined above and below may be made using any conventional catalyst, such as a chromium catalyst, a single site catalyst, including metallocenes and non-metallocenes as well known in the field, or a Ziegler Natta catalyst.
• a chromium catalyst such as a chromium catalyst, a single site catalyst, including metallocenes and non-metallocenes as well known in the field, or a Ziegler Natta catalyst.
• the preferred are any conventional Ziegler Natta catalysts and the choice of an individual catalyst used to make znLLDPE, respectively, is not critical.
• Preferred Ziegler Natta catalysts comprise a transition metal component and an activator.
• the transition metal component comprises a metal of Group 4 or 5 of the Periodic System (IUPAC) as an active metal. In addition, it may contain other metals or elements, like elements of Groups 2, 13 and 17.
• the transition metal component is a solid. More preferably, it has been supported on a support material, such as inorganic oxide carrier or magnesium halide. Examples of such catalysts are given, among others in WO 95/35323, WO 01/55230, WO 2004/000933, WO2004/000902, EP 810235 and WO 99/51646.
• the polyethylene composition is produced using a ZN catalysts disclosed in WO2004/000902, WO 2004/000933 or EP 688794.
• said layer (A) of said Multilayer film consists of said multimodal LLDPE.
• said multimodal LLDPE present in said Layer (A) comprises, preferably consists of, a LMW polymer component and a HMW polymer component as defined above.
• said blend of LMW polymer component and HMW component of said multimodal LLDPE is obtainable by a sequential multistage polymerization process using a slurry polymerization reactor, preferably loop reactor, and gas phase reactor, in any order, preferably as loop-gas phase polymerization process.
• said Monolayer film said monolayer consists of said multimodal LLDPE. More preferably said multimodal LLDPE present in said sole layer of the Monolayer film comprises, preferably consists of, a LMW polymer component and a HMW polymer component as defined above. Further preferably said blend of LMW polymer component and HMW component of said multimodal LLDPE is obtainable by a sequential multistage polymerization process using a slurry polymerization reactor, preferably loop reactor, and gas phase reactor, in any order, preferably as loop-gas phase polymerization process.
• a monolayer film, as well known, as the Monolayer film of the invention is a film consisting of only one layer, thus the following discussion of other layers applies only for the Multilayer film of the invention.
• Optional layer(s) (Ai) as defined above or below may comprise or consists of same or different polymer composition.
• at least one layer (Ai) comprises preferably one or more LLDPE composition as defined above or below.
• At least one layer (Ai), when present, may comprise HDPE.
• layer (A 1 ) comprising a LLDPE preferably comprises same LLDPE as defined for layer (A) above and below. Also preferably, when LLDPE is present in layer (A 1 ), then said layer (Ai) consists of said LLDPE.
• Film comprises one layer (A 1 ).
• layer (B) of Film provide preferably a gloss value of more than 60%, when determined according to ASTM D 2457 measured at angle 60° using a blown film sample.
• the preferable thickness distribution ranges are described below under "Film properties".
• a blown Film Sample of layer (B) with a thickness of 50 ⁇ m was used for the determination, however it is to be understood that the thickness is not limited thereto, but can be varied, preferably within the below given thickness distribution range.
• the layer (B) of Film can be defined alternatively, and preferably, according to first alternative of the invention as comprising a polymer composition selected from a group comprising, preferably consisting of, low density polyethylene composition (referred herein as LDPE), a copolymer of ethylene with one or more of comonomers selected from vinyl acetate and acrylate, LLDPE with Mw/Mn of less than 8 or polypropylene polymer.
• LDPE low density polyethylene composition
• LLDPE low density polyethylene composition with Mw/Mn of less than 8 or polypropylene polymer.
• Said group of polymers of layer (B) as defined in first and second alternative definitions of the invention are typically well known in the field and are commercially available or can be produced according to polymerization process described in literature.
• the polymer of said layer (B) is selected from a group of polymers as defined in the first alternative.
• Said layer (B) comprises preferably LDPE composition, an ethylene alkyl acrylate polymer (e.g. an ethylene C1-10 alkyl acrylate polymer), such as ethylene methyl acrylate (EMA), ethylene ethyl acrylate (EEA) and ethylene butyl acrylate (EBA), or any mixture thereof, preferably LDPE or EVA.
• an ethylene alkyl acrylate polymer e.g. an ethylene C1-10 alkyl acrylate polymer
• EMA ethylene methyl acrylate
• EAA ethylene ethyl acrylate
• EBA ethylene butyl acrylate
• LDPE means herein a low-density ethylene homopolymer produced in high-pressure polymerization process.
• LDPEs are well known in the art and they typically contain long chain branching which differentiates LDPEs from linear low-density polyethylene, LLDPE, polymers, such as znLLDPE and mLLDPE polymers.
• LLDPE linear low-density polyethylene
• LDPE has typically a MFR 2 of at least 0.05 g/10 min, preferably in the range 0.1-20 g/10 min, more preferably 0.3-10 g/10 min, still more preferably 0.5-5 g/10 min.
• the density of the LDPE is preferably 905-940 kg/m 3 , more preferably 910 to 937 kg/m 3 , e.g.
• the Vicat softening temperature of LDPE present in layer (B) is preferably 60-200 0 C, more preferably 80-150 0 C, e.g. about 90-110 0 C.
• the Tm of the LDPE present in layer (B) is preferably 70- 18O 0 C, more preferably 90-140 0 C, e.g. about 110-120 0 C.
• LDPEs suitable for Film and for layer (B) are any conventional LDPEs, e.g. commercially known LDPEs or they may be prepared according to any conventional high pressure polymerisation (HP) process in a tubular or autoclave reactor using a free radical formation.
• HP processes are very well known in the field of polymer chemistry and described in the literature, see e.g. Vieweg, Schely and Schwarz: Kunststoffoff Hanbuch, Band IV, Polyolefins, Carl Hanser Verlag (1969), pages 39-51.
• Typical pressures are from 1000 to 3000 bar.
• the polymerization temperature is preferably 150-350 0 C.
• the free radical initiators are commonly known, e.g. organic peroxide based initiators.
• the copolymer of ethylene with one or more acrylate comonomer may have an acrylate content of 1 to 40 wt%, preferably 2 to 30 wt%, more preferably 3 to 28 %, especially 5 to 25 wt%.
• EVA ethylene vinyl acetate copolymers
• MFR2 in the range 0.01-20 g/10 min, more preferably 0.1-10 g/10 min.
• MFR 2 0.2-5 g/10 min.
• the vinyl acetate content of EVA is in the range 1 to 40 wt%, preferably 2 to 30 wt%, more preferably 3 to 28 %, especially 5 to 25 wt%.
• ethylene acrylate and vinyl acetate copolymers are very well known and commercially available (e.g. from DuPont) or produced according to or analogously to the polymerisation methods descried in the literature for the preparation of ethylene acrylate and vinyl acetate copolymers, preferably in a high pressure polymerisation using organic peroxides in a manner well known in the art.
• the HP based copolymers are also referred as LDPE copolymers.
• preferable copolymers of ethylene for layer (B) are LDPE copolymers, such as EMA 1 EEA 1 EBA or EVA, preferably EVA.
• the propylene polymer option as a layer (B) polymer can be any known propylene polymer (PP) including PP well known as propylene homo polymer, propylene random copolymer and heterophasic block copolymer of propylene. All these are very well known in the field of polymers and are commercially available or can be produced using the convention polymerization processes.
• the propylene polymer properties are selected in a known manner to be suitable for film preparation.
• LLDPE has narrower MWD than the LLDPE of layer (A) 1 such as less than 8.
• LLDPE may be unimodal or multimodal and may be znLLDPE or mLLDPE.
• polymers suitable for layer (B) are not limited to above, but other polymers can also be used within the scope defined in claims.
• Polymer compositions suitable as said layer (B) material when produced to a blown film consisting of said polymer composition and having a film thickness of 50 ⁇ m, preferably have a gloss value of 60% or more, preferably of 75 % or more, more preferably of 85 % or more when defined according to ASTM D 2457 measured at 60° angle. It is even more preferred when said gloss value of said polymer composition is up to 99%, measured as defined above.
• layer (B) comprises at least LDPE, more preferably consists of LDPE.
• layer (B) comprises at least EVA, preferably consists of EVA.
• EMA, EEA, EBA and EVA can be used alone or additionally in embodiments wherein increased barrier for infra red radiation (IR), i.e. decreased IR radiation transmittance, is desired for Film in order to provide good thermal effect. Further these materials may be blended with an other polymer, such as those exemplified above, for example blends of two or more EMA, EEA, EBA, or EVA polymers, or mixtures thereof.
• Optional layer(s) (B 1 ) as defined above or below may comprise or consists of same or different polymer composition.
• at least one layer (B 1 ) comprises preferably comprise one or more polymer composition selected from a group as defined above and below for layer (B).
• layer(s) (B 1 ), when present, preferably comprises one or more of EMA, EEA, EBA and EVA, preferably EVA.
• layer(s) (Bi) may comprise or consist of same polymer composition as layer (B).
• layer(s) (B 1 ) may comprise or consist of different polymer composition as layer (B). If layer(s) (B 1 ) comprise, preferably consists of, a different polymer composition, it is preferably selected from a group as defined for layer (B) above or below.
• Film comprises one layer (B 1 ).
• Layers (A), (B) and, if present, optional layers (A 1 ) and (B 1 ), of Film may each independently contain conventional additives as defined above. As well known this can be added to the polymer composition e.g. during the preparation of the polymer of during the film preparation process.
• the different polymer components in any of layers (A) and (B) and in optional layers (A 1 ) and/or (B 1 ), are typically intimately mixed prior to layer formation, for example using a twin screw extruder, preferably a counter-rotating extruder.
• the layered structure of the film of the invention may be prepared by any conventional film formation process including extrusion procedures, such as cast film or blown film extrusion, lamination processes or any combination thereof. Preferred methods are coextrusion and lamination, more preferably coextrusion.
• the multilayer film comprising layers (A), (B) and the optional layers (A 1 ) and/or (B 1 ) is formed by blown film extrusion, more preferably by blown film coextrusion processes.
• the compositions providing layers (A) 1 (B) and optionally layers (A 1 ) and/or (B 1 ) can typically be produced by extrusion through an annular die, blowing into a tubular film by forming a bubble which is collapsed between nip rollers after solidification. This film can then be slit, cut or converted as desired.
• the blown (co)extrusion can be effected at a temperature in the range 160 0 C to 240 0 C, and cooled by blowing gas (generally air) at a temperature of 10 to 50 0 C to provide a frost line height of 1 to 8 times the diameter of the die.
• blowing gas generally air
• the blow up ratio should generally be in the range 1.2 to 6, preferably 1.5 to 4.
• the Monolayer film of the invention may be formed using the above described extrusion methods, such as blow extrusion, whereby said one layer may be formed by extruding one layer or as blown film coextrusion, wherein e.g. 3 layers, each of which consisting of the same LLDPE composition, are blown coextruded to form a final film, wherein said 3 layers of the same LLDPE composition form together one film layer.
• extrusion methods such as blow extrusion
• said one layer may be formed by extruding one layer or as blown film coextrusion, wherein e.g. 3 layers, each of which consisting of the same LLDPE composition, are blown coextruded to form a final film, wherein said 3 layers of the same LLDPE composition form together one film layer.
• Film thickness can vary.
• Film has a total thickness of at least 30 ⁇ m, preferably at least 50 ⁇ m.
• the upper limit is not critical and may be e.g. 400 ⁇ m or less.
• Preferred thickness may vary in the range of 50 to 300 ⁇ m, preferably 75 to 250 ⁇ m, more preferably 100 to 200 ⁇ m.
• the layer thickness distribution (%) of Film can be tailored depending on the end use.
• the Film of (A)/(B)-structure of the invention may have a layer thickness distribution (%) of (5-95%)/(95-5%), typically (90-50%)/(10-50%), preferably (80-20%)/(20-80%) calculated from the final Film thickness of 100%.
• the layer thickness distribution (%) is preferably A/B of (90-60%)/(10-40%), more preferably (85- 75%)/(15-25%) calculated from the final Film thickness of 100%.
• layers (A) and (A 1 ) may together form have a thickness distribution (%) as defined above for layer (A) in a (A)/(B) Film.
• layers (A) and (A 1 ) together may form 5- 95%, typically 90-50%, preferably 90-65%, more preferably 85-75%, of the final Film (100%).
• the layer (A 1 ) forms typically 10-90%, preferably 40-60%, of the combined thickness of layers (A) and (A 1 ).
• layers (B) and (B 1 ) together total the layer thickness distribution (%) as defined above for layer (B) in said (A)/(B) Film.
• the layer (B 1 ) forms typically 10-90%, preferably 40-60%, of the combined thickness of layers (B) and (B 1 ).
• the Film properties are measured using a film sample having a thickness of 150 ⁇ m and prepared as defined below in "Film Sample Preparation”. It is noted again that, although for the property determination herein said Film Sample was used, however the below given property definitions apply for other Film variants as well, including other layer thicknesses, thickness distributions (%), number of layers and final Film thicknesses within the claimed scope, e.g. defined above in the description as preferable ranges, subgroups and/or embodiments. The used determination methods are defined later below under “Determination methods”.
• the Monolayer film of the invention has i.a. very good light scattering properties.
• the haze values as given below for the Film in accordance with the present invention apply also for the Monolayer film as also described above.
• Preferably said Monolayer film has also the preferable haze and film thickness combination as given below.
• said Monolayer film has also very good mechanical properties.
• the multilayer film of the invention (Film) has very good mechanical properties.
• Film of the invention has preferably tear strength (ISO 6383/2) in transverse direction (TD) of at least 10 N, preferably at least 15 N, more preferably at least 20 N.
• Upper limit of said tear resistance of Film is not critical an may be e.g. of less than 50 N.
• Film of the invention has typically a tensile strength (ISO 527-3) in machine direction (MD) of at least 30 MPa, preferably at least of 35 MPa.
• the upper limit of said tensile strength (MD) of Film is not critical an may be e.g. less than 60 MPa
• Tensile strength (ISO 527-3) in TD of Film is preferably of at least 25 MPa, more preferably at least of 30 MPa. In embodiments where very good mechanical properties are beneficial, Film may provide even higher tensile strength in TD, such as at least 35 MPa. Upper limit of said tensile strength of Film is not critical and may be e.g. less than 60 MPa in TD.
• the impact strength (ISO 7765-1 , method "A") determined as dart drop is preferably at least 300 g, preferably at least 500 g, more preferably at least 700 g when determined using a film sample of thickness of 150 ⁇ m. In embodiments wherein high impact strength is desired, then Film may have impact strength of at least 1000 g or even at least 1200 g.
• the Film of the invention has also very good light transmission properties.
• Haze value of said Film is preferably at least 40% more, preferably at least 50%, more preferably at least 60%, when determined according to ASTM D 1003, irrespective from which side of said Film the haze is determined.
• Upper limit of haze of Film is not critical and may be e.g. less than 80%.
• layer (A) preferably comprises, more preferably consists of, a multimodal znLLDPE and layer (B) comprises, preferably consists of, LDPE
• the Film has preferably a haze value of at least 65%.
• a Film in accordance with the present invention displaying the haze values indicated above has a thickness of 75 ⁇ m or more, more preferably 100 ⁇ m or more, such as from 100 to 200 ⁇ m.
• Film of the invention has preferably a Gloss (ASTM D 2457, at angle 60°) of at least 50%, preferably of at least 60%, when measured from layer (B) side of Film.
• Upper limit of said gloss is not critical and may be e.g. less than 90%.
• Film of the invention has preferably a Gloss (ASTM D 2457, at angle 60°) of not more than 30%, preferably of not more than 20%, when measured from layer (A) side of Film.
• Lower limit of said gloss of Film from layer (A) side may typically be at least 1%.
• transmission of direct light (angle 0°) of Film of the invention may be at least 80 %, preferably at least 90 %, more preferably at least 94 %, irrespectively from which side of Film.
• Upper limit of said transmission of direct light of Film is less than 100%.
• Transmission of diffuse light (scattered light) of Film of the invention is preferably at least 80 %, more preferably at least 84 %, or in high diffuse film embodiments said Film can provide transmission of diffuse light even as high as at least 85 %, irrespectively from which side of Film the transmission of diffuse light haze is determined.
• Upper limit of said transmission of diffuse light of Film is less than 100%.
• the IR transmittance of Film of the invention is suitably low, typically in the range of from 75 to 45% when using a film sample of thickness of 150 ⁇ m.
• Film may be selected from one of the following independent embodiment, in a given layer order:
• layer (A) and optional layer (Ai) comprise, preferably consists of, a multimodal znLLDPE,
• layer (A) and optional layer (A 1 ) comprise, preferably consists of, a multimodal znLLDPE,
• Said Film with preferable layer structures as defined above may be selected from one of the following, in a given layer order: (i) A/B, (ii) (Ay(A 1 V(B) and (iii) (Ay(B 1 V(B).
• Multilayer film as described herein and as defined in the claims represents the preferred embodiment of the present invention.
• Density of the materials was measured according to ISO 1183:1987 (E), method D, with isopropanol-water as gradient liquid.
• the cooling rate of the plaques when crystallising the samples was 15 C/min. Conditioning time was 16 hours.
• MFR 2 , MFR 5 and MFR 2 i were measured according to ISO 1133 at 190 0 C at loads of 2.16, 5.0, and 21.6 kg respectively.
• Flow rate ratio FRR 2 i/ 2 is calculated from MFR 2 i/MFR 2 .
• Mw 1 Mn and MWD were measured by Gel Permeation Chromatography (GPC) according to the following method:
• a Waters 150CV plus instrument, equipped with refractive index detector and online viscosimeter was used with 3 x HT6E styragel columns from Waters (styrene-divinylbenzene) and 1 ,2,4- trichlorobenzene (TCB, stabilized with 250 mg/L 2,6-Di tert butyl-4-methyl-phenol) as solvent at 140 0 C and at a constant flow rate of 1 mL/min.
• Tm and Tcr both were measured according to ISO 11357-1 on Perkin Elmer DSC-7 differential scanning calorimetry. Heating curves were taken from -1O 0 C to 200 0 C at 10°C/min. Hold for 10 min at 200 0 C. Cooling curves were taken from 200 0 C to -1O 0 C at 10 0 C per min. Melting and crystallization temperatures were taken as the peaks of endotherms and exotherms. The degree of crystallinity was calculated by comparison with heat of fusion of a perfectly crystalline polyethylene, i.e. 290 J/g.
• Comonomer content (mol%) was determined based was determined by C 13 NMR.
• the C 13 NMR spectra of the polymers were recorded on Bruker 400MHz spectrometer at 130 0 C from samples dissolved in 1 ,2,4-trichlorobenzene/benzene-d6 (90/10 w/w).
• Tear resistance (determined as Elmendorf tear (N)): Applies for the measurement both in machine direction and in transverse direction. The tear strength was measured according ISO 6383/2 using a Film Sample. The force required to propagate tearing across a film sample was measured using a pendulum device. The pendulum swings under gravity through an arc, tearing the specimen from pre-cut slit. The specimen was fixed on one side by the pendulum and on the other side by a stationary clamp. The tear resistance was the force required to tear the specimen. The relative tear resistance (N/mm) can be calculated by dividing the tear resistance by the thickness of the film.
• Tensile modulus (secant modulus, 0.05-1.05%) was measured according to ASTM D 882-A using a Film Sample. The speed of testing was 5mm/min. The test temperature was 23°C. Width of the film was 25 mm.
• Tensile Strength was measured according to ISO 527-3 using a Film Samples. The speed of testing was 500 mm/min. The test temperature is 23°C. Width of the film was 25 mm.
• Elongation at break was determined according to ISO 527-3 using a Film Sample.
• a Light Source was placed above the Film Sample and light was illuminated perpendicular onto or with above given angle on said Film Sample. Light that transmitted through the Film Sample then entered an external integrated sphere arranged behind (below) the Film Sample. The amount of light at different wavelengths of transmitted light was measured with a spectrophotometer.
• the light to illuminate the Film Sample was first passed through an external integrated sphere arranged above the Film Sample, which external sphere created a scattered light beam which was then directed to pass through the Film Sample into a second external integrated sphere arranged behind (below) the Film Sample.
• the amount of light at different wavelengths that were transmitted through the Film Sample was measured with a spectrophotometer.
• IR transmittance was measured by subjecting an infrared radiation source above the Film Sample and finally the amount of IR-radiation that transmitted through the Film Sample was measured.
• a Film Sample with a thickness of 50 ⁇ m was prepared as a three-layer structure ABC using a 3-layer Windm ⁇ ller&H ⁇ lscher Varex coextrusion line for blow-film with a blow up ratio of 2.3 and a frost line height of 600 mm.
• the extruder had a diameter of 200 mm and a die gap of 1.0 mm.
• the output rate was 98 kg/h and the die temperature was set to 240 0 C.
• a three- layer structure of A/B/C 20 ⁇ m/20 ⁇ m/10 ⁇ m was prepared.
• said polymer composition to be tested or the polymer composition of said layer was used for forming each layer of the 3-layer structure, i.e. each layer consisted of the same polymer composition the properties of which were to be determined.
• a Film Sample with a thickness of 150 ⁇ m was prepared as a three-layer structure ABC using a 3-layer Windm ⁇ ller&H ⁇ lscher Varex coextrusion line for blow-film with a blow up ratio of 2.1 and a frost line height of 500 mm.
• the extruder had a diameter of 250 mm and a die gap of 0.8 mm.
• the output rate was 90 kg/h and the die temperature was set to 240 0 C.
• the layers AJAJB were prepared which corresponds to AJB of 125/25 ⁇ m.
• LLDPE1 The multimodal znLLDPE polymer used in the films of examples of the invention was prepared as follows: Multimodal znLLDPE polymer was prepared in a pilot scale multistage reactor system containing a loop reactor and a gas phase reactor. A prepolymerisation step preceded the actual polymerisation step. The prepolymerisation stage was carried out in slurry in a 50 dm 3 loop reactor at about 80 °C in a pressure of about 65 bar using the polymerisation catalyst prepared according to Example 1 of WO 2004/000902 and triethylaluminium as the cocatalyst. The molar ratio of aluminum of the cocatalyst to titanium of the catalyst was about 20.
• Ethylene was fed in a ratio of (20Og of C2)/(1g/catalyst). Propane was used as the diluent and hydrogen was fed in amount to adjust the MFR2 of the prepolymer to about 10 g/10 min.
• the obtained slurry together with prepolymerised catalyst and triethyl aluminum cocatalyst were transferred to the actual polymerisation step, i.e. introduced into a 500 dm 3 loop reactor, wherein a continuous feed of propane, ethylene and hydrogen was also introduced.
• the ratio of H2/C2 in the reaction mixture was 240 mol/kmol.
• the mol-ratio of 1-butene comonomer to ethylene, C4/C2 was 570mol/kmol.
• the loop reactor was operated at 95 0 C temperature and 60 bar pressure.
• the polymer obtained from the loop reactor at a production rate of about 30 kg/h had MFR2 of 300 g/10 min and a density of about 951 kg/
• the slurry was then transferred to a fluidised bed gas phase reactor, where also additional ethylene, 1-butene comonomer and hydrogen were added, together with nitrogen as an inert gas to produce the HMW component in the presence of the LMW component.
• the ethylene content in gas phase reactor was 19 mol-%
• the ratio of H2/C2 in the recycle gas was 7 mol/kmol
• the ratio of C4/C2 was 460 mol/kmol.
• the gas phase reactor was operated at a temperature of 80 0 C and a pressure of 20 bar.
• the production rate of the polymer was about 75 kg/h.
• the split (wt%) loop/gas phase was 41/59.
• the polymer obtained from the gas phase reactor had.
• the comonomer content was 7.6 wt%.
• the reactor powder was then stabilised with conventional additives and pelletised in a known manner using CIM90P counter-rotating twin screw extruder manufactured by Japan
• the pelletized final polymer product had Mw of 233 000 g/mol, Mw/Mn of 17,
• the LLDPE 1 used had a haze value of 60-65 % when measured according to ASTM D 1003 using a blown Film Samples consisting of LLDPE 1 and prepared as described above for Film Samples for polymer composition properties, but having a film thicknesses varying between 37-40 ⁇ m.
• LDPE1 used in the examples of the invention and comparative examples was commercially available LDPE grade produced by high-pressure polymerization, supplied by Borealis.
• LDPE1 had a MFR2 of 1.2 g/10min and Density 922 kg/m 3 .
• LDPE2 used in the examples of the invention and comparative examples was commercially available LDPE grade produced by high-pressure polymerization, supplied by Borealis. LDPE2 had a MFR2 0.9, density 922 kg/m 3 . EVA1 used in the examples of the invention and comparative examples was commercially available ethylene vinyl acetate LDPE grade produced by high-pressure polymerization, supplied by Borealis. EVA 1 had a MFR2 of 0.25 g/10min and vinyl acetate content of 14%.
• a three layer structure ABC was prepared with a coextrusion line given above in "Film Sample Preparation" for blow-film with a blow up ratio of 2.3 and a frost line height of 600 mm.
• the extruder had a diameter of 200 mm and a die gap of 1.0 mm.
• the output rate was 98 kg/h and the die temperature was set to 240 0 C.
• a three-layer structure of AJBIC 20 ⁇ m/20 ⁇ m/10 ⁇ m was prepared, with layers A and B consisting of LLDPE1 and layer C consisting of LDPE1.
• the gloss of the two outer layers was determined and the LLDPE 1 outer layer (A) displayed a gloss of 13, while the LDPE1 side (B) displayed a gloss of 80.
• Such a difference in gloss of the layers however surprisingly did not affect the light transmission (see Figure 1 : ⁇ ABC with C turned towards light source; ⁇ ABC with A turned towards light source; ⁇ LLDPE1 film; x LDPE1 film).
• a standard LDPE singly layer film was evaluated, prepared from the LDPE 1 material according to above blown coextrusion method but using LDPE1 in each of the three layers to obtain a "single" layer film with thickness 50 ⁇ m.
• Figure 1 shows a comparison of light transmission for the three film samples identified above.
• a single layer film of the LLDPE material alone has been evaluated.
• This comparative film sample was prepared from LLDPE1 according to above blown coextrusion method but using LLDPE1 in each of the three layers to obtain a "single" layer film with thickness 50 ⁇ m.
• the layer structure of the invention displays the best light radiation properties, irrespective of the orientation of the film, i.e. the layer being directed to the light source (LLDPE layer or LDPE layer).
• the single layer LLDPE material has an insufficient light transmission.

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