Multilayered polyolefin-based films

The invention relates to a heat seal film based on a polyolefin suitable for autoclaving. The invention also relates to methods of making and using a heat sealable film capable of being sterilized in an autoclave.

BACKGROUND OF THE INVENTION [0002] In an autoclave process (retort process), the packaged food product is sterilized in a container in order to obtain a product with an extended shelf life. Polymeric films used for autoclavable packaging must withstand strong heating (typically 121 ° C and above) and high humidity. The structure of currently existing food packaging foils suitable for autoclaving includes at least three functional layers: a sealable layer, a barrier layer and an intermediate layer between them. The weldable layer is usually a polyolefin, preferably polypropylene due to heat resistance. The barrier layer is polyamide (PA) or a copolymer of ethylene and vinyl alcohol (EVOH), or polyvinylidene chloride (PVDC), preferably PA, which maintains mechanical strength and barrier properties in relation to oxygen during the process carried out in an autoclave. The intermediate layer forms a binding interlayer between the two incompatible layers. It is usually a polyolefin functionalized with maleic anhydride (MAH), specifically MAH-g-PP or MAH-gPE. Since the weldable layer is preferably polypropylene (PP), the MAH-g-PP is usually chosen as the functionalized polyolefin for the intermediate layer. However, the MAH-g-PP processing degrades PP and causes a significant increase in the melt flow index and difficulty in matching the viscosity for coextrusion of the film. In addition, washing is required to remove the PP oligomers, and thus the cost of production is high. The intermediate layer forms a binding interlayer between the two incompatible layers. It is usually a polyolefin functionalized with maleic anhydride (MAH), specifically MAH-g-PP or MAH-gPE. Since the weldable layer is preferably polypropylene (PP), the MAH-g-PP is usually chosen as the functionalized polyolefin for the intermediate layer. However, the MAH-g-PP processing degrades PP and causes a significant increase in the melt flow index and difficulty in matching the viscosity for coextrusion of the film. In addition, washing is required to remove the PP oligomers, and thus the cost of production is high. The intermediate layer forms a binding interlayer between the two incompatible layers. It is usually a polyolefin functionalized with maleic anhydride (MAH), specifically MAH-g-PP or MAH-gPE. Since the weldable layer is preferably polypropylene (PP), the MAH-g-PP is usually chosen as the functionalized polyolefin for the intermediate layer. However, the MAH-g-PP processing degrades PP and causes a significant increase in the melt flow index and difficulty in matching the viscosity for coextrusion of the film. In addition, washing is required to remove the PP oligomers, and thus the cost of production is high. MAH-g-PP is usually chosen as the functionalized polyolefin for the intermediate layer. However, the MAH-g-PP processing degrades PP and causes a significant increase in the melt flow index and difficulty in matching the viscosity for coextrusion of the film. In addition, washing is required to remove the PP oligomers, and thus the cost of production is high. MAH-g-PP is usually chosen as the functionalized polyolefin for the intermediate layer. However, the MAH-g-PP processing degrades PP and causes a significant increase in the melt flow index and difficulty in matching the viscosity for coextrusion of the film. In addition, washing is required to remove the PP oligomers, and thus the cost of production is high.

[0003] It would be desirable to provide an alternative intermediate layer that maintains the required weld strength and does not cause problems with haze or shrinkage and enables co-extrusion. SUMMARY OF THE INVENTION [0004] The invention provides a multilayer structure comprising a polyolefin layer (layer A), an intermediate layer (layer B) and a barrier layer (layer C), each layer having opposite faces in adhered contact with another layer in which structure. the layer A has an upper face and a bottom face and comprises a polyolefin, preferably polypropylene;

layer B has an upper face and a bottom face and includes:

a) a crystalline block composite component (CBC) comprising:

i) an ethylene polymer (EP) comprising at least 90 mole% polymerized ethylene based on the weight of the ethylene polymer;

ii) a crystalline alpha-olefin based polymer (CAOP) and iii) a block copolymer comprising (a) a block of ethylene polymer containing at least 90 mol% of polymerized ethylene based on the weight of the ethylene polymer block and ( b) crystalline alpha-olefin crystalline block (CAOB);

b) a polyolefin elastomer; homogeneously branched ethylene / alpha-olefin copolymer;

c) polyethylene grafted with maleic anhydride (MAH-g-PE) or polypropylene grafted with maleic anhydride (MAH-g-PP) and, optionally

d) polypropylene or polyethylene; and

The layer C comprises polyamide (PA) or a copolymer of ethylene and vinyl alcohol (EVOH) and has an upper face and a bottom face, the upper face of the layer C adhering to the undersurface of the face layer B.

BRIEF DESCRIPTION OF THE DRAWINGS [0005]

Figure 1 shows the DSC profile for CBC1.

Figure 2 shows TREF for CBC 1.

Figure 3 shows HTLC for CBC1.

Figure 4 shows a schematic of the stripping of a cast film.

Figure 5 shows the delamination analysis for Ex. 16, 18 and H before and after the autoclave process.

Figure 6 shows the delamination analysis for Ex. 23, L and N before and after the autoclave process.

Figure 7 shows the seal strength of the film measured from the bottom of the thermoformed cup.

as determined by transmission electron spectroscopy, light scattering, X-ray scattering and other method known in the art. Blends are not laminates, but one or more laminate layers may contain a blend. [0008] "Polymer" means a compound made by polymerizing monomers of the same or a different type. The generic term "polymer" therefore includes the term "homopolymer", usually used to describe polymers made from only one type of monomer, and the term "interpolymer" as defined below. It also includes all forms of interpolymers, e.g. random, block, etc. The terms "ethylene polymer / α-olefin" and "propylene / α-olefin polymer" indicate interpolymers, as described below. It should be noted that although the polymer is often referred to as "made from" monomers,

[0009] "Interpolymer" means a polymer made by polymerizing at least two different monomers. This generic term includes copolymers, it is usually used to refer to polymers prepared from two or more different monomers and includes polymers made from more than two monomers, e.g. terpolymers, tetrapolymers, etc.

[0010] "Polyolefin", "polyolefin polymer", "polyolefin resin" and like terms means a polymer made from a simple olefin (also called an alkane of the general formula CnH2n) as a monomer. Polyethylene is made by polymerizing ethylene with or without one or more komoonomers, polypropylene by polymerizing propylene with or without one or more komoonomers, etc. Thus, polyolefins include interpolymers, such as ethylene / α-olefin copolymers, propylene / α-olefin copolymers, e.t.c.

[0011] The "melting point" as used herein (also referred to as melting peak with respect to the shape of the plotted DSC curve) is typically measured by DSC (differential scanning calorimetry) technique for measuring the melting temperatures or peaks of polyolefins as described in USP5,783,638. It should be noted that many blends

EP 2 895 328 comprising two or more polyolefins will have more than one temperature or melting peak; many separate polyolefins will have only one temperature or melting peak.

[0012] The multilayer structures have three or more layers from layer A, layer B and layer C in a structure like AB / C, or preferably in structure AB / CB / D, in which A is a polyolefin layer, C is a barrier layer, B it is an interlayer that provides adhesion between the polyolefin layer and the barrier layer, and D is a weldable layer. Layer A and layer D may have the same or different composition. Optionally, 7-layer structures and structures comprising more layers may be included to add functionality, e.g. to AB / C or A / B / CB / D repeating units.

[0013] The components of the layer B may be present in the following amounts with respect to the total weight of the B layer polymers: 20 wt. up to 90% by weight, preferably 40-60% by weight CBC; optionally 0 wt.% up to 30% by weight, preferably 10% by weight up to 30% by weight a polyolefin elastomer; 10 wt% up to 30% by weight polyethylene grafted with maleic anhydride (MAH-g-PE); and, optionally, 0 wt. up to 20% by weight polypropylene or 0 wt.% up to 20% by weight polyethylene. The concentration of grafted MAH in the B-layer may be in the range of 0.05 to 1.0%. Alternatively, MAH-g-PE can be replaced by maleic anhydride grafted polypropylene (MAH-g-PP) or a combination of MAH-g-PE and MAH-g-PP.

[0014] The formulation of the intermediate layer, layer B, comprises a polyolefin elastomer. Suitable polyolefin elastomers include any elastomer based on polyethylene or polypropylene, including a homogeneously branched ethylene / alpha-olefin copolymer, a propylene / alpha-olefin interpolymer, and an ethylene-propylene diene diene rubber (EPDM).

[0015] The homogeneous branched ethylene / alpha-olefin copolymer can be made with a single site catalyst, such as a metallocene catalyst or stiffened catalyst, and usually has a melting point lower than 105, preferably lower than 90, more preferably lower than 85, even more preferably lower than 80, and even more preferably lower than 75 ° C. The melting point is measured using differential scanning calorimetry (DSC) as described in USP5,783,638. The α-olefin is preferably a C3-20 linear, branched or cyclic α-olefin. Examples of C3-20 α-olefins include propene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene. α-olefins may also have a cyclic structure, such as cyclohexane or cyclopentane, resulting in an α-olefin such as 3-cyclohexyl-propene (allylcyclohexane) and vinylcyclohexane. Some cyclic olefins, such as norbornene and related olefins, although in the classic sense, the terms are not α-olefins, can be used instead of some or all of the α-olefins described above for the purposes of the present invention. Similarly, styrene and its related olefins (e.g., α-methylstyrene, etc.) are α-olefins for the purposes of the present invention. Illustrative homogeneously branched ethylene / alpha-olefin copolymers include ethylene / propylene, ethylene / butene, ethylene / 1-hexene, ethylene / 1-octene, ethylene / styrene, and the like. Illustrative terpolymers include ethylene / propylene / 1-octene, ethylene / propylene / butene, ethylene / butene / 1-octene and ethylene / butene / styrene. The copolymers can be random or blocky. such as norbornene and related olefins, although in the classic sense, the terms are not α-olefins, for the purposes of the present invention may be used instead of some or all of the α-olefins described above. Similarly, styrene and its related olefins (e.g., α-methylstyrene, etc.) are α-olefins for the purposes of the present invention. Illustrative homogeneously branched ethylene / alpha-olefin copolymers include ethylene / propylene, ethylene / butene, ethylene / 1-hexene, ethylene / 1-octene, ethylene / styrene, and the like. Illustrative terpolymers include ethylene / propylene / 1-octene, ethylene / propylene / butene, ethylene / butene / 1-octene and ethylene / butene / styrene. The copolymers can be random or blocky. such as norbornene and related olefins, although in the classic sense, the terms are not α-olefins, for the purposes of the present invention may be used instead of some or all of the α-olefins described above. Similarly, styrene and its related olefins (e.g., α-methylstyrene, etc.) are α-olefins for the purposes of the present invention. Illustrative homogeneously branched ethylene / alpha-olefin copolymers include ethylene / propylene, ethylene / butene, ethylene / 1-hexene, ethylene / 1-octene, ethylene / styrene, and the like. Illustrative terpolymers include ethylene / propylene / 1-octene, ethylene / propylene / butene, ethylene / butene / 1-octene and ethylene / butene / styrene. The copolymers can be random or blocky. for the purposes of the present invention, they may be used in place of some or all of the α-olefins described above. Similarly, styrene and its related olefins (e.g., α-methylstyrene, etc.) are α-olefins for the purposes of the present invention. Illustrative homogeneously branched ethylene / alpha-olefin copolymers include ethylene / propylene, ethylene / butene, ethylene / 1-hexene, ethylene / 1-octene, ethylene / styrene, and the like. Illustrative terpolymers include ethylene / propylene / 1-octene, ethylene / propylene / butene, ethylene / butene / 1-octene and ethylene / butene / styrene. The copolymers can be random or blocky. for the purposes of the present invention, they may be used in place of some or all of the α-olefins described above. Similarly, styrene and its related olefins (e.g., α-methylstyrene, etc.) are α-olefins for the purposes of the present invention. Illustrative homogeneously branched ethylene / alpha-olefin copolymers include ethylene / propylene, ethylene / butene, ethylene / 1-hexene, ethylene / 1-octene, ethylene / styrene, and the like. Illustrative terpolymers include ethylene / propylene / 1-octene, ethylene / propylene / butene, ethylene / butene / 1-octene and ethylene / butene / styrene. The copolymers can be random or blocky. ethylene / styrene and the like. Illustrative terpolymers include ethylene / propylene / 1-octene, ethylene / propylene / butene, ethylene / butene / 1-octene and ethylene / butene / styrene. The copolymers can be random or blocky. ethylene / styrene and the like. Illustrative terpolymers include ethylene / propylene / 1-octene, ethylene / propylene / butene, ethylene / butene / 1-octene and ethylene / butene / styrene. The copolymers can be random or blocky.

[0016] More specific examples of homogeneously branched ethylene / alpha-olefin interpolymers useful in this invention include homogeneously branched, linear ethylene / alpha-olefin copolymers (e.g., TAFMER® from Mitsui Petrochemicals Company Limited and EXACT® from Exxon Chemical Company) and homogeneously branched essentially linear ethylene / alpha-olefin polymers (e.g. AFFINITY polyethylene)^™ and ENGAGE^™ available from The Dow Chemical Company). Substantially linear ethylene copolymers are particularly preferred and are described in more detail in USP 5,272,236, 5,278,272 and 5,986,028. In practice, this invention may be

Also, blends of any of these interpolymers are used. In the context of this invention, homogeneously branched ethylene / alpha-olefin interpolymers are not olefin block copolymers.

[0017] A polypropylene that can be used as a polyolefin layer, layer A, a sealable layer, layer D, if present, and optionally in the intermediate layer, layer B, can be a homopolymer (hPP), a polypropylene random copolymer (rcPP), a polypropylene copolymer impact (hPP + at least one elastomeric impact modifier) ​​(ICPP) or high impact polypropylene (HIPP), high melt strength polypropylene (HMS-PP), isotactic polypropylene (iPP), syndiotactic polypropylene (sPP) and combinations thereof.

[0018] A polypropylene that can be used in a polyolefin layer, layer A, a weldable layer, layer D, if present, and optionally in the intermediate layer, layer B, can also be a propylene / alpha-olefin interpolymer. The propylene / alpha-olefin interpolymer has a content of substantially isotactic propylene sequences. Propylene / alpha-olefin interpolymers include propylene-based elastomers (PBE). The term "substantially isotactic triad of propylene" means that the sequences have an isotactic triad (mm) as measured by¹³C NMR greater than 0.85; alternatively greater than 0.90; in another possibility greater than 0.92; and other than 0.93. Isotactic triads are well known in the art and are described in, for example, USP5,504,172 and International Publication No. WO00 / 01745, which relates to an isotactic sequence with a triad unit in a cosmymer molecule chain defined by the spectrum¹³C NMR.

[0019] The propylene / alpha-olefin interpolymer has a melt flow rate in the range of 0.1 to 500 grams per 10 minutes (g / 10min), measured according to ASTM D-1238 (at 230 ° C / 2.16 Kg). All individual values ​​and subranges from 0.1 to 500 are included herein, for example, the melt flow rate can be from the lower limit of 0.1 g / 10min, 0.2g / 10min or 0.5g / 10min to the upper limit of 500 g / 10min, 200g / 10min, 100g / 10min or 25g / 10min. For example, the propylene / alpha-olefin copolymer may have a melt flow index in the range of 0.1 to 200 g / 10min, or alternatively, the propylene / alpha-olefin copolymer may have a melt flow rate in the range of 0.2 to 100 g / 10min, or alternatively, the propylene / alpha-olefin copolymer may have a melt flow rate in the range of 0.2 to 50g / 10min, or alternatively,

[0020] The propylene / alpha-olefin interpolymer has a crystallinity in the range of at least 1 weight percent (heat of fusion (Hf) of at least 2 joules / gram (J / g)) up to 30 weight percent (Hf less than 50 J / g) . All individual values ​​and subranges from 1 weight percent (heat of fusion (Hf) of at least 2 J / g) to 30 weight percent (Hf less than 50 J /) g are included herein and disclosed, for example, the crystallinity can be from the lower limit 1 weight percent (Hf at least 2 J / g), 2.5 percent (Hf at least 4 J / g) or 3 percent (Hf at least 5 J / g) up to an upper limit of 30 weight percent (Hf less than 50 J g), 24 weight percent (Hf less than 40 J / g), 15 weight percent (Hf less than 24.8 J / g) or 7 weight percent (Hf less than 11 J / g). E.g, the propylene / alpha-olefin copolymer may have a crystallinity ranging from at least 1 weight percent [0021] (Hf at least 2 J / g) to 24 weight percent (Hf less than 40 J / g); or alternatively, the propylene / alpha-olefin copolymer may have a crystallinity in the range of at least 1 weight percent (Hf every

At least 2 J / g) to 15 weight percent (Hf less than 24.8 J / g), or alternatively the propylene / alphaolefin copolymer may have a crystallinity in the range of at least 1 weight percent (Hf at least 2 J / g) up to 7 weight percent (Hf less than 11 J / g), or alternatively, the propylene / alpha olefin copolymer may have a crystallinity in the range of Hf less than 8.3 J / g. The crystallinity was measured by differential scanning calorimetry (DSC) as described in USP 7,199,203. The propylene / alpha-olefin copolymer comprises units derived from propylene and polymeric units derived from one or more alpha-olefin comonomers. Examples of the comonomers used to make the propylene / alpha-olefin copolymer are C2 and C4 to C10 alpha-olefins, for example, C2, C4, C6 and C8 alpha-olefins.

[0022] The propylene / alpha-olefin interpolymer contains from 1 to 40 weight percent of one or more alpha-olefin comonomers. All single values ​​and subranges from 1 to 40 weight percent are included herein and disclosed, for example, the comonomer content may be from the lower limit of 1 weight percent, 3 weight percent, 4 weight percent, 5 weight percent, 7 weight percent or 9 weight percent. up to an upper limit of 40 percent by weight, 35 percent by weight, 30 percent by weight, 27 percent by weight, 20 percent by weight, 15 percent by weight, 12 percent by weight, or 9 percent by weight. For example, the propylene / alpha-olefin copolymer contains from 1 to 35 weight percent of one or more alpha-olefin comonomers, or, alternatively,

[0023] The propylene / alpha-olefin interpolymer has a density of typically less than 0.895 g / cm³ or alternatively less than 0.890 g / cm³, or alternatively less than 0.880 g / cm³, or alternatively less than 0.870 g / cm³. The propylene / alpha-olefin interpolymer has a density generally greater than 0.855 g / cm 3³ or alternatively greater than 0.860 g / cm³ or alternatively greater than 0.865 g / cm³.

[0024] The propylene / alpha-olefin interpolymer has a melting point (T m) of usually less than 120 ° C or alternatively <100 ° C, or alternatively <90 ° C, or alternatively <80 ° C, or alternatively <70 ° C, and heat of fusion (Hf) usually less than 70 Joules per gram (J / g) measured by differential scanning calorimetry (DSC) as described in USP 7,199,203.

[0025] The propylene / alpha-olefin interpolymer has a molecular weight distribution (MWD), defined as the weight average molecular weight divided by number average molecular weight (Mw / Mn, 3.5 or less, or 3.0 or less, or from 1 , 8 to 3.0.

[0026] Such propylene / alpha-olefin interpolymers are further described in USP66,60,635 and 6,525,157. Such propylene / alpha-olefin interpolymers are commercially available from The Dow Chemical Company, under the trade name VERSIFY or from ExxonMobil Chemical Company, under the trade name VISTAMAXX.

[0027] Polypropylene which can be used in the polyolefin layer, layer A, the weldable layer, layer D, if present, and possibly in the intermediate layer, layer B, can also be EPDM materials. The EPDM materials are linear interpolymers of ethylene, propylene and a non-conjugated diene, such as 1,4-hexadiene, dicyclopentadiene or ethylidene norbornene. A preferred class A of interpolymers that have the properties disclosed herein is obtained from the polymerization of ethylene, propylene and a non-conjugated diene to form an EPDM elastomer. Suitable non-conjugated dienes as monomers can be straight-chain, branched or cyclic hydrocarbon dienes with 6 to 15 carbon atoms.

EP 2 895 328

Examples of suitable unconjugated dienes include, but are not limited to, straight-chain acyclic dienes, such as 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene, branched-chain acyclic dienes, as 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7,8-cadadiene and mixed isomers of dihydromirycene and dihydroocinene, mononuclear alicyclic dienes such as 1,3-cyclopentadiene 1,4-cyclohexadiene, 1,5-cyclooctadiene and 1,5-cyclododecadiene and polycyclic condensed and bridged ring dienes, such as tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, bicyclo- (2,2,1) -hepta-2,5 diene; alkenyl-, alkylidene-, cycloalkenyl-cycloalkylideneorbornenes, 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5- (4-Cyclopentenyl) -2-norbomene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene and norbornadiene. Of the dienes usually used for EPDM production, particularly preferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene (MNB) and dicyclopentadiene (DCPD). Particularly preferred dienes are 5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).

[0028] In some embodiments, the EPDM polymers have an ethylene content of 50% to 75% by weight and a propylene content of 20% is 49% by weight and a nonconjugated diene content of 1% to 10% by weight, all weights being related to the total weight of the polymer. . Examples of representative EPDM polymers for use include Nordel IP 4770R, Nordel 3722 IP available from The Dow Chemical Company, Midland, MI, Vistalon 3666 available from ExxonMobil, Baton Rouge, LA and Keltan 5636A available from DSM Elastomers Americas, Addis, LA.

[0029] EPDM polymers, also known as elastomeric copolymers of ethylene, higher alpha-olefin and polyene, have molecular weights from 20,000 to 2,000,000 Daltons or more. Their physical form varies from wax materials to rubbers to hard plastics like polymers. They have a viscosity in a dilute solution (DSV) of 0.5 to 10 dl / g, measured at 30 ° C for a solution of 0.1 grams of polymer in 100 cm³ toluene. EPDM polymers also have a Mooney viscosity of more than 50 ML (1 + 4) at 125 ° C and a density of 0.870 g / cm³ up to 0.885 g / cm³ or from 0.875 g / cm³ up to 0.885 g / cm³.

[0030] The polyethylene optionally used in the intermediate layer, layer B, is selected from ultra-low density polyethylene (ULDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), polyethylene high density (HDPE), high density polyethylene and high strength alloy (HMS-HDPE), ultrahigh density polyethylene (UHDPE) and combinations thereof. In a further embodiment, the polyethylene has a density of more than 0.950 g / cm³ (ie HDPE).

[0031] MAH-g-PE used in the intermediate layer, layer B, is polyethylene grafted with maleic anhydride. The grafted polyethylene may be one of polyethylenes as described above. The amount of maleic anhydride grafted onto the polyethylene chain is greater than 0.05 weight percent to 2.0 weight percent. (with respect to the weight of the olefin interpolymer) as determined by titration analysis, FTIR analysis or any other suitable method. More preferably, the amount is greater than 0.25 weight percent to 2.0 weight percent, and in yet another embodiment this amount is greater than 0.3 weight percent to 2.0 weight percent. In a preferred embodiment, 0.5 weight percent to 2.0 percent by weight of maleic anhydride is seeded.

[0032] The MAH-g-PE vaccination process may be initiated by the decomposition of the initiators to form free radicals, including compounds containing azo groups, carboxyl peroxy acids and peroxyesters, alkyl hydroperoxides and di alkyl and diacyl peroxides. Many of these compounds and their properties are described (Reference: J. Branderup, E. Immergut, E. Grulke, ed. "Polymer

EP 2 895 328

Handbook, "4th ed., Wiley, New York, 1999, Section II, pp. 1-76.) Preferred radicals that are formed by decomposing the initiator are oxygen free radicals. A more preferred initiator is selected from carboxylic peroxyester, peroxyketals, Some of these preferred initiators, usually used to modify the structure of polymers, are mentioned in the patent No. US7,897,689, in a table extending from col48, line 13 through col. 49, line 29. Alternatively, the process Vaccinations for MAH-g-PE can be initiated by free radicals generated by thermal oxidation.

[0033] MAH-g-PP concentrate may optionally be used. The grafted polyethylene may be one of the polypropylenes as described for layer A. The amount of maleic anhydride grafted onto the polyethylene chain is greater than 0.05 weight percent to 2.0 weight percent. (based on the weight of the olefin interpolymer), as determined by titration analysis, FTIR analysis or any other suitable method. More preferably, the amount is greater than 0.25 weight percent to 2.0 weight percent, and still in another embodiment that amount is greater than 0.3 weight percent to 2.0 weight percent. In a preferred embodiment, 0.5 weight percent to 2.0 percent by weight of maleic anhydride is seeded.

[0034] Optionally, MAH-g-PE can be replaced by or used together with various grafted polyolefins that include radical-radically reacted compounds. These compounds include unsaturated molecules, each containing at least one heteroatom. These compounds include, but are not limited to, maleic anhydride, dibutyl maleate, dicyclohexyl maleate, diisobutyl maleate, dioctadecyl maleate, N-phenylmaleimide, citraconic anhydride, tetrahydrophthalic anhydride, bromomaleic anhydride, chloromaleic anhydride, 5-norbornene-2-anhydride, 3-dicarboxylic acid, methyl-5-norbornene-anhydride, alkenyl succinic anhydride, maleic acid, fumaric acid, diethyl fumarate, itaconic acid, citraconic acid, crotonic acid and appropriate esters, imides,

[0035] The barrier layer, layer C, may comprise one or more of polyamides (nylons), ethylene and vinyl alcohol copolymers (EVOH), polyvinylidene chloride, polycarbonate or a combination of two or more of these ingredients and may contain scavengers and heavy metal compounds such as Cobalt with MXD6 nylon.

[0036] EVOH comprises a vinyl alcohol copolymer containing 27 to 44 mole% ethylene, and is produced, for example, by hydrolysis of vinyl acetate copolymers. EVOH is available as EVAL ™ from Kuraray and Noltex ™ from Nippon Goshei.

[0037] The polyamide may comprise polyamide 6, polyamide 9, polyamide 10, polyamide 11, polyamide 12, polyamide 6,6, polyamide 6/66 and an aromatic polyamide, such as polyamide 6I, polyamide 6T, MXD6 or a combination of two or more of them. .

[0038] The compositions disclosed herein optionally may contain an antioxidant or stabilizer. Any antioxidant known to a person skilled in the art may be used in the adhesive composition disclosed herein. Non-limiting examples of suitable antioxidants include antioxidants such as alkyl diphenylamines, phenyl-α-naphthylamine, alkyl- or aralkyl-substituted-phenyl-α-naphthylamines, alkylated p-phenylenediamines, tetramethyl-diaminodiphenylamine and the like, and sterically hindered phenolic compounds such as 2.6 -di-t-butyl-4-methylphenol, 1,3,5-trimethyl-2,4,6-tris (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) benzene, tetrakis [(methylene ( 3,5-di-t-butyl-47

EP 2 895 328 (hydroxyhydrocinnate)) methane (e.g. IRGANO^XTM 1010, from Ciba Geigy, New York); octadecyl-3,5-di-t-butyl-4-hydroxycinnamate (e.g. IRGANO^XTM 1076, commercially available from Ciba Geigy) and combinations thereof.

The amount of antioxidant in the composition, if present, may comprise from more than 0 to 1 weight percent, from 0.05 to 0.75 weight percent or from 0.1 to 0.5 weight percent of the total weight of the composition.

[0039] In further embodiments, the compositions disclosed herein optionally may comprise a UV stabilizer that can prevent or reduce the degradation of the composition by UV radiation. Any UV stabilizer known to a person skilled in the art may be used in the adhesive composition disclosed herein. Non-limiting examples of suitable UV stabilizers include benzophenones, benzotriazoles, aryl esters, oxanilides, acrylic esters, formamidine, carbon black, sterically hindered amines, nickel quenchers, phenolic antioxidants, metal salts, zinc compounds and combinations thereof. The amount of UV stabilizer in the composition, if used, may be from greater than 0 to 1 weight percent, from 0.05 to 0.75 weight percent or from 0.1 to 0.5 weight percent of the total weight of the composition.

[0040] In further embodiments, the compositions disclosed herein optionally may contain a colorant or a pigment. Any dyeing agent or pigment known to the person skilled in the art may be used in the adhesive composition disclosed herein. Non-limiting examples of suitable colorants or pigments include inorganic pigments such as titanium dioxide and carbon black, phthalocyanine pigments and other organic pigments such as IRGAZIN®, CROMOPHTAL®, MONASTRAL®, CINQUASIA®, IRGALITE®, ORASOL®, all available from Ciba Specialty Chemicals, Tarrytown, NY. The amount of colorant or pigment in the composition, if used, may be from more than 0 to 10 weight percent, from 0.1 to 5 weight percent, or from 0.5 to 2 weight percent of the total weight of the composition.

[0041] A composition for the film B in a film according to the present invention, often referred to as an "tie" layer, is chosen to adhere to the layer C and optionally to A (or optionally to another layer) during the production of the film according to the invention. or, preferably, by co-extrusion or, alternatively, but less preferably, by a lamination process (such as extrusion lamination, thermal lamination or adhesive lamination). As noted above, layer B contains a composite crystalline block copolymer resin (CBC).

[0042] The term "block copolymer" or "segment copolymer" refers to a polymer comprising two or more different regions or segments (referred to as "blocks") connected in a linear manner, i.e. to a polymer containing chemically different units that are connected (covalently bounded) ends with respect to the polymerized functional groups, not by grafting or as side groups. In a preferred embodiment, the blocks differ in the amount or type of comonomer incorporated therein, density, amount of crystallinity, type of crystallinity (e.g., polyethylene versus polypropylene), the size of the crystals specific for the polymer in such composition, type or degree of tacticity (isotactic or syndiotactic), region regularity or regio-irregularity, number of branches, including long-chain or hyper-branching branches, homogeneity or other chemical or physical features. The block copolymers according to the invention are characterized by an exceptional distribution of both the polydispersity of the polymer (PDI or Mw / Mn) and the block length distribution, thanks in a preferred embodiment to the shuttling agent effect in combination with the catalyst (s). ).

[0043] The term "crystalline block composite" (CBC) (including the term "crystalline block copolymer composite") refers to a composite comprising three parts: a crystalline ethylene-based polymer (CEP), a crystalline alpha-olefin-based polymer (CAOP) and block copolymer that has a crystalline block

The ethylene block (CEB) and the crystalline alpha-olefin block (CAOB), wherein the CEB block in the block copolymer has the same composition as the CEP in the block composite, and the CAOB in the block copolymer has the same composition as the CAOP in the block composite. The three parts are present together as one component. In addition, the breakdown due to the composition between the amount of CEP and CAOP will be the same as between the respective blocks in the block copolymer. Block copolymers can be linear or branched. More specifically, each of the respective block segments may contain long chain branches, but the copolymer block segment is substantially linear as opposed to the grafted or branched blocks. It is desirable that the crystalline block composites, when prepared in a continuous process, have a PDI of from 1.7 to 15, preferably from 1.8 to 10, preferably from 1.8 to 5, more preferably from 1.8 to 3.5. Such crystalline block composites are described in, for example, the following complex patent applications: PCT / US11 / 41189, US13 / 165054, PCT / US11 / 41191; US13 / 165073, PCT / US11 / 41194 and US

13/165096; all reported on June 21, 2011.

[0044] CAOB refers to highly crystalline blocks of polymerized alpha-olefin units in which the monomer is present in an amount greater than 90 mole%, preferably greater than 93 mole%, more preferably greater than 95 mole% and preferably greater than 96 mole% . In other words, the comonomer content in CAOBs is less than 10 mole% and preferably less than 7 mole%, more preferably less than 5 mole% and most preferably less than 4 mole%. CAOBs with propylene crystallinity have suitable melting points which are 80 ° C and above, preferably 100 ° C and above, more preferably 115 ° C and above, and most preferably 120 ° C and above. In some embodiments, the CAOB includes all or substantially all of the propylene units. On the other hand, CEB refers to blocks of polymerised ethylene units in which the comonomer content is 10 mole% or less, preferably between 0 mole% and 10 mole%, more preferably between 0 mole% and 7 mole%, and most preferably between 0 mole% and 5% mol. Such CEB have suitable melting points, which are preferably 75 ° C and above, more preferably 90 ° C and 100 ° C and above.

[0045] & quot; Hard & quot; segments refer to highly crystalline blocks of polymerised units in which the monomer is present in an amount greater than 90 mole percent and preferably greater than 93 mole percent, more preferably greater than 95 mole percent and most preferably greater than 98 mole percent. In other words, the comonomer content in the hard segments is most preferably less than 2 mole percent, more preferably less than 5 mole percent and preferably less than 7 mole percent and less than 10 mole percent. In some embodiments, the hard segments comprise all or substantially all of the propylene units. On the other hand, the "soft" segments refer to amorphous, substantially amorphous or elastomeric blocks of polymerized units,

The CBCs are preferably prepared by a process comprising contacting an addition polymerizable monomer or mixture of monomers under addition polymerization conditions with a composition comprising at least one addition polymerization catalyst, cocatalyst and chain shuttling agent under different process conditions in two or more amounts. reactors operating under steady state polymerization conditions or in two or more reactor zones operating under conditions

Polymerization with piston flow. In a preferred embodiment, the CBCs comprise a block polymer fraction that has the most likely distribution of block lengths.

[0047] Suitable methods useful for making block composites and crystalline block composites can be found, for example, in US2008 / 0269412, published October 30, 2008.

When a block polymer comprising a crystalline ethylene block (CEB) and a crystalline alpha-olefin block (CAOB) in two reactors or zones is produced, CEB can be produced in the first reactor or zone, and CAOB in the second reactor or zone or CAOB generated in the first reactor or zone, and the CEB in the second reactor or zone. It is more preferred to produce CEB in the first reactor or zone with the added shuffling agent. The presence of increased levels of ethylene in the reactor or CEB generating zone will generally lead to a much higher molecular weight in this reactor or zone than in the CAOB reactor or zone. Fresh shuffle chains will reduce the MW of polymer in the reactor or CEB generating zone,

[0049] When reactors or zones operate in series, it is necessary to maintain various reaction conditions so that one reactor produces CEB and the other reactor produces CAOB. The transfer of ethylene from the first reactor to the second reactor (in series) or from the second reactor back to the first reactor through the solvent and monomer return system is preferably minimized. There are many unit operations to remove ethylene, but because ethylene is more volatile than the higher alpha olefin, the only simple way is to reduce the leakage pressure from the CEB generating reactor and the ethylene stripping. A more preferred approach is to avoid additional unit operations and use much higher ethylene reactivity relative to higher alpha olefins so that the conversion of ethylene in the CEB reactor reaches 100%.

[0050] Suitable catalysts and catalyst precursors for use in the production of CBSs include metal complexes such as those disclosed in WO2005 / 090426, especially those disclosed from page 20, lines 30 to pages 53, lines 20. Suitable catalysts are also disclosed in US2006 / 0199930, US 2007/0167578, US 2008/0311812, US 7,355,089 B2 or WO 2009/012215.

[0051] Preferably, the CBCs comprise propylene, 1-butene or 4-methyl-1-pentene and one or more comonomers. Preferably, the CBC block polymers comprise in polymerized form propylene and ethylene and / or one or more C4-20 α-olefin comonomers and / or one or more additional copolymerizable comonomers or include 4-methyl-1-pentene and ethylene and / or one or more C4-20 α-olefin comonomers, or include 1-butene and ethylene, propylene, ethylene and / or one or more C5-20 α-olefin comonomers and / or one or more additional copolymerizable comonomers. Additional suitable copolymerizable comonomers are selected from diolefins, cyclic olefins and cyclic diolefins, halogenated vinyl compounds and vinylidene aromatic compounds.

[0052] The comonomer content of the produced CBC can be measured using any suitable technique, preferably a technique based on nuclear magnetic resonance spectroscopy (NMR). It is highly desirable that some or all of the polymer blocks include amorphous or relatively amorphous polymers, such as copolymers of propylene, 1-butene or 4-methyl-1-pentene and comonomer, especially random copolymers of propylene, 1-butene or 4-methyl-1. -pentene with ethylene and the other polymer blocks (hard segments), if they are to mainly include propylene, 1-butene or 4-methyl-1-pentene in

EP 2 895 328 of the polymerized form. Preferably, such segments are highly crystalline or stereospecific polypropylene, polybutene or poly-4-methyl-pentene, especially isotactic homopolymers.

[0053] Still further preferably, the block copolymers in CBC comprise from 10 to 90 weight percent of crystalline or relatively hard segments and 90 to 10 weight percent of amorphous or relatively amorphous segments (soft segments), preferably from 20 to 80 weight percent of crystalline or relatively hard segments and 80 to 20 weight percent of amorphous or relatively amorphous segments (soft segments), most preferably 30 to 70 weight percent of crystalline or relatively hard segments and 70 to 30 weight percent of amorphous or relatively amorphous segments (soft segments). In soft segments, the mole percent of the comonomer may be in the range of from 10 to 90 mole percent, preferably from 20 to 80 mole percent, and most preferably from 33 to 75 mole%. Where the comonomer is ethylene, preferably it is present in an amount of 10 mole% to 90 mole%, more preferably from 20 mole% to 80 mole%, and most preferably from 33 mole% to 75 mole%. Preferably, the copolymers contain hard segments that are propylene in 90 mole% to 100 mole%. The hard segment may be more than 90 mole%, preferably more than 93 mole%, more preferably more than 95% and most preferably greater than 98 mole% propylene. Such hard segments have suitable melting points which are 80 ° C and above, preferably 100 ° C and above, more preferably 115 ° C and above, and most preferably 120 ° C and above. which in 90 mol% to 100 mol% is propylene. The hard segment may be more than 90 mole%, preferably more than 93 mole%, more preferably more than 95% and most preferably greater than 98 mole% propylene. Such hard segments have suitable melting points which are 80 ° C and above, preferably 100 ° C and above, more preferably 115 ° C and above, and most preferably 120 ° C and above. which in 90 mol% to 100 mol% is propylene. The hard segment may be more than 90 mole%, preferably more than 93 mole%, more preferably more than 95% and most preferably greater than 98 mole% propylene. Such hard segments have suitable melting points which are 80 ° C and above, preferably 100 ° C and above, more preferably 115 ° C and above, and most preferably 120 ° C and above.

[0054] CBC preferably have a Tm greater than 100 ° C, preferably greater than 120 ° C and more preferably greater than 125 ° C. Preferably, the MFR of the block composite is from 0.1 to 1000 dg / min, more preferably from 0.1 to 50 dg / min and more preferably from 0.1 to 30 dg / min.

[0055] Preferably, the composite block polymers comprise ethylene, propylene, 1-butene or 4-methyl-1-pentene and optionally one or more comonomers in the polymerized form. Preferably, the block copolymers in the crystalline block composites comprise in the polymerized form ethylene, propylene, 1-butene or 4-methyl-1-pentene and optionally one or more C4-20 α-olefin comonomers. In addition, suitable comonomers are selected from diolefins, cyclic olefins and cyclic diolefins, halogenated vinyl compounds and vinylaromatic compounds.

[0056] Comonomer content in the prepared composite block polymers can be measured using any suitable technique, preferably techniques based on nuclear magnetic resonance (NMR) spectroscopy.

Preferably, the crystalline block composite polymers according to the invention contain from 0.5 to 95% by weight. CEP, from 0.5 to 95% by weight CAOP and from 5 to 99% by weight block copolymer. More preferably, the crystalline block composite polymers contain from 0.5 to 79% by weight. CEP, from 0.5 to 79% by weight CAOP and from 20 to 99% by weight block copolymer, more preferably from 0.5 to 49% by weight. CEP, from 0.5 to 49% by weight CAOP and from 50 to 99% by weight block copolymer. Weight percentages are relative to the total weight of the crystalline block composite. The sum of the weight percent of CEP, CAOPi block copolymer equals 100%.

[0058] Preferably, the block copolymers in CBC contain from 5 to 95 weight percent of crystalline ethylene blocks (CEB) and 95 to 5 weight percent. crystalline alpha-olefin blocks (CAOB). They can contain 10% by weight. up to 90% by weight CEB and 90 wt% up to 10% by weight CAOB. More preferably, the block copolymers contain 25 to 75 wt. CEB and 75 to 25 wt% CAOB, and even more preferably contain 30 to 70 wt. CEB and 70 to 30 wt% CAOBA.

[0059] In some embodiments, the block composites of the invention have a crystalline block composite (CBCI) index, as defined below, which is greater than zero but less than 0.4 or is from 0.1 to 0.3. In other embodiments, the CBCI is greater than 0.4 and up to 1.0. In some embodiments, the CBCI ranges from 0.1 to 0.9, from 0.1 to 0.8 from 0.1 to 0.7, or from 0.1 to 0.6. In addition, the CBCI may be in the range of 0.4 to 0.7, from 0.5 to 0.7, or from 0.6 to 0.9. In some embodiments, the CBCI ranges from 0.3 to 0.9, from 0.3 to 0.8, or from 0.3 to 0.7, from 0.3 to 0.6, from 0.3 to 0. , 5, or from 0.3 to 0.4. In other embodiments, the CBCI ranges from 0.4 to 1.0, from 0.5 to 1.0, or from 0.6 to 1.0, from 0.7 to 1.0, from 0.8 to 1. , 0, or from 0.9 to 1.0. [0060] Further preferably,

[0061] The overall composition of each resin is determined by DSC, NMR, gel permeation chromatography, dynamic mechanical spectroscopy and / or transmission electron micrograph, respectively. To assess the efficiency of the block copolymer, and in particular the block composite index, xylene fractionation and high-liquid liquid chromatography fractionation ("HTLC") can still be used. These techniques are described in more detail in patent application publications No. US2011-0082257, US20110082258 and US2011-0082249, all published on April 7, 2011.

[0062] Crystalline block composites that have CAOP and CAOB comprised of crystalline polypropylene and CEP and CEB composed of crystalline polyethylene can not be fractionated by conventional methods. Techniques based on solvent or temperature fractionation, for example, using xylene fractionation, solvent / non-solvent separation, temperature elution fractionation or crystallization fractionation with crystallization are not able to cleave block copolymer, since CEB and CAOB co-crystallize with CEP and CAOP, respectively . However, using a method such as high-temperature liquid chromatography, which separates polymer chains using a combination of a mixed solvent / non-solvent and a graphite column, the crystalline polymers such as polypropylene and polyethylene can be separated from each other and from the block copolymer. [0063] For crystalline block composites, the amount of PP isolated is less than if the polymer were a simple blend of the iPPF homopolymer (in this example CAOP) and polyethylene (in this example CEP). Consequently, the polyethylene fraction contains a significant amount of propylene which would not be present if the polymer were a simple blend of iPP and polyethylene. To calculate this "extra propylene", a mass balance can be performed to estimate the crystalline block block index based on the amount of the polypropylene and polyethylene fractions and the wt% of propylene present in each fraction that has been separated by HTLC. The polymers contained in the crystalline block composite include iPP-PE diblock, unbound iPP and unbound PE,

[0064] As a result of adding up the weight% of propylene in each component in the polymer, a total weight% of propylene (in the entire polymer) is obtained. This mass balance equation can be used to calculate the amount of iPP and PE present in the diblock copolymer. This mass balance equation can also be used to calculate the amount of iPP and PE in a double blend or extended to a triple or non-blended blend. In the case of a crystalline block composite, the total amount of iPP or PE is contained in the blocks present in the diblock and unbound iPP and PE polymers.

EP 2 895 328 wt. Generally = wPP (wt% C3PP) + wPE (wt% C3PE) Equal. 1 where wPP = weight percentage of PP in the polymer wPE = mass fraction of PE in the polymer% wt.CO3PP = weight proportion of propylene in the PP component or in the% wt% block. C3PE = weight proportion of propylene in the PE component or in the block [0065] It should be noted that the total wt.% propylene (C3) or some other composition values ​​that relate to the total amount of C3 present in the entire polymer, preferably are measured by the C13 NMR technique. wt% The propylene in the iPP block (wt% C 3 PP) is set to 100 or, if it is different based on DSC melting point, NMR measurement or other composition evaluation, this value can be inserted in its place. Similarly% wt. The propylene in the PE block (% by weight of C3PE) is set at 100 or, if different based on DSC melting point, NMR measurement or other composition evaluation,

[0066] Based on Equation 1, the overall weight ratio of the PP present in the polymer from the total mass balance C3 measured in the polymer can be calculated using Equation 2. Alternatively, it can also be estimated based on the mass balance of monomer and comonomer consumption during polymerization. Generally, this represents the amount of PP and PE present in the polymer regardless of whether it is present in the unbound components or in the diblock copolymer. In the case of a conventional blend, the proportion by weight of PP and the proportion by weight of PE corresponds to the individual amounts present in the polymer. In the case of a crystalline block composite, it is assumed that the weight ratio of PP to PE also corresponds to the average ratio in blocks between PP and PE present in this statistical block copolymer.

wt% C3ogóiny - wt% C3pe wpp = Equ. 2 wt% C 3 PP - wt% C3PE where wPP = weight percent PP present in the entire polymer% wt. C3PP = weight fraction of propylene in PP component or in wt% block. C3PE = weight proportion of propylene in the PE component or in the block [0067] Equation 3 to 5 uses the amount of PP isolated as measured by HTLC to determine the amount of polypropylene present in the diblock copolymer. The amount isolated or separated first in the HTLC analysis shows "unbound PP" and its composition is representative of the hard PP block present in the diblock copolymer. By inserting the total% C3 by weight in the entire polymer on the left side of Equation 3, and the PP weight fraction (isolated from HTLC) and the PE weight fraction (separated by HTLC) on the right side of Equation 3, one can calculate the weight% C3 in the PE fraction using equations 4 and 5. The PE fraction is described as a fraction separated from unbound PP that contains diblock and unbound PE. It is assumed that the composition of the isolated PP is the same as the wt% of propylene in the iPP block as previously described.

^{wt% C3}general ^{= w}PPwyizolowany^{(wt% C 3}PP^{) + w}PE-fraction^{(wt% C 3}PE-fraction^{) Equal 3} ^^^^% LBWCol. -PWPProled (%. Wag.C3pp)% Wag.C3pE-fraction = ⁱⁿPE-fraction ⁱⁿpE-fraction ^{= 1-} WPP-isolated ^{Eq. 5}

Eq. 4 where wPPisolated = weight percentage of isolated PP by HTLC method wPE-fraction = weight percentage of PE separated by HTLC, containing diblock and non-bound PE

EP 2 895 328 wt. C3PP =% by weight propylene in PP, which is the same amount of propylene as present in the PP block and unbound PP% by weight C3-fraction = wt% propylene in the PE fraction, which was separated by HTLC wt% Generalized) = total wt% of propylene in the entire polymer [0068] Amount in wt% C3 in the polyethylene fraction with HTLC represents the amount of propylene present in the block copolymer fraction which is above the amount present in the "unbound polyethylene".

[0069] The only way to obtain the presence of "additional" propylene in the polyethylene fraction is the presence of PP in this fraction, and therefore the PP polymer chain must be connected to the PE polymer chain (or else could be isolated with the PP fraction separated by HTLC). Thus, the PP block remains bound to the PE block until the PE fraction is separated.

[0070] The amount of PP present in the diblock is calculated using Equation 6.

^^ ^^ _ _ wt% wt% C3pE_frakęja-C3pE ^^ ^^ _ _

Wpp-diblock = Equal 6 wt% C3PP - wt% C3PE in which% wt. C3-fraction = wt% propylene in the PE fraction that was separated by HTLC (Equation 4) wt% C3PP = wt% propylene in the PP component or block (predetermined) wt% C3PE = wt% propylene in the component or block of PE (as defined previously) wPP-diblock = wt% PP in diblock separated with the PE fraction by HTLC [0071] The amount of diblock present in the PE fraction can be estimated by assuming that the ratio of the PP block to The PE block is the same as the overall PP to PE ratio present in the entire polymer. For example, if the overall ratio of PP to PE in the entire polymer is 1: 1, then the ratio of PP to PE in the diblock is also assumed to be 1: 1. Thus, the weight fraction of the diblock present in the PE fraction would be the weight ratio of PP in diblock (wPP-diblock) multiplied by two.

[0072] In order to determine the estimated amount of diblock present in the entire polymer, the amount of diblock in the PE fraction evaluated is multiplied by the weight fraction of the PE fraction measured in HTLC.

[0073] To determine the estimated crystalline block composite index, the amount of the block copolymer is determined using equation 7. To determine the estimated CBCI, the calculated weight percentage of diblet in the PE fraction according to Equation 6 is divided by the total weight fraction of the PP fraction (as calculated in Equation 2) and then multiplied by the weight fraction of the PE fraction. The CBCI value may be in the range of 0 to 1, with 1 being 100% diblock, and zero being for a material such as a traditional bland or random copolymer.

WPP - diblock

CBCI = - Wpp - Equal fraction 7

WPP where wPP-diblock = weight share of PP in diblock separated with PE fraction by HTLC (Equation 6) wPP = weight percentage of PP in polymer wPE-share = weight percentage of PE separated from HTLC, containing diblock and unbound PE (Equation 5) ] For example, if the iPP-PE polymer contains a total C3 amount of 62.5 wt%. and is prepared under conditions which result in the formation of a PE polymer with 10 wt.% C3 and iPP polymer containing 97.5 wt.% C3, PE and PP weight shares are respectively 0.400, 0.600 (as calculated using Equation 2). Since the percentage of PE is 40.0 wt% and the iPP is 60.0 wt%, the relative ratio of the PE blocks: PP is expressed as 1: 1.5.

[0075] Thus, if the skilled person will separate the polymer by HTLC and isolate 28% by weight. PP and 72 wt% PE fraction, this would be an unexpected result and would lead to the conclusion that a fraction of the block copolymer was present. If then calculated from equations 4 and 5, the C3 content in the PE fraction (wt% C3PE fraction) is

EP 2 895 328

48.9 wt.%, The PE fraction containing the additional propylene, has a weight fraction of the PE polymer of 0.556 and a weight percentage of PP polymer 0.444 (wPP-diblock, calculated using Equation 6).

[0076] Since the PE fraction contains PP with a weight fraction of 0.444, it should be combined with an additional PE polymer, whose weight fraction is 0.293 based on a block ratio of 1.5: 1. Thus, the weight fraction of the diblock present in the PE fraction is 0.741; the calculated weight percentage of the diblock present in the whole polymer is 0.533. The composition for the entire polymer is described as follows: 53.3 wt. diblock iPP-PE, 28 wt. PP polymer and 18.7 wt.% PE polymer. The crystalline block composite index (CBCI) is the approximate weight fraction of the diblock fraction present in the entire polymer. For example, it is described above that the CBCI for the crystalline block composite is 0.533.

[0077] The crystalline block composite index (CBCI) provides the approximate value of the amount of block copolymer in the crystalline block composite, assuming that the ratio of CEB to CAOB in diblock is the same as the ratio of crystalline ethylene to crystalline alpha-olefin in the entire crystalline block composite. This assumption is important for these statistical olefin block copolymers and is based on the knowledge of individual catalyst kinetics and the polymerization mechanism during the production of diblocks by catalysis with chain shuffling as described herein.

[0078] The calculation of CBCI is based on the analytical observation that the amount of free CAOP is lower than the total amount of CAOP that was produced in the polymerization. The remaining CAOP is associated with CEB to form a diblock copolymer. Because the PE fraction separated by HTLC contains both CEP and diblock copolymer, the observed amount of propylene in this fraction is higher than the amount in CEP. This difference can be used to calculate CBCI.

[0079] It is possible to calculate the minimum and maximum amount of the block copolymer present in the polymer based solely on analytic observations without knowing the polymerization statistics and to distinguish in this way the crystalline block composite from the common copolymer or copolymer blends.

[0080] The upper limit of the amount of block copolymer present in the crystalline block composition, inDBMax, is obtained by subtracting the proportion of unbound PP measured by HTLC from unity as in Equation 8. This maximum assumes that the PE fraction from HTLC is completely diblock and that all ethylene crystalline is bound to crystalline PP, without any unbound PE. Only the CBC non-diblocked material is part of the PP separated by HTLC.

WDBMax = 1 - WPP-isolated

Eq. [0081] The lower limit of the amount of the block copolymer present in the crystalline block composite, in DBMin, corresponds to a situation where little to no PE is associated with PP. This lower limit is obtained by subtracting the amount of unbound PP measured by HTLC from the total amount of PP in the sample as set forth in Equation 9.

WDBMin = 1 - WPP equiv. Equal [0082] Furthermore, the crystalline block composite index will be between these two values: wDBMin <CBCI <wDBMax.

[0083] As can be seen from the polymerization mechanism for producing the crystalline block composite, CBCI is the best approximate value of the actual contribution of the diblock copolymer in the composite. IN

In the case of unknown polymer samples, wBMin can be used to determine if the material is a crystalline block composite. In the case of a physical blend of PE and PP, the overall weight percentage of PP should be equal to% by weight. PP with HTLC and the lower limit of diblock content, Equation 9, is zero. When this analysis refers to a PP sample that does not contain PE, both the PP weight fraction and the amount of PP obtained from HTLC are 100% and again the lower limit of the diblock content, Equation 9, is zero. Finally, when this analysis refers to a PE sample that does not contain PP, then both the PP weight fraction and the PP weight fraction recovered by HTLC are zero and the lower limit for diblock, Equation 9, is zero. Since the lower limit of the diblock content is not more than zero in each of these three cases,

Differential Scanning Calorimetry (DSC) [0084] Differential scanning calorimetry is used to measure, among others, the heat of melting of the crystalline block and block composites and is performed on a TA Instruments Q1000 DSC equipped with RCS cooling accessories and an autosampler. Nebulizer nitrogen with a flow of 50 ml / min is used. The sample is pressed into a thin film and melted in the press at about 190 ° C and then cooled in air to room temperature (25 ° C). Then 3-10 mg of material is cut, accurately weighed and placed in a light aluminum crucible (about 50 mg), which is then closed with a cap. The thermal behavior of the sample is tested according to the following temperature profile: the sample is heated quickly to 190 ° C and the isotherm is maintained for 3 minutes to remove the previous thermal history. The sample is then cooled to -90 ° C at a cooling rate of 10 ° C / min and maintained at -90 ° C for 3 minutes. The sample is then heated to 190 ° C at a heating rate of 10 ° C / min. Cooling and second heating curves are recorded. For CBC melting heat measurements and specific BC resins as known and routinely performed by those skilled in the art, the baseline for calculations is plotted from the flat initial section before the onset of melting (usually in the range of about -10 to about 20 ° C for all types materials) and until the melting point for the second heating curve.

[0085] Another suitable resin (e) which (e) can be used in the layer B in the block composite comprises:

i) an ethylene polymer containing at least 80 mole% polymerized ethylene, preferably at least 85 mole%, more preferably at least 90 mole% and most preferably at least 93 mole% of polymerised ethylene;

ii) a crystalline alpha-olefin-based polymer (CAOP); and iii) a block copolymer comprising (a) an ethylene polymer block containing at least 80 mole% polymerized ethylene, preferably at least 85 mole%, more preferably at least 90 mole% and most preferably at least at least 93 mole% of polymerized ethylene and (b) crystalline alpha-olefin block (CAOB).

[0086] A preferred suitable resin (e) CBC for the layer B has CAOB in an amount (in part (iii)) in the range of 30 to 70% by weight (based on (iii)), preferably at least 40% by weight, more preferably at least 45% by weight and most preferably 50 wt. and preferably up to 60 wt.% and preferably up to 55 wt.% (in each case the ethylene polymer is in addition). It has also been found that the CBC resin (s) suitable for the B layer has a (crystalline) block composite index of at least 0.1, preferably at least 0.3, preferably at least 0.5 and more preferably at least 0, 7. Another method of characterizing the appropriate resin (s) relevant for layer B is MFR in the range of 1 to 50 dg / min; preferably at least 2, more preferably at least 3 and preferably up to 40, and preferably up to 30 g / min.

In general, CBCs that can be used in layer B of the present invention will have melting heat values ​​(reflecting a relatively high ethylene content in CEP and CEB) of at least 85 Joules per gram (J / g), more preferably at least 90 J / g, as measured by DSC. In another case, the melting heat values ​​for polymers of these types usually have a maximum in the region of 125 J / g. For heat melting measurements, generally known and routinely performed by those skilled in the art, the DSC proceeds as generally described below under nitrogen at 10 ° C / min from 23 ° C to 220 ° C, a constant temperature of 220 ° C is maintained, drops to 23 ° C at a rate of 10 ° C / min and returns to 220 ° C at a rate of 10 ° C / min. The data from the second heating is used to calculate the heat of fusion in the transition to the molten state.

[0089] The content of the unsaturated organic compound in the grafted polyolefin is at least 0.01 wt%, and preferably at least 0.05 wt%, based on the total weight of the polyolefin and the organic compound. The maximum amount of unsaturated organic compound may vary as desired, but usually does not exceed 10% by weight, preferably does not exceed 5% by weight, and more preferably does not exceed 2% by weight. This unsaturated organic compound content in the grafted polyolefin is measured by titration, e.g. a grafted polyolefin / xylene solution is titrated with a potassium hydroxide solution (KOH). The MAH functionality may be present in the polyolefin e.g. by grafting or even by copolymerization with an olefin monomer.

[0090] The unsaturated organic compound may be grafted onto a polyolefin by a known technique such as those described in patents US3,236,917 and 5,194,509. For example, in the '917 patent the polymer is introduced into a two-roll blender and stirred at 60 ° C. The unsaturated organic compound is then added together with a free radical initiator, such as, for example, benzoyl peroxide and the ingredients are mixed at 30 ° C until completion of the vaccination. In the '509 patent, the procedure is similar to that the reaction temperature is higher, e.g. 210 to 300 ° C, and the free radical initiator is not used or is used at a lower concentration [0091] An alternative and preferred method of vaccination is depicted in USP 4,950,541 by use of a twin-screw degassing extruder as a mixing device. The polymer and the unsaturated organic compound are mixed and reacted in the extruder at temperatures at which the reactants are melted and in the presence of a free radical initiator. Preferably, the unsaturated organic compound is injected into the zone maintained under pressure in the extruder.

[0092] Above, in the description of the use of polymeric components for producing a laminate or layered structures there are several terms that are regularly used and defined as below.

[0093] "Layer" means a single thickness, coating or layer spread on the surface in a continuous or discontinuous manner or covering the surface.

[0094] "Multi-layer" means at least two layers.

[0095] "Face," "planar surface," and like terms when referring to films or layers, mean the surfaces of the layers that are in contact with opposing and adjacent surfaces of the joining layers. The face surfaces exist in contrast to the edge surface. The foil or rectangular layer has two faces and four edge surfaces. The circular layer has two faces and one continuous edge surface.

EP 2 895 328 [0096] & quot; Adhering contact & quot; and like terms mean that one face of one layer and one face of another layer are in contact in which they contact and bond to one another, so that one layer can not be removed from the second layer without damaging the contact faces of both layers.

[0097] "Close relationship" and like terms mean that two or more components, e.g. two polymer layers or a polymer layer and an electronic device, or a polymer layer and a glass covered sheet, etc., combine with one another. in such a way, e.g. by co-extrusion, lamination, coating, etc., that the interface formed by their combination is separated from their immediate external environment.

[0098] The multilayer film or sheet structures of the present invention, depending on the intended use thereof, can be designed to meet certain property requirements, such as in the area of ​​physical properties including hardness, transparency, tensile strength, interlayer adhesion and resistance to heat.

[0099] In some embodiments, the total thickness of the structure may be in the range of 25 μm (micron) - 2.5 cm or preferably, 50 μm (micron) to 1 mm. In some embodiments, layer B has a thickness of 4 μm (microns) to 50 μm (microns).

[0100] In addition to multilayer film structures, the invention also includes any multilayer structure, including injection molded and blow molded containers and bottles, tubes, tubes, wires and cables, and films, and sheets including laminates. Examples of structures include those that are disclosed, for example, in CA 2 735 182, in US2003 / 0215655, US2004 / 0241360 and US2007 / 0160788. These structures include rigid molded rigid products, multilayer film structures that have annular profiles and extrusion-molded coextruded articles.

EXAMPLES [0101] Experimental multi-layered test films (layers indicated by letters, e.g. A, B and C) as summarized in the Tables below are made from the thermoplastic resins shown in Table 1. Where indicated, Melt Flow Indicators (MFR) are measured according to ASTM D1238 (230C / 2, 1 6kg) and given in grams for 10 minutes (g / 10 min) and values ​​of melt index (MI) are measured according to ASTM D1238 (190C / 2.16kg) and reported in g / 10 min. Density is measured according to ASTM D792 and given in grams per cubic centimeter (g / cm³).

Autoclave process [0102] Autoclave treatment is carried out in a Contexxor yarn evaporator. The foils are cut into pieces 200X15 mm in the machine direction and welded on permanent sealing strips at 150 ° C for 1 second. Four seals were prepared and the bags were kept empty. Empty bags were sterilized in the evaporator at 122 ° C for 40 min.

Adhesion Test [0103] For the adhesion test, the films were welded lengthwise in a direction perpendicular at 150 ° C for 1 sec. 15 mm wide and 100 mm long strips were cut from the welded area. Adhesion was measured along the machine's working direction. Delamination was initiated by carefully opening the seal. Samples are torn off at a rate of 125 mm min^-1 at ambient temperature in the INSTRON 5564 dynamometer. At least 5 samples are tested and the average of the load peak is recorded.

EP 2 895 328

Fogging Test [0104] Haze of the film is measured based on the method according to ISO 14782. Adhesion and haze are measured both before and after autoclaving.

Test of heat-seal strength [0105] The heat-weld strength test is based on the ASTM test method F88, STM for testing the weld strength of elastic barrier materials. The force needed to separate the test strip of material in which the weld is located is measured. The method of destroying the sample is also identified. The samples are cut into a 15 mm wide strip. The result of the test is the amount of force required to stretch the weld or the force required to break the film in cases where the film breaks up before the weld separates.

Optical microscopy [0106] Optical sections approximately 5 μm thick (microns) at 120 ° C were collected to prepare the samples using a diamond knife in a Leica UCT microtome equipped with a FCS cryochamber. The sections were transferred to a microscope slide with a drop of Dow Corning E-200 silicone oil and covered with a glass lid before analysis. To view the optical sections under a Carl Zeiss Axiolmager Z1m microscope, light passing through a bright field under differential interference differential lighting was used and photographs were taken using a HRc digital camera.

Materials [0107]

Table 1 Description of materials_

<td>stuff</td><td>Description</td>

<td>CBC1</td><td>50/50 EP / iPP, 90 wt% C2 in EP, 3.6 MFR (g / 10 min at 230 ° C / 2.16 Kg)</td>

<td>CBC2</td><td>50/50 EP / iPP, 90 wt% C2 in EP, 7.0 MFR</td>

<td>CBC3</td><td>50/50 EP / iPP, 90 wt% C2 in EP, 6.3 MFR</td>

<td>CBC4</td><td>50/50 EP / iPP, 90 wt% C2 in EP, 8.5 MFR</td>

<td>MAHPECONC1</td><td>AMPLIFY TY1053H, MAH-g-HDPE, 0.965 g / cm³, 2MI (g / 10 min at 190 ° C / 2.16 Kg</td>

<td>PP H357-09R</td><td>Polypropylene homopolymer, 9.5 MFR, Brask</td>

<td>AFFINITY EG 8200</td><td>Polyolefin elastomer, 0.870 g / cm³, 5.0 MI, The Dow Chemical Company</td>

<td>AFFINITY PL1850</td><td>A polyolefin plastomer, 0.900 g / cm³, 3.0 MI, The Dow Chemical Company</td>

<td>HDPE KS10100</td><td>HDPE, 0.953 g / cm³, 4.0 MI, The Dow Chemical Company</td>

<td>MAHPECONC2</td><td>MAH-g-HDPE, 0.960 g / cm³, 6.0 MI, 2.0 wt% MAH, The Dow Chemical Company</td>

<td>MAHPPCON</td><td>MAH-g-PP, 500 MI, 0.7 wt% MAH, The Dow Chemical Company</td>

<td>ELITE 5100G</td><td>LLDPE, 0.920 g / cm³, 0.85 MI, The Dow Chemical Company</td>

<td>ELITE 5940G</td><td>MDPE, 0.940 g / cm³, 0.85 MI, The Dow Chemical Company</td>

<td>ENGAGE 8150</td><td>Elastomer poliolefinowy, 0,870 g/cm³, 0.5 MI, The Dow Chemical Company</td>

<td>INFUSE OBC 9500</td><td>Olefin block copolymer, Density = 0.877 g / cm³, 5.0 MI, The Dow Chemical Company</td>

<td>AMPLIFY TY 2551</td><td>Resins for an intermediate layer based on PP in the form of a formulation, 5.0 MFR, The Dow Chemical Company</td>

<td>PPTIE1</td><td>Resins for an intermediate layer based on PP in the form of a formulation, 5.5 MFR, 0.14 wt% Level of vaccination with MAH, The Dow Chemical Company</td>

<td>ADMER QF551</td><td>Resins for an intermediate layer based on PP in the form of a formulation, 5.2 MFR, Mitsui Chemicals</td>

<td>PP R7051-10N</td><td>Random polypropylene copolymer, 10 MFR, Brask</td>

<td>PP R35208-R</td><td>Random polypropylene copolymer, 8 MFR, Braskem</td>

<td>Polyamide UBE 5033B</td><td>Copolymer polyamide 6/66, UBE Engineering Plastics, SA</td>

<td>PP 6D83K</td><td>Random polypropylene copolymer, 1.9 MFR, Brask</td>

<td>Polyamide Ultramid ™ C33L01</td><td>Copolymer polyamide 66/6, BASF</td>

<td>Polyamide Ultramid ™ B36 01</td><td>Polyamide 6, BASF</td>

EP 2 895 328

<td>EVOH EVAL ™ H171B</td><td>EVOH with 38 mol% ethylene, Kuraray Co., Ltd.</td>

<td>EVOH EVAL ™ LR171B</td><td>EVOH with 27 mol% ethylene, Kuraray Co., Ltd.</td>

<td>PP H110-02N</td><td>Polypropylene homopolymer, 2.0 MFR, Brask</td>

<td>Polyamide Ultramid ™ C40LN07</td><td>Copolymer polyamide 66/6, BASF</td>

<td>EVOH EVAL ™ F171B</td><td>EVOH with 32 mole% ethylene, Kuraray Co., Ltd.</td>

<td>DOWLEX 2045G</td><td>LLDPE, 0.920 g / cm³, 1 MI, The Dow Chemical Company</td>

<td>AMPLIFY TY 1353</td><td rowspan="2">Resin for an intermediate layer based on PE in the form of a formulation, 2 MI, The Dow Chemical Company. Resin for an intermediate layer based on PE in the form of a formulation, 2.3 MI, The Dow Chemical Company</td>

<td>AMPLIFY TY 1228B</td>

<td>Irganox B225</td><td>BASF</td>

<td>Irganox B215</td><td>BASF</td>

Synthesis of a crystalline block composite

[0108] Catalyst-1 ([[rel-2 ', 2 "' - [(1R, 2R) -1,2-cyclohexanediylbis (methyleneoxy-KO)] bis [3- (9H-carbazol-9-yl) -5-methyl- [1,1-biphenyl] -2-ol- O.O]] (2 -)] dimethyl-hafnium) and cocatalyst-1, a mixture of methyl di (C145 alkyl) ammonium salt tetrakis (pentafluorophenyl) borate, produced by reaction of a long-chain trialkylamine (Armeen ™ M2HT, available from Akzo-Nobel, Inc.), HCl and Li [B (C6F5) 4], essentially as disclosed in USP5,919,983, Prz 2, was purchased from Boulder Scientific and used without further purification.

[0109] CSA-1 (diethylzine or DEZ) and cocatalyst-2 (modified with methylalumoxane (MMAO)) were purchased from Akzo Nobel and used without further purification. The solvent for the polymerization reaction is a mixture of hydrocarbons (ISOPAR^®E), which can be obtained from ExxonMobil Chemical Company, purified prior to use on a 13-X molecular sieve bed.

[0110] The crystalline block composites of the present Examples are designated CBC1-CBC4. They are made using two stirred tank reactors (CSTR) connected in series. The first reactor had a volume of about 45 liters (12 gallons) while the second reactor had a volume of about 98 liters (26 gallons). Each reactor is filled hydraulically and set to operate in steady-state conditions. Monomers, solvent, hydrogen, catalyst-1, cocatalyst-1, cocatalyst-2 and CSA-1 are fed into the first reactor according to the process conditions shown in Table 2. The contents of the first reactor as described in Table 2 flows into the second reactor in series. Additional monomers, solvent, hydrogen, catalyst-1, cocatalyst-1 and optionally cocatalyst-2 are added to the second reactor.

Table 2. Process conditions in a reactor for producing a crystalline block composite

<td></td><td colspan="2">CBC1</td><td colspan="2">CBC2</td><td colspan="2">CBC3</td><td colspan="2">CBC4</td>

<td>Reactor</td><td>1-y</td><td>2nd</td><td>1-y</td><td>2nd</td><td>1-y</td><td>2nd</td><td>1-y</td><td>2nd</td>

<td></td><td>reactor</td><td>reactor</td><td>reactor</td><td>reactor</td><td>reactor</td><td>reactor</td><td>reactor</td><td>reactor</td>

<td>Reactor temperature control (° C)</td><td>118</td><td>110</td><td>140</td><td>135</td><td>141</td><td>135</td><td>153</td><td>130</td>

<td>Batch of solvent</td><td>65.8</td><td>65.8</td><td>96.2</td><td>111.1</td><td>109.8</td><td>111.1</td><td>155.6</td><td>45.8</td>

<td>(kg / hour) ((pound / hour))</td><td>(145)</td><td>(145)</td><td>(212)</td><td>(245)</td><td>(242)</td><td>(245).</td><td>(343)</td><td>(101)</td>

<td>Propylene feed</td><td>0.90</td><td>14.08</td><td>2.48</td><td>22.4</td><td>2.47</td><td>22.12</td><td>1.5</td><td>20.0</td>

<td>(kg / hour) ((pound / hour))</td><td>(1.98)</td><td>(31.03)</td><td>(5.46)</td><td>(49.3)</td><td>(5.44)</td><td>(48.76)</td><td>(3,4)</td><td>(44.1)</td>

<td>Ethylene feed (kg / hour) ((pound / hour))</td><td>12.6 (27.8)</td><td>0.0</td><td>21.4 (47.1)</td><td>0.0</td><td>21.3 (47.0)</td><td>0.0</td><td>18.9 (41.7)</td><td>0</td>

<td>Hydrogen charge (SCCM)</td><td>9.6</td><td>9.2</td><td>9.6</td><td>9.9</td><td>9.5</td><td>0.0</td><td>0</td><td>0</td>

EP 2 895 328

<td>Concentration of ethylene in the reactor (g / l)</td><td>3.25</td><td>-</td><td>3.84</td><td>-</td><td>4.41</td><td>-</td><td>2.06</td><td>-</td>

<td>Conc. propylene in the reactor (g / l)</td><td>-</td><td>2.00</td><td>-</td><td>2.00</td><td>-</td><td>2.26</td><td>-</td><td>2.42</td>

<td>Efficiency Catalyst (gPoles / gM) * 1.0E6</td><td>5.166</td><td>0.167</td><td>0.86</td><td>0,025</td><td>0.706</td><td>0,075</td><td>0,247</td><td>0.138</td>

<td>Catalyst flow</td><td>0.53</td><td>0.43</td><td>0.89</td><td>0.97</td><td>0.21</td><td>0.81</td><td>0.14</td><td>0.24</td>

<td>(kg / hour) ((pound / hour))</td><td>(1.16)</td><td>(0.95)</td><td>(1.96)</td><td>(2.14)</td><td>(0.47)</td><td>(1.78)</td><td>(0.31)</td><td>(0.53)</td>

<td>Conc. Catalyst (ppm)</td><td>5</td><td>196</td><td>thirty</td><td>900</td><td>150</td><td>500</td><td>600</td><td>600</td>

<td>Flow</td><td>0.67</td><td>0.42</td><td>0.67</td><td>0.98</td><td>0.64</td><td>0.51</td><td>0.28</td><td>0.24</td>

<td>kokatalizatora-1 (kg / hour) ((pound / hour))</td><td>(1.48)</td><td>(0.93)</td><td>(1.47)</td><td>(2.16)</td><td>(1.41)</td><td>(1.12)</td><td>(0.62)</td><td>(0.53)</td>

<td>Conc. cocatalyst-1 (ppm)</td><td>50</td><td>2000</td><td>400</td><td>7500</td><td>500</td><td>8000</td><td>2729</td><td>7082</td>

<td>Flow of cocatalyst-2 (kg / hour) ((pound / hour))</td><td>0.41 (0.91)</td><td>0.00</td><td>0</td><td>0.14 (0.30)</td><td>0.54 (1.18)</td><td>0.34 (0.75)</td><td>0.327 (0.72)</td><td>0.331 (0.73)</td>

<td>Conc. cocatalyst-2 (ppm)</td><td>1494</td><td>0</td><td>0</td><td>2686</td><td>1993</td><td>1993</td><td>3442</td><td>1893</td>

<td>DEZ flow (kg / h) ((pound / hour))</td><td>0.50 (1.10)</td><td>0.00</td><td>0.88 (1.94)</td><td>0</td><td>0.86 (1.89)</td><td>0</td><td>0.68 (1.49)</td><td>0</td>

<td>Conc. DEZ (ppm)</td><td>30000</td><td>0</td><td>30000</td><td>0</td><td>30000</td><td>0</td><td>30000</td><td>0</td>

Table 3 - Physical properties of the crystalline block composite

<td>Example</td><td>MFR (230 ° C / 2.16 kg)</td><td>wt% PP from separation HTLC</td><td>mw kg / mol</td><td>Mw / Mn</td><td>Total wt.% C2</td><td>Tm (° C) Peak1 (Peak 2)</td><td>tc (° C)</td><td>Enthalpy of the alloy (J / g)</td>

<td>CBC1</td><td>3.6</td><td>13.2</td><td>146</td><td>2.8</td><td>46.7</td><td>130 (114)</td><td>97</td><td>126</td>

<td>CBC2</td><td>7.0</td><td>14.2</td><td>128</td><td>4.0</td><td>46.9</td><td>132 (108)</td><td>91</td><td>97</td>

<td>CBC3</td><td>7.5</td><td>19.4</td><td>109</td><td>2.8</td><td>48.3</td><td>129 (108)</td><td>91</td><td>91</td>

<td>CBC4</td><td>10.1</td><td>20.3</td><td>92</td><td>3.5</td><td>48.1</td><td>130 (105)</td><td>90</td><td>103</td>

Table 4 shows the ratio of iPP to EP as well as the approximate index of crystalline block composite for CBC1-CBC4.

Table 4 The approximate index of the crystalline block composite

<td>A sample</td><td>wt% iPP</td><td>wt% EP</td><td>wt% C2 in EP</td><td>Index of crystalline block composite</td>

<td>CBC1</td><td>49</td><td>51</td><td>90</td><td>0.729</td>

<td>CBC2</td><td>50</td><td>50</td><td>90</td><td>0.707</td>

<td>CBC3</td><td>50</td><td>50</td><td>90</td><td>0.633</td>

<td>CBC4</td><td>50</td><td>50</td><td>90</td><td>0,566</td>

[0111] Figure 1 shows the DSC profile for CBC1. The DSC profile shows a melting peak at 129 ° C, which is representative of CAOP and CAOB and 113 ° C, which corresponds to CEP and CEB. The observed enthalpy of the alloy was 115 J / g and the glass transition temperature observed was -11 ° C.

[0112] Figure 2 shows the TREF analysis of CBC1. The TREF elution profile shows that CBC1 is highly crystalline and, unlike the melting profile, DSC exhibits little or no separation of CEP and CAOP

EP 2 895 328 or a block copolymer. The measured scavenging fraction was only 2.4% by weight, which also indicates the high crystallinity of the components in CBC1.

[0113] Figure 3 shows HTLC analysis for CBC1. The CBC1 elution profile in HTLC showed that 13.2 wt.% Was eluted. early elution peak in an amount between 1-2 ml and 86.8 wt.% a later elution peak in an amount between 3-5 ml. From the concentration and composition measurement, it was determined that the early elution peak was isolated PP, which is CAOP and is representative of CAOB. This is indicated by the composition profile in% by weight. current C3. The second peak and the later elution peak are rich in C2 and have a C3 gradient. It can be interpreted that this peak is a PE phase and contains a block copolymer and a CEP. The composition gradient indicates that the block copolymer elutes earlier and CEP is eluted last.

Examples of cast film

Compounding the Formulations Into the Intermediate [0114] Blends for the intermediate layer formulation were prepared by mixing using 30mm TSE (Leistritz machine). The extruder had five heated zones, a feed zone and a 3 mm band nozzle. The feed zone is cooled by water flowing through its core, while the remaining zones 1-5 and the nozzle are electrically heated and regulated by the cooling air to specific temperatures depending on the mixed materials. The following temperature settings are used in the extrusion process: zones 1-5 are heated to 130, 186, 190, 190 and 190 ° C, and the nozzle is heated to 190 ° C. The drive unit for the extruder works at 150 rpm. The mixing formulations are shown in Table 5.

Table 5. Formulations for an intermediate layer for poured foils

<td>Example</td><td>hPP H357 -09R (%)</td><td>MAHPECON C1 (%)</td><td>CBC 1 (%)</td><td>CBC 2 (%)</td><td>AFFINITY EG 8200 (%)</td><td>AFFINITY PL1850 (%)</td><td>HDPE KS10100 (%)</td><td>Irganox B225 (%)</td>

<td>AND</td><td></td><td>20</td><td></td><td>0</td><td></td><td>80</td><td></td><td>0.2</td>

<td>1</td><td></td><td>20</td><td>20</td><td></td><td></td><td>60</td><td></td><td>0.2</td>

<td>2</td><td></td><td>20</td><td></td><td>20</td><td></td><td>60</td><td></td><td>0.2</td>

<td>3</td><td></td><td>20</td><td></td><td>thirty</td><td></td><td>50</td><td></td><td>0.2</td>

<td>4</td><td></td><td>20</td><td></td><td>40</td><td></td><td>40</td><td></td><td>0.2</td>

<td>5</td><td></td><td>20</td><td></td><td>50</td><td></td><td>thirty</td><td></td><td>0.2</td>

<td>6</td><td>25</td><td>20</td><td></td><td>40</td><td></td><td>15</td><td></td><td>0.2</td>

<td>7</td><td></td><td>20</td><td></td><td>20</td><td>20</td><td></td><td>40</td><td>0.2</td>

<td>8</td><td></td><td>20</td><td></td><td>40</td><td>20</td><td></td><td>20</td><td>0.2</td>

[0115] For comparison with a formulation for an intermediate layer based on INFUSE OBC, INFUSE OBC 9500 (OBC) is mixed with INFUSE OBC 9500 grafted with MAH (MAH-g-OBC) or with MAHPECONC1. In order to produce MAH-g-OBC, the ZSK-92 megakompaunder with 11 drums (45 L / D) is used. The OBC resin is fed from the K-Tron T-60 feeder. MAH is injected at drum 3, port 1 using the Lewa pump. The peroxide / oil mixture (50/50 w / w) was injected at drum 3, port 2, using a Prominent Sigma plunger pump. The temperature of the drum is set at 80 ° C for zone 1 and 225 ° C for zones 2 to 11. A vacuum pump is used for degassing the drum 9. The screw speed is 200 to 230 rpm, the torque is in the range from 56% to 61%. The feeding rate of OBC1 is set at 680.4 kg / h. (1500 pounds / hour). The administered formulation contains 1.70% MAH, 0, 20% peroxide / mineral oil (50/50, w / w). The final vaccination level of MAH is 1.1% and the melt index MAH-g-OBC is 3.0 (2.16 kg, 190 ° C). For casting, OBC is dry mixed with MAH-g-OBC or MAHPECONC1.

Film casting process [0116] A five-layer film with A / B / C / B / A structure (Figure 4) is extruded on a 5-layer Collins 5-Layer Cast Line. The total thickness of the film is 150 [mu] m, where A is the epidermal layer

EP 2 895 328 (40 μm), B is the intermediate layer (10 μm) and C is the barrier layer (50 μm). UBE 5033B polyamide is used as the barrier layer, and Dow PP R7051-10N (10 MFR) is used as the epidermal layer. The line has 5 extruders. Extruders 1 and 5 are used for the skin layers, extruders 2 and 4 are used for the intermediate layers, and the extruder 3 for the barrier layer. Temperature profiles in extruders are shown in Table 6.

Table 6. Conditions in extruders for poured film

<td>extruders</td><td>zone</td><td colspan="2">Temperature (° C)</td>

<td rowspan="5"># 1 and # 5 (for the PP layer)</td><td>Zone 01</td><td>set</td><td>180</td>

<td>Zone 02</td><td>set</td><td>225</td>

<td>Area 03</td><td>set</td><td>235</td>

<td>Zone 04</td><td>set</td><td>240</td>

<td>Stop-T</td><td>The actual</td><td>228</td>

<td rowspan="6"># 2 and # 4 (for the intermediate layer)</td><td>Zone 01</td><td>set</td><td>180</td>

<td>Zone 02</td><td>set</td><td>225</td>

<td>Area 03</td><td>set</td><td>235</td>

<td>Zone 04</td><td>set</td><td>240</td>

<td>Area 05</td><td>set</td><td>240</td>

<td>Stop-T</td><td>The actual</td><td>227</td>

<td rowspan="6"># 3 (for the polyamide layer)</td><td>Zone 01</td><td>set</td><td>210</td>

<td>Zone 02</td><td>set</td><td>240</td>

<td>Area 03</td><td>set</td><td>250</td>

<td>Zone 04</td><td>set</td><td>250</td>

<td>Area 05</td><td>set</td><td>250</td>

<td>Stop-T</td><td>The actual</td><td>243</td>

[0117] Formulations for intermediate layers used for the cast film are shown in Table 6. Ex. A1 and Prz.1-5 contain a polyolefin plastomer represented by AFFINITY PL 1850. In these examples, a constant load of MAH-g-HDPE (MAHPECONC1) is maintained. Before the process in autoclave Prz. A1 and Prz. 1-5 show excellent interlayer adhesion in the range of 13 to 15 N / 15mn. After the autoclave process, however, adhesion for Prz. A1 has become weak. The addition of 20% CBC1 (Prov 1) to the intermediate layer formulation significantly improves the adhesion of the autoclave. In Prz. 2-5 the amount of CBC2 is increased from 20% to 50%. The adhesion value increases when the concentration of CBC2 increases. When the concentration of CBC2 in the intermediate layer formulation varies between 40% (Prov 4) and 50% (Prov 5), the value of the adhesion after autoclave is comparedinto the intermediate layer based on polypropylene (Prov. B). Paragraphs 4 and 5 show a good smoothness of the film after the autoclave.

[0118] In Prov. 6 in addition to CBC2, 25% polypropylene is added. After the autoclave the adhesion value between the layered 6.1 N / 15mm is obtained. In Prz. 7 and 8 n, the polyolefin plastomer represented by AFFINITY PL1850 is replaced with HDPE KS10100. With the addition of 40% CBC2 in Prz. 8, an excellent adhesion value of 9.4 N / 15mm is obtained after the autoclave. Prov. 8 shows a good smoothness of the film after the autoclave.

[0119] Comparative examples (A2 and A3) based on the INFUSE OBC formulation show good adhesion before and after the autoclave; however, the foil has significant wrinkles due to shrinkage after the autoclave. Prov. A3 has a high haze after the autoclave as a result of melting and recrystallization during the autoclave process.

[0120] As for haze, Prov. 5 is better than Prz. B, while Prz. 8 is comparable to Prz. B.

EP 2 895 328

Table 7. Results of interlayer adhesion and haze for cast film (The skin layer is

PP R7051-10N, and the core layer is UBE 5033B polyamide

<td rowspan="2">Example</td><td colspan="7">Formulations for an intermediate layer</td><td colspan="2">Adhesion (N / 15 nun)</td><td colspan="2">Haze (%)</td>

<td>hPP H357-09R (%)</td><td>MAHPEC-ONC1 (%)</td><td>σ'o WHAT ABOUT</td><td>CBC2 (%)</td><td>ABOUT about CM 00 ABOUT LU with LL LL &lt;</td><td>AFFINITY PL1850 (%)</td><td>σ'O ABOUT about ω LU 0_ Q X</td><td>In front of autoclave</td><td>After the autoclave</td><td>In front of autoclave</td><td>After the autoclave</td>

<td>A1</td><td></td><td>20</td><td></td><td>0</td><td></td><td>80</td><td></td><td>12.9</td><td>0.8</td><td>2.5</td><td>11.9</td>

<td>1</td><td></td><td>20</td><td>20</td><td></td><td></td><td>60</td><td></td><td>14.1</td><td>6.2</td><td>2.3</td><td>12.6</td>

<td>2</td><td></td><td>20</td><td></td><td>20</td><td></td><td>60</td><td></td><td>13.5</td><td>3.6</td><td>2.6</td><td>8.4</td>

<td>3</td><td></td><td>20</td><td></td><td>thirty</td><td></td><td>50</td><td></td><td>13.8</td><td>5.6</td><td>2.3</td><td>8.9</td>

<td>4</td><td></td><td>20</td><td></td><td>40</td><td></td><td>40</td><td></td><td>13.7</td><td>7.5</td><td>2.7</td><td>9.6</td>

<td>5</td><td></td><td>20</td><td></td><td>50</td><td></td><td>thirty</td><td></td><td>15.1</td><td>11.0</td><td>2.5</td><td>9.4</td>

<td>6</td><td>25</td><td>20</td><td></td><td>40</td><td></td><td>15</td><td></td><td>4.1</td><td>6.1</td><td>2.7</td><td>13.1</td>

<td>7</td><td></td><td>20</td><td></td><td>20</td><td>20</td><td></td><td>40</td><td>13.2</td><td>1.2</td><td>3.9</td><td>14.7</td>

<td>8</td><td></td><td>20</td><td></td><td>40</td><td>20</td><td></td><td>20</td><td>14.0</td><td>9.4</td><td>3.4</td><td>13.9</td>

<td>A2</td><td colspan="7">80% INFUSE OBC 9500 + 20% MAH-g -INFUSE</td><td>10.0</td><td>6.1</td><td>5.2</td><td>16.0</td>

<td>A3 *</td><td colspan="7">80% INFUSE OBC 9500 + 20% MAHPECONC1</td><td>10.1</td><td>7.8</td><td>12.3</td><td>47.1</td>

<td>B</td><td colspan="7">ADMER QF 551</td><td>14.2</td><td>9.6</td><td>3.3</td><td>13.8</td>

The epidermal layer is PP R35208-R, 8 MFR random copolymer

Examples of blown film

Preparation of the formulation onto the layer by mixing [0121] The blends for the intermediate layer formulation used for the blown film tests are blended in a Coperion ZSK 26 twin screw extruder. The screw diameter is 25.5 mm with a channel depth of 4.55 mm. A feed rate of 22.7 kg / h is used. (50 pounds / hour) and screw speed 500 rpm. The drum length is 100 mm for 15 drums covering the entire process section. In the extrusion process, the following temperatures are set: zones 1-2 are heated to 140 ° C, and other zones and nozzles are heated to 190 ° C. The mixed material was extruded through two nozzles with a hole to a 4.9-meter (16 feet) cold water bath. The bands were then passed through a Berlyn Air Knife air knife to remove excess water. When the bands have been cooled and dried they are granulated in a Lab Tech granulator.

Table 8. Formulation for an intermediate layer for blown film

<td>glue d</td><td>MAHPECON C1</td><td>MAHPECON C2</td><td>MAHPPCON C</td><td>CBC 3</td><td>Engage E 8150</td><td>ELIT E 5100 G</td><td>ELITE 5940GB22 5</td><td>B22 5</td>

<td>9, 14</td><td>20</td><td>0</td><td>0</td><td>50</td><td>20</td><td>0</td><td>10</td><td>0.2</td>

<td>10</td><td>20</td><td>0</td><td>0</td><td>50</td><td>20</td><td>10</td><td>0</td><td>0.2</td>

<td>11.15</td><td>20</td><td>0</td><td>0</td><td>60</td><td>20</td><td>0</td><td>0</td><td>0.2</td>

<td>12</td><td>0</td><td>12</td><td>0</td><td>60</td><td>20</td><td>0</td><td>8</td><td>0.2</td>

<td>13</td><td>0</td><td>0</td><td>20</td><td>60</td><td>20</td><td>0</td><td>0</td><td>0.2</td>

<td>16</td><td>20</td><td>0</td><td>0</td><td>80</td><td>0</td><td>0</td><td>0</td><td>0.2</td>

Blow molding process on the Lab Tech blow line. [0122] Five-layer AB / CB / A films are blown on the Lab Tech 5-Layer Blown Film Line. The diameter of the extruder nozzle is 75 mm, and the slot is 2 mm. Blow-up ratio (BUR) is 2.7, and the width of the flattened film is 32.3 cm (12.7 inches). Receiving speed (nip

EP 2 895 328 speed) is 4.1 m / min (13.5 ft / min). The total thickness of the film is 100 μm, where A is the skin layer, B is the intermediate layer and C is the barrier layer. Dow PP 6D83K is used as the epidermal layer. Both polyamide and EVOH are used as a barrier layer. When the Ultramid ™ C33L01 polyamide is used as the barrier layer, the sandwich structure is AB / CB / A (30/10/20/10/30 μm).

When EVOH EVAL ™ H171B is used as the barrier layer, the sandwich structure is AB / CB / A (35/10/10/10/35 μm). The line has 5 extruders. Extruders 1 and 5 are used for the skin layers, extruders 2 and 4 are used for the intermediate layers, and the extruder 3 for the barrier layer. Temperature profiles in extruders are shown in Table 9 for samples with polyamide as a barrier layer. Temperature profiles in extruders are shown in Table 10 for EVOH samples as a barrier layer.

Table 9. Conditions in the extruder for the Lab Tech film blowing line for samples with a polyamide film

<td>extruders</td><td>zone</td><td>Temperature</td><td>((° F))</td><td>(° C)</td>

<td rowspan="5">Extruders 1 and 5: PP (6D83K)</td><td>Zone 01</td><td>set</td><td>(400)</td><td>204</td>

<td>Zone 02</td><td>set</td><td>(425)</td><td>218</td>

<td>Area 03</td><td>set</td><td>(385)</td><td>196</td>

<td>Zone 04</td><td>set</td><td>(385)</td><td>196</td>

<td>Nozzle</td><td>set</td><td>(430)</td><td>221</td>

<td rowspan="4">Extruders 2 and 4: Indirect</td><td>Zone 01</td><td>set</td><td>(375)</td><td>191</td>

<td>Zone 02</td><td>set</td><td>(400)</td><td>204</td>

<td>Area 03</td><td>set</td><td>(385)</td><td>196</td>

<td>Nozzle</td><td>set</td><td>(430)</td><td>221</td>

<td rowspan="4">Extruder 3: Polyamide (Ultramid ™ C33L01 or Polyamide UBE 5033B)</td><td>Zone 01</td><td>set</td><td>(400)</td><td>204</td>

<td>Zone 02</td><td>set</td><td>(450)</td><td>232</td>

<td>Area 03</td><td>set</td><td>(450)</td><td>232</td>

<td>Nozzle</td><td>set</td><td>(450)</td><td>232</td>

Table 10. Conditions in the extruder for the Lab Tech film blow molding line for samples with an EVOH layer

<td>extruders</td><td>zone</td><td>Temperature</td><td>((° F))</td><td>(° C)</td>

<td rowspan="5">Extruders 1 and 5: PP (6D83K)</td><td>Zone 01</td><td>set</td><td>(400)</td><td>204</td>

<td>Zone 02</td><td>set</td><td>(425)</td><td>218</td>

<td>Area 03</td><td>set</td><td>(385)</td><td>196</td>

<td>Zone 04</td><td>set</td><td>(385)</td><td>196</td>

<td>Nozzle</td><td>set</td><td>(430)</td><td>221</td>

<td rowspan="4">Extruders 2 and 4: Indirect</td><td>Zone 01</td><td>set</td><td>(375)</td><td>191</td>

<td>Zone 02</td><td>set</td><td>(400)</td><td>204</td>

<td>Area 03</td><td>set</td><td>(385)</td><td>196</td>

<td>Nozzle</td><td>set</td><td>(430)</td><td>221</td>

<td rowspan="4">Extruder 3: EVOH (EVAL ™ H171B)</td><td>Zone 01</td><td>set</td><td>(330)</td><td>166</td>

<td>Zone 02</td><td>set</td><td>(400)</td><td>204</td>

<td>Area 03</td><td>set</td><td>(400)</td><td>204</td>

<td>Nozzle</td><td>set</td><td>(430)</td><td>221</td>

[0123] The adhesion and haze results of the polyamide containing blown film structures are shown in Table 11. Prior to autoclaving process Prz.9 to 13 exhibit excellent adhesion both before and after the autoclave compared to the PP-based intermediate layers (Provide C and D). It should be noted that in Prz. 9-11 uses MAH-g-HDPE (MAHPECONC1) as MAH-grafted polyolefin in Prz.

MAH-g-HDPE (MAHPECONC2) is used as the MAH-grafted polyolefin, whereas in Prz. 13 uses MAH-g-PP (MAHPPCONC) as the MAH-grafted polyolefin. Prov. 16 contains only MAH-g-HDPE (MAHPECONC1) and CBC 3 and does not contain an elastomer. Regarding the haze, Prov. 9-13 have a value of 6 to 8% before the autoclave and 13 to 15% after the autoclave. Prov. 9-13 also show a good smoothness of the film after the autoclave.

EP 2 895 328

Table 11. Results of interlayer adhesion and haze for the intermediate layer for blown films made on the Lab Tech line (The barrier layer is C33L01 polyamide)

<td rowspan="2">At -Quad</td><td colspan="7">Formulations for an intermediate layer</td><td colspan="2">Adhesion (N / 15 mm)</td><td colspan="2">Haze (%)</td>

<td>MAHPE CO NC1</td><td>MAHPEC About NC2</td><td>MAHPP CO NC</td><td>CB C3</td><td>ENGAGE 8150</td><td>ELITE 5100G</td><td>ELITE0 5940G</td><td>In front of autoclave</td><td>After autoclave</td><td>In front of autoclave</td><td>After autoclave</td>

<td>9</td><td>20</td><td>0</td><td>0</td><td>50</td><td>20</td><td>0</td><td>10</td><td>11.1</td><td>10, 5</td><td>8.3</td><td>14, 8</td>

<td>10</td><td>20</td><td>0</td><td>0</td><td>50</td><td>20</td><td>10</td><td>0</td><td>10.9</td><td>9.4</td><td>7.9</td><td>13, 8</td>

<td>11</td><td>20</td><td>0</td><td>0</td><td>60</td><td>20</td><td>0</td><td>0</td><td>12.6</td><td>10, 1</td><td>8.3</td><td>14, 7</td>

<td>12</td><td>0</td><td>12</td><td>0</td><td>60</td><td>20</td><td>0</td><td>8</td><td>10.3</td><td>11.4</td><td>6.9</td><td>13, 9</td>

<td>13</td><td>0</td><td>0</td><td>20</td><td>60</td><td>20</td><td>0</td><td>0</td><td>12.2</td><td>9.3</td><td>5.8</td><td>13, 7</td>

<td>* 16</td><td>20</td><td>0</td><td>0</td><td>80</td><td>0</td><td>0</td><td>0</td><td>6.1</td><td>5.1</td><td>6.7</td><td>13, 1</td>

<td>C</td><td colspan="7">TY2451</td><td>7.9</td><td>6.9</td><td>10.2</td><td>15.0</td>

<td>D *</td><td colspan="7">PPTIE1</td><td>7.9</td><td>6.1</td><td>6.9</td><td>13, 1</td>

<td>In Prz</td><td colspan="5">16 and D is a UBE 5033B polyamide barrier layer.</td><td></td><td></td><td></td><td colspan="3"></td>

[0124] The adhesion and haze results of the EVOH ™ blown film structures (EVAL ™ H171B) are shown in Table 12. Ex. 14 and 15 show excellent adhesion both before and after the autoclave compared to the PP-based intermediate layer (fore).

Table 12. Results of interlayer adhesion and haze for the intermediate layer for blown films made on the Lab Tech line (The barrier layer is EVOH EVAL ™ H171B)

<td rowspan="2">pr with.</td><td colspan="7">Formulations for an intermediate layer</td><td colspan="2">Adhesion (N / 15 mm)</td>

<td>MAHPEC ONC 1</td><td>MAHPECO NC 2</td><td>MAHPPC ON C</td><td>CBC 3</td><td>Enga GE 8150</td><td>ELIT E 5100 G</td><td>ELIT E 5940 G</td><td>In front of autoclave m</td><td>After autoclave e</td>

<td>14</td><td>20</td><td>0</td><td>0</td><td>50</td><td>20</td><td>0</td><td>10</td><td>8.7</td><td>10.6</td>

<td>15</td><td>20</td><td>0</td><td>0</td><td>60</td><td>20</td><td>0</td><td>0</td><td>5.2</td><td>8.3</td>

<td>E</td><td colspan="7">TY2451</td><td>2.7</td><td>2.5</td>

Blown film process on an Alpine blowing line [0125] Five-layer A / B / C / B / D film films are blown on a 7-layer Alpine 7-Layer Blown Film Line. Layer A is a weldable layer, B is an intermediate layer, C is a barrier layer and D is an epidermal layer. PP 6D83K is used as a weldable layer A. Both polyamide (Ultramid ™ C40LN07) and EVOH (EVAL ™ F171B) are used as the barrier layer C. PP H110-02N is used as the skin layer D. The nozzle diameter is 250 mm and the gap nozzle 2 mm. The nozzle capacity is 202.7 kg / m (11.35 pounds per inch) of the nozzle circumference. The blow-up ratio (BUR) is 2.5, and the draw down ratio is 7.86. Films with a total thickness of 100 μm and 50 μm were produced. The reception speed is 14.2 m / min (46, 5 ft / min) for 100 um thick films, while the pickup rate is 28.3 m / min (93.0 ft / min) for 50 um thick films. When polyamide C40LN07 is used as the barrier layer, the layered structure is as follows: A / B / C / B / D (34/6/20/6/34%). When EVOH F171B is used as the barrier layer, the layered structure is as follows: A / B / C / B / D (39/6/10/6/39%). The line has 7 extruders. The extruders 1 and 2 are applied to the heat-sealable layer A, the extruders 3 and 5 are applied to the intermediate layer B, the extruder 5 to the barrier layer, and the extruders 6 and 7 are applied to the skin layer D. The temperature profiles in the extruders are shown in Table 13 for samples with polyamide as a barrier layer. Temperature profiles in extruders are shown in Table 13 for samples with polyamide as a barrier layer.

EP 2 895 328

Table 13. Conditions in the extruder for the Lab Tech film blowing line for samples with a polyamide film

<td>extruders</td><td>zone</td><td>Temperature</td><td>((° F))</td><td>(° C)</td>

<td rowspan="3">Extruders 1 and 2: RCP (6D83K)</td><td>Zone 1</td><td>set</td><td>(150)</td><td>66</td>

<td>Area 25</td><td>set</td><td>(400)</td><td>204</td>

<td>Area 68</td><td>set</td><td>(450)</td><td>232</td>

<td rowspan="3">Extruders 3 and 5: Indirect</td><td>Zone 1</td><td>set</td><td>(70)</td><td>21</td>

<td>Area 25</td><td>set</td><td>(380)</td><td>193</td>

<td>Area 67</td><td>set</td><td>(450)</td><td>232</td>

<td rowspan="3">Extruder 4: Polyamide (Ultramid ™ C40LN07)</td><td>Zone 1</td><td>set</td><td>(350)</td><td>177</td>

<td>Area 25</td><td>set</td><td>(425)</td><td>218</td>

<td>Area 68</td><td>set</td><td>(450)</td><td>232</td>

<td rowspan="3">Extruders 6 and 7: PP (H110)</td><td>Zone 1</td><td>set</td><td>(350)</td><td>177</td>

<td>Area 25</td><td>set</td><td>(400)</td><td>204</td>

<td>Area 68</td><td>set</td><td>(450)</td><td>232</td>

<td>Nozzle</td><td colspan="2">set</td><td>(450)</td><td>232</td>

Table 14. Conditions in the extruder for Lab Tech Blow Blowing Line for samples with EVOH layer

<td>extruders</td><td>zone</td><td>Temperature</td><td>((° F))</td><td>(° C)</td>

<td rowspan="3">Extruders 1 and 2: RCP (6D83K)</td><td>Zone 1</td><td>set</td><td>(150)</td><td>66</td>

<td>Zone 2-5</td><td>set</td><td>(400)</td><td>204</td>

<td>Zone 6-8</td><td>set</td><td>(450)</td><td>232</td>

<td rowspan="3">Extruders 3 and 5: Indirect</td><td>Zone 1</td><td>set</td><td>(70)</td><td>21</td>

<td>Zone 2-5</td><td>set</td><td>(380)</td><td>193</td>

<td>Zone 6-7</td><td>set</td><td>(450)</td><td>232</td>

<td rowspan="4">Extruder 4: EVOH (EVAL ™ F171B)</td><td>Zone 1</td><td>set</td><td>(315)</td><td>157</td>

<td>Zone 2-3</td><td>set</td><td>(415)</td><td>213</td>

<td>Zone 4-5</td><td>set</td><td>(420)</td><td>216</td>

<td>Zone 6-8</td><td>set</td><td>(450)</td><td>232</td>

<td rowspan="3">Extruders 6 and 7: PP (H110)</td><td>Zone 1</td><td>set</td><td>(350)</td><td>177</td>

<td>Zone 2-5</td><td>set</td><td>(400)</td><td>204</td>

<td>Zone 6-8</td><td>set</td><td>(450)</td><td>232</td>

<td>Nozzle</td><td colspan="2">set</td><td>(450)</td><td>232</td>

[0126] The test results for a 100 um thick film containing a polyamide layer produced on an Alpine film blowing line are shown in Table 15. The standard deviation in the adhesion test is given in brackets. Prov. 16 to 18 show comparable adhesion strength both before and after the autoclave compared to intermediate layers based on PP (Prov. F, G and H). Also haze in Prz. 1619 is similar to comparative examples. Prov. 9-13 also show a good smoothness of the film after the autoclave. [0127] Optical microscopy is performed to identify the interlaminar delamination. As shown in Figure 5, a test of the optical cross-section of the tear-off structure being tested indicates that the destruction takes place in the same place for Prov. 16, 18 and H.

EP 2 895 328

Table 15. Results of interlayer adhesion and haze for the intermediate layer for 100 μm films produced on the Alpine film roll line (The barrier layer is C40LN07 polyamide)

<td rowspan="2">glue d</td><td rowspan="2">MAHP ECON C1</td><td rowspan="2">MAHP ECON C2</td><td rowspan="2">CBC 3</td><td rowspan="2">Engage E 8150</td><td rowspan="2">ELITE 5940G</td><td colspan="2">Dia. adhesion (N / 5nmm)</td><td colspan="2">Dia. adhesion J%)</td>

<td>In front of autoclave m</td><td>After autokla know</td><td>In front of autoclave m</td><td>After autoclave</td>

<td>16</td><td>20</td><td></td><td>50</td><td>20</td><td>10</td><td>7.6 (2.1)</td><td>9.1 (0.6)</td><td>16.5</td><td>18.0</td>

<td>17</td><td>20</td><td></td><td>60</td><td>20</td><td></td><td>9.1 (0.1)</td><td>8.6 (0.2)</td><td>16.6</td><td>17.6</td>

<td>18</td><td></td><td>12</td><td>60</td><td>20</td><td>8</td><td>8.5 (0.2)</td><td>13.0 (0.6)</td><td>16.4</td><td>17.6</td>

<td>F</td><td colspan="5">YOU 2551</td><td>9.5 (0.5)</td><td>9.8 (0.4)</td><td>19.2</td><td>21.7</td>

<td>G</td><td colspan="5">PPTIE1</td><td>9.7 (2.0)</td><td>9.0 (0.3)</td><td>16.2</td><td>17.6</td>

<td>H</td><td colspan="5">Admer QF551</td><td>8.3 (0.6)</td><td>8.4 (0.2)</td><td>16.8</td><td>18.6</td>

[0128] The test results for a 100 um thick film containing a um layer comprising an EVOH (EVAL ™ F171B) film formed on the Alpine film blowing line are shown in Table 16. The standard deviation in the adhesion test is given in brackets. Prov. 19 to 21 have stronger adhesion both before and after the autoclave than the intermediate layer based on PP (Prov 1 to K).

Table 16. Results of interlayer adhesion and haze for the intermediate layer for blown films made on the Alpine line (The barrier layer is EVOH EVAL ™ H171B)

<td rowspan="2">glue d</td><td rowspan="2">MAHP ECON 1</td><td rowspan="2">MAHP ECON 2</td><td rowspan="2">CBC 3</td><td rowspan="2">Engage E 8150</td><td rowspan="2">ELITE 5940G</td><td colspan="2">Dia. adhesion (N / 15mm)</td><td colspan="2">Dia. adhesion J%)</td>

<td>In front of autoclave m</td><td>After autoclave e</td><td>In front of autoclave m</td><td>After autoclave e</td>

<td>19</td><td>20</td><td></td><td>50</td><td>20</td><td>10</td><td>9.1 (0.3)</td><td>9.8 (0.7)</td><td>18.5</td><td>19.4</td>

<td>20</td><td>20</td><td></td><td>60</td><td>20</td><td></td><td>9.1 (0.3)</td><td>9.7 (0.3)</td><td>17.5</td><td>18.1</td>

<td>21</td><td></td><td>12</td><td>60</td><td>20</td><td>8</td><td>9.1 (0.6)</td><td>9.2 (0.3)</td><td>16.4</td><td>18.4</td>

<td>AND</td><td colspan="5">YOU 2551</td><td>5.6 (0.2)</td><td>5.1 (0.1)</td><td>20.1</td><td>20.1</td>

<td>J</td><td colspan="5">PPTIE1</td><td>6.4 (0.4)</td><td>5.6 (0.1)</td><td>17.2</td><td>16.7</td>

<td>K</td><td colspan="5">Admer QF551</td><td>8.1 (0.5)</td><td>7.3 (0.1)</td><td>17.1</td><td>18.6</td>

Blown film on Lab Tech line with PE-based structure [0129] An attempt for an intermediate polyethylene / polyamide was carried out to check whether the invention could be used as an intermediate polyethylene / polyamide. Similar five-layer films with the structure A / B / C / B / A were blown on the stretch line of 5-layer Lab Tech films. The diameter of the extruder nozzle is 75 mm and the nozzle gap is 2 mm. The blown ratio (BUR) is 2.5, and the width of the flattened film is 0.30 meters (11.6 inches). The reception speed is 4.4 m / min (14.5 ft / min). The total thickness of the film is 100 μm, where A is the epidermal layer, B the intermediate layer and C the barrier layer. DOWLEX 2045G was used as the skin layers. Ultramid ™ C33L01 polyamide was used as the barrier layer. The layered structure was followed by A / B / C / B / A (30/10/20/10/30 um). The line has 5 extruders. Extruders 1 and 5 are used for the skin layers, extruders 2 and 4 are used for intermediate layers, and extruder 3 for barrier layers. Temperature profiles in extruders are shown in Table 17.

EP 2 895 328

Table 17. Conditions in the extruder for the Lab Tech film blowing line for polyethylene / polyamide structures

<td>extruders</td><td>zone</td><td>Temperature</td><td>((° F))</td><td>(° C)</td>

<td rowspan="5">Extruders 1 and 5: DOWLEX 2045G</td><td>Zone 01</td><td>set</td><td>(375)</td><td>190</td>

<td>Zone 02</td><td>set</td><td>(420)</td><td>215</td>

<td>Area 03</td><td>set</td><td>(375)</td><td>190</td>

<td>Zone 04</td><td>set</td><td>(375)</td><td>190</td>

<td>Nozzle</td><td>set</td><td>(430)</td><td>221</td>

<td rowspan="4">Extruders 2 and 4: Indirect</td><td>Zone 01</td><td>set</td><td>(375)</td><td>190</td>

<td>Zone 02</td><td>set</td><td>(400</td><td>204</td>

<td>Area 03</td><td>set</td><td>(390)</td><td>199</td>

<td>Nozzle</td><td>set</td><td>(420)</td><td>215</td>

<td rowspan="4">Extruders 3: Polyamide (Ultramid ™ C33L01)</td><td>Zone 01</td><td>set</td><td>(400)</td><td>204</td>

<td>Zone 02</td><td>set</td><td>(450)</td><td>232</td>

<td>Area 03</td><td>set</td><td>(450)</td><td>232</td>

<td>Nozzle</td><td>set</td><td>(450)</td><td>232</td>

[0130] Intermediate layers according to the invention, PP-based intermediate layers and PE-based intermediate layers are compared in Table 18. For intermediate layers PE / polyamide the minimum acceptable level of adhesion for 101.6 μm film (4 mils) is above ~ 7 N / 15mm. . As can be seen in Table 18, intermediate layers based on PP, Ex. L and M, do not meet the requirements for adhesion, while Prov. 22 and 23 according to the invention and commercial PE-based intermediate layers (Prov. N and O) meet the requirement for adhesion.

[0131] A comparison of lesions in the peel test revealed a difference at the delamination site, Figure 6. The destruction of the connection between the intermediate layer and the polyamide layer occurred for formulations made with the intermediate layer 23 of the invention, Figure 6a. The same delamination site was observed for an AMPLIFY TY 1353 based PE layer (Prov. N), Figure 6c. However, for an intermediate layer based on PP, Prz. L, the destruction of the connection occurred between the outer layer of DOWLEX 2045G and the intermediate layer based on PP, Figure 19b. Poor compatibility between PP and PE caused the division boundary intermediate / DOWLEX 2045G with poor bonding and spot destruction.

Table 18. Results for blown films containing DOWLEX 2045G as the epidermal layer

<td>Category</td><td>Prov s.</td><td>MAHP ECON C1</td><td>CBC 3</td><td>Engage E 8150</td><td>ELITE 5940G</td><td>Adhesion (N / 15 mm)</td><td>Haze (%)</td>

<td rowspan="2">An intermediate layer according to the invention</td><td>22</td><td>20</td><td>50</td><td>20</td><td>10</td><td>7.5</td><td>12.3</td>

<td>23</td><td>20</td><td>60</td><td>20</td><td>0</td><td>7.1</td><td>12.6</td>

<td rowspan="2">An intermediate layer based on PP</td><td>L</td><td colspan="4">ADMER QF 551</td><td>5.7</td><td>12.4</td>

<td>M</td><td colspan="4">AMPLIFY TY 2551</td><td>5.3</td><td>13.8</td>

<td rowspan="2">An intermediate layer based on the EP</td><td>N</td><td colspan="4">AMPLIFY TY 1353</td><td>7.8</td><td>14.7</td>

<td>ABOUT</td><td colspan="4">AMPLIFY TY 1228B</td><td>8.9</td><td>13.8</td>

Examples of thermoforming [0132] A thermoforming test was carried out to check whether the invention could be used as an intermediate layer for thermoforming applications. Seven-layer films with AB / C / D / CB / E structure were blown on the 7-layer Alpine 7-Layer Blown Film Line. Layer A is a weldable layer (RCP 6D83K), B is an intermediate layer, C is a polyamide (Ultramid ™ B36 01), D is EVOH (EVAL ™ LR171B) and E is PP H110-02N. The layered structure is as follows: A / B / C / D / CB / E (22.5% / 7.5% / 12.5% ​​/ 15.0% / 12.5% ​​/ 7.5% / 22.5 %). The film thickness is 152 μm (6 mils). The total processing is 192.8 kg / hour. (425 pounds / hour). The diameter of the extruder nozzle is 250 mm and the nozzle gap is 2 mm. The nozzle capacity is 244.7 kg / m (13.7 lb. in) of the nozzle circumference. The degree of blow (BUR) is 2.5, and the loss factor is 5.24. Films with a total thickness of 152.4 were produced

EP 2 895 328 μm (6 mils). The reception speed is 10.9 m / min (35.9 ft / min). The line has 7 extruders. Extruder 1 is applied to heat sealable layer A, extruders 2 and 6 are used for intermediate layers B, extruder 3 and 5 for layer C, extruder 4 for layer D, and extruder 7 for layer E. Temperature profiles in extruders are shown in Table 19 .

Table 19. Conditions in the extruder for _ the Alpine film blown line for the thermoforming mold

<td>extruders</td><td>zone</td><td>Temperature</td><td>((° F))</td><td>(° C)</td>

<td rowspan="3">Extruders 1 and 7</td><td>Zone 1</td><td>set</td><td>(70)</td><td>21</td>

<td>Zone 2-5</td><td>set</td><td>(380)</td><td>193</td>

<td>Zone 6-8</td><td>set</td><td>(450)</td><td>232</td>

<td rowspan="3">Extruders 2 and 6</td><td>Zone 1</td><td>set</td><td>(70)</td><td>21</td>

<td>Zone 2-5</td><td>set</td><td>(350)</td><td>177</td>

<td>Zone 6-7</td><td>set</td><td>(400)</td><td>204</td>

<td rowspan="2">Extruders 3 and 5</td><td>Zone 1</td><td>set</td><td>(420)</td><td>216</td>

<td>Zone 2-8</td><td>set</td><td>(500)</td><td>260</td>

<td rowspan="3">Extruder 4</td><td>Zone e 1</td><td>set</td><td>(400</td><td>204</td>

<td>Zone 2-5</td><td>set</td><td>(450)</td><td>232</td>

<td>Zone 6-8</td><td>set</td><td>(460)</td><td>238</td>

<td>Nozzle</td><td colspan="2">set</td><td>(500)</td><td>260</td>

[0133] The blown films were then thermoformed on a Multivac R530 thermoforming machine. The thermoforming depth was 63.5 mm. The nozzle temperature was 135 ° C, with a 7-second break for heating and 5-sec. break for forming. After stretching, a cup of 18 (length) X 12 (width) X 6 (depth) cm was made. The backsheet in the cup produced has a thickness of 25.4 μm (1.0 mils). The adhesion and heat-seal test is carried out on a film taken from the bottom of the cup produced.

[0134] After thermoforming, the intermediate layer of the invention, Prov. 24, has a value of adhesion 2.4 N / 15mm in front of the autoclave, which is comparable with an intermediate layer based on PP, Ex. P, (2.9 N / 15mm).

After autoclave Prz. 24 shows significantly higher adhesion than the comparative example of P.

Table 20. Adhesion of films taken from the bottom of a thermoformed cup

<td>Category</td><td>Example</td><td>MAHPECONC1</td><td>CBC4</td><td>AFFINITY EG 8100</td><td>Irgano x B215</td><td>Attach in front of the autoclave</td><td>Adhesion to the autoclave (N / 15 mm)</td>

<td>indirect according invention</td><td>24</td><td>20</td><td>59.82</td><td>20</td><td>0.18</td><td>2.4</td><td>6.3</td>

<td>Intermediate based on PP</td><td>P</td><td colspan="4">AMPLIFY TY 2551</td><td>2.9</td><td>4.4</td>

[0135] The heat resistance of the thermoformed films taken from the bottom of the thermoformed cups is shown in Figure 7. Resistance of the weld in Ex. 24 is significantly higher than in the comparative example of P.