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    • 专利摘要:
    blown film grade showing superior rigidity, transparency and processing behavior. the present invention relates to blown extrusion film comprising a polypropylene composition, said polypropylene composition comprises a random propylene copolymer, a high melt strength polypropylene, a polypropylene and optionally a bleach, where the random propylene copolymer comprises units derived from propylene and at least one other c2-20 alpha olefin, high melt strength polypropylene has a g 'branch index of less than 1.0, polypropylene (b) has an mfr2 (230 ° c) of at least 400 g / 10 minutes, the bleach comprises at least one alpha nucleating agent, and yet where the ramification index g 'of the random polypropylene copolymer and the ramification index g' of the polypropylene are greater than the ramification index g ' of high melt strength polypropylene, the random propylene copolymer has a melt flow rate mfr2 (230 ºc) lower than polypropylene, the blown extrusion melt film melting and / or polypropylene composition (i) satisfies equation (i) tm - tc <30 (i) where tm is the melting temperature (ºc) constituting up to more than 50% of the total melting enthalpy hm of the blown film fusion of extrusion or polypropylene composition; tc is the crystallization temperature (ºc) of the extrusion melt blown film or polypropylene composition; and / or (ii) has a melt flow rate mfr2 (230 ºC) of 1.0 to 5.5 g / 10 minutes.
    公开号:BR112012015156B1
    申请号:R112012015156-8
    申请日:2010-12-15
    公开日:2020-05-12
    发明作者:Klaus Bernreitner；Niedersüss Klaus；Markus Gahleitner
    申请人:Borealis Ag；
    IPC主号:
    专利说明:

    Descriptive Report of the Invention Patent for FILTER EXTRUDED BY BLOW, AND PACKAGING MATERIAL.
    [0001] The present invention relates to new extruded blown films and their use.
    [0002] Polypropylenes succeed more and more to replace polyethylene in many technical fields when very often the new generation of polypropylene has improved properties compared to conventional polyethylene materials. This also applies to the field of blown extrusion films where polypropylene takes advantage of molecular engineering to overcome previous material disadvantages for blowing extruded film production. It is currently possible to manufacture blown extrusion films on polypropylene bases. For example, EP 1 842 872 A2 describes blown films based on a polypropylene containing nucleating agents. However, the mechanical properties can still be improved. Also the processing of such material is still unlikely.
    [0003] The extruded blow film process is very useful and efficient for the production of film (semi-finished state) that can be used for all different types of packaging. Compared to a molded film process, it is cheaper to invest, less energy consumption and also very flexible in handling. When processing polypropylene the main challenges with this process are transparency and processing. It is very difficult to obtain good transparency because the polymer melt is extruded into the air and blown from the inside until the required dimension is reached. Cooling is therefore done by air (molten film has contact with a so-called cooling roll: metal cooling surface) and at the same time a multiaxial orientation is imposed on the material (so-called stretch ratio). In order to have good processing behavior the material has to achieve a good stability of the bubble created
    Petition 870190132049, of 12/12/2019, p. 4/55
    2/43 immediately after exiting the die. To achieve good bubble stability, a certain level of resistance to melting is required. However, until now a good fusion resistance has been paid for with high levels of turbidity.
    [0004] In the same way the objective of the present invention is to provide a film extruded by blowing from a high speed conversion process with an excellent combination of rigidity, hardness and transparency.
    [0005] The verification of the present invention is that the extruded blow film comprises a polypropylene composition comprising a branched polypropylene, such as Y / H shaped polypropylene, that is, a polypropylene with high melt strength, and also a polypropylene with high melt flow rate.
    [0006] In the same way the present invention is directed in a first embodiment to a blow-extruded film comprising a polypropylene composition, said polypropylene composition comprises a random propylene copolymer (R-PP), polypropylene with high melt strength (HMS-PP), a polypropylene (B) and optionally a bleach (C), where (a) the random propylene copolymer (R-PP) comprises units derived from propylene and at least one other C2-20 alpha olefin.
    (b) optionally polypropylene with high melt strength (HMS-PP) has a g 'branching index of less than 1.0, preferably a g' branching index of 0.9 or less, (c) polypropylene (B ) has an MFR2 (230 o C) measured according to ISO 1133 of at least 400 g / 10 minutes, (d) the bleach (C) comprises at least one alpha nucleating agent (N), and where (i) the random propylene copolymer (R-PP) and the poly
    Petition 870190132049, of 12/12/2019, p. 5/55
    3/43 propylene (B) are (chemically) different from polypropylene with high melt strength (HMS-PP), preferably the ramification index g 'of the random propylene copolymer (R-PP) and the ramification index g' of polypropylene (B) are superior to the g 'branching index of high melt strength polypropylene (HMS-PP), (ii) the random propylene copolymer (R-PP) is (chemically) different from polypropylene (B), preferably the random propylene copolymer (R-PP) has a melt flow rate MFR2 (230 o C) measured according to ISO 1133 lower than polypropylene (B), (iii) the extruded film by a molten blow and / or the composition of polypropylene (α) satisfies equation (I)
    Tm - Tc <30 (I) where
    Tm is the melting temperature [ o C] constituting more than 50% of the total melting enthalpy Hm of the molten blow extruded film or the polypropylene composition measured by DSC according to ISO 11357-3;
    Tc is the crystallization temperature [ o C] of the blown film extruded film or of the polypropylene composition measured by DSC according to ISO 11357-3 and / or (β) has an MFR2 melting flow rate (230 o C) measured according to ISO 1133 from 1.0 to 5.5 g / 10 minutes.
    Preferably the blow-extruded film defined above and / or the polypropylene composition defined above has (a) a strain-hardening factor (SHF) of
    1.2 to 3.0 measured at a strain rate of 3.0 s -1 and a Hencky strain of 3.0, and / or (b) a gel content determined as the insoluble fraction in
    Petition 870190132049, of 12/12/2019, p. 6/55
    4/43 hot xylene (XHI) of 1.0% or less by weight.
    [0007] Alternatively the present invention is directed to a second embodiment of a blow-extruded film comprising a polypropylene composition, said polypropylene composition comprises a random propylene copolymer (R-PP), a polypropylene with high melt strength ( HMS-PP), a polypropylene (B) and optionally a bleach (C), where (a) the random propylene copolymer (R-PP) comprises units derived from propylene and at least one other C2-20 alpha olefin.
    (b) optionally polypropylene with high melt strength (HMS-PP) has a g 'branching index of less than 1.0, preferably a g' branching index of 0.9 or less, (c) polypropylene (B ) has an MFR2 (230 o C) measured according to ISO 1133 of at least 400 g / 10 minutes, (d) the bleach (C) comprises at least one alpha nucleating agent (N), and where (i) the random propylene copolymer (R-PP) and polypropylene (B) are (chemically) different to the polypropylene with high melt strength (HMS-PP), preferably the ramification index g 'of the random propylene copolymer (R- PP) and the branching index g 'of polypropylene (B) are higher than the branching index g' of polypropylene with high melt strength (HMS-PP), (ii) the random propylene copolymer (R-PP) is ( chemically) different from polypropylene (B), preferably the random propylene copolymer (R-PP) has MFR2 melt flow rate (230 o C) measured according to ISO 1133 lower than polypropylene (B), (iii) the film extruded by fused blow and / or the polypropylene composition has
    Petition 870190132049, of 12/12/2019, p. 7/55
    5/43 (a) a strain hardening factor (SHF) of 1.2 to 3.0 measured at a strain rate of 3.0 s -1 and a Hencky strain of 3.0, and / or (b ) a gel content determined as the insoluble fraction in hot xylene (XHI) of 1.0% or less by weight.
    [0008] Preferably, the blow-extruded film and / or the polypropylene composition of the second embodiment (a) satisfies equation (I)
    Tm - Tc <30 (I) where
    Tm is the melting temperature [ o C] constituting more than 50% of the total melting enthalpy Hm of the blown film extruded film or of the polypropylene composition measured by DSC according to ISO 11357-3;
    Tc is the crystallization temperature [ o C] of the extruded film by a molten blow or of the polypropylene composition measured by DSC according to ISO 11357-3 and / or (b) has a melt flow rate MFR2 (230 o C) measured according to ISO 1133 from 1.0 to 5.5 g / 10 minutes.
    [0009] Preferably the blow-extruded film comprises as a polymer composition only the polypropylene compositions as defined above (in the first and second modes). Thus, the blow-extruded film can still comprise additives, but not yet polymers such as those being part of the polypropylene composition. In addition, the polypropylene compositions as defined above (in the first and second embodiments) comprise in a preferred embodiment as polymer components only the random propylene copolymer (R-PP), the polypropylene (B) and the polypropylene with high melt strength (HMS -PP), as defined above and further details below. So also the film ex
    Petition 870190132049, of 12/12/2019, p. 8/55
    6/43 blown by final blowing comprises, in a preferred embodiment, only random propylene copolymer (R-PP), polypropylene (B) and high melt strength polypropylene (HMS-PP) as defined in the present invention as polymer components .
    [00010] It has been surprisingly found that such a blown film has superior properties compared to known blown extrusion films. The blow-extruded film of the present invention is characterized by exceptionally low turbidity values, good rigidity and good processing parameters (see Table 1).
    [00011] In what follows the present invention is described in more detail.
    [00012] An essential requirement of the inventive blow-extruded film is the specific correlation between melting temperature Tm and the crystallization temperature Tc of the blow-extruded film and / or the polypropylene composition being part of said film. In the same way, it is preferred that the blow-extruded film and / or the polypropylene composition being part of said film satisfies equation (I), more preferably equation (Ia), even more preferably equation (Ib)
    Tm -Tc < : 30 (I), Tm -Tc < 25 (Ia), Tm -Tc < 22 (Ib),
    on what
    Tm is the melting temperature [ o C] constituting more than 50% of the total melting enthalpy Hm of the blown film extruded film or of the polypropylene composition measured by DSC according to ISO 11357-3;
    Tc is the crystallization temperature [ o C] of the blown film extruded film or the polypropylene composition measured by
    Petition 870190132049, of 12/12/2019, p. 9/55
    7/43
    DSC according to ISO 11357-3.
    [00013] Additionally or alternatively the film extruded by blowing and / or the polypropylene composition being part of said film is characterized by a specific melt flow rate. The melt flow rate depends mainly on the average molecular weight. This is due to the fact that long molecules provide less material flow than short molecules. An increase in molecular weight means a decrease in the MFR value. The melt flow rate (MFR) is measured in g / 10 minutes of the polymer discharged through a set die under specified conditions of temperature and pressure and the viscosity measure of the polymer, which, in turn, for each type of polymer is influenced mainly by its molecular weight, but also by its degree of branching. The melt flow rate measured under a load of 2.16 kg at 230 ° C (ISO 1133) is represented as MFR2 (230 o C). Likewise, it is preferred that the inventive blow extruded film and / or the polypropylene composition being part of said film has an MFR2 (230 o C) of at least 0.5 g / 10 minutes, such as at least 1.0 g / 10 minutes, more preferably in the range of 1.5 to 5.5 g / 10 minutes, even more preferably in the range of 1.5 to 4.5 g / 10 minutes, even more preferably from 1.5 to 4, 0 g / 10 minutes, even more preferably 2.0 to 4.0 g / 10 minutes.
    [00014] Also, as established above, the new film extruded by blowing, that is, the polypropylene composition being part of said film, has to comprise a polypropylene with high melt strength (HMS-PP). Such types of polymers improve the melt strength of the polypropylene composition. In the same way, it is preferred that the blow-extruded film and / or the polypropylene composition being part of said film is further characterized by a deformation-hardening behavior. So it is appreciated that the fil
    Petition 870190132049, of 12/12/2019, p. 10/55
    8/43 m and extruded by blowing and / or the polypropylene composition being part of said film presents a strain hardening factor (SHF) of 1.2 to 3.0, more preferably of 1.4 to 2.8, still more preferably 1.5 to 2.7, measured at a strain rate of 3.0 s -1 and a Hencky strain of 3.0. The exact measurement process is defined in the example section.
    [00015] Still the blow-extruded film and / or the polypropylene composition being part of said film can be additionally defined by the gel content. The gel content is a good indicator for the chemical modification of the blown film, the composition of polypropylene or its components. In the same way, the film extruded by blowing and / or the polypropylene composition being part of said film is characterized by a relatively moderate gel content, that is, not more than 1.00%, by weight, even more preferred, no more than 0.80% by weight, even more preferred not greater than 0.50% by weight, determined as the relative amount of boiling xylene insoluble polymer (hot xylene insoluble fraction, XHI). On the other hand, the film extruded by blowing and / or the polypropylene composition being part of said film has to comprise a certain amount of polypropylene with high melt strength (HMS-PP). In the same way the amount of gel content in the blow-extruded film and / or in the polypropylene composition being part of said film is preferably more than 0.15% by weight, more preferably at least 0.27% by weight . Thus, a preferred range for the gel content of the blown film extruded and / or the polypropylene composition being part of said film is 0.05 to 0.90%, by weight, as 0.15 to 0.90%, by weight, more preferred 0.26 to 0.8%, by weight.
    [00016] It is further appreciated that the film extruded by blowing and / or the polypropylene composition being part of said film is free of any elastomeric component, such as ethylene propylene rubber.
    Petition 870190132049, of 12/12/2019, p. 11/55
    9/43
    In other words, the polypropylene composition being part of the blown extruded film should not be a heterophasic polypropylene composition, that is, a system consisting of a polypropylene matrix in which an elastomeric phase is dispersed. Such systems are characterized by a high soluble content in cold xylene. Of course, the blow-extruded film as a whole is also preferably free of a heterophasic polypropylene composition. Likewise, the blow-extruded film and / or the polypropylene composition being part of said film differs from such a heterophasic system by previously having a low soluble content in cold xylene (XCS). Therefore, the film extruded by blowing and / or the polypropylene composition being part of said film preferably presents a fraction soluble in cold xylene (XCS) not exceeding 15.0% by weight, more preferably not exceeding 14.0% by weight. weight, even more preferably not more than 12.0% by weight, as not more than 11.5% by weight.
    [00017] Also, the blow-extruded film and / or the polypropylene composition being part of said film can be specified by the number of comonomer units other than propylene within the blow-extruded film and the polypropylene composition being part of said film , respectively. In the same way it is appreciated that the amount of C2-20 alpha olefin derived units other than propylene is not more than 7.0% by weight, preferably not more than 6.0% by weight, as not more than 5 , 5%, by weight, in the blow-extruded film and / or the polypropylene composition being part of said film.
    [00018] In what follows, the present blow-extruded film is further defined by the polymer components within the polypropylene composition.
    [00019] The random propylene copolymer (R-PP) comprises units derived from propylene and at least one other C2-20 alpha
    Petition 870190132049, of 12/12/2019, p. 12/55
    10/43 olefin, preferably at least one other C2-10 alpha olefin. Similarly, the random propylene copolymer (R-PP) comprises units derived from propylene and at least one other alpha olefin selected from the group consisting of ethylene C4 alpha olefin, C5 alpha olefin, C6 alpha olefin, C7 alpha olefin, C7 alpha olefin, C9 alpha olefin and C10 alpha olefin. More preferably, the random propylene copolymer (R-PP) comprises propylene-derived units and at least one other alpha olefin selected from the group consisting of ethylene, 1butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1- nonene, and 1decene, where ethylene, 1-butene and 1-hexene are preferred. In particular, it is preferred that the random propylene copolymer (R-PP) consists of units derived from propylene and ethylene. The number of units derived from C2-20 alpha olefins other than propylene in the random propylene copolymer (R-PP) is in the range of 1.0 to 7.0% by weight, more preferably 1.5 to 6.0 % by weight, even more preferably 2.0 to 5.5% by weight.
    [00020] Preferably the random propylene copolymer (RPP) is isotactic. Likewise, it is appreciated that the random propylene copolymer (R-PP) has a high pentad concentration, that is, greater than 90 mol%, more preferably greater than 92 mol%, even more preferably greater than 93% mol and even more preferably greater than 95 mol%, as greater than 99 mol%.
    [00021] A requirement in the present invention is that units derived from C2-20 alpha olefins other than propylene within the propylene copolymer (R-PP) are randomly distributed. Randomness indicates the number of isolated comonomer units, that is, those that have no other comonomer units in the vicinity, compared to the total amount of comonomers in the polymer chain. In a preferred embodiment, the randomness of the copolymer
    Petition 870190132049, of 12/12/2019, p. 13/55
    11/43 random leno (R-PP) is at least 30%, more preferably at least 50%, even more preferably at least 60%, and even more preferably at least 65%.
    [00022] It is further appreciated that the soluble xylene content of the random propylene copolymer (R-PP) is rather low. Likewise, the random propylene copolymer (R-PP) preferably presents a fraction soluble in cold xylene (XCS) measured according to ISO 6427 (23 o C) not more than 14.0% by weight, more preferably not more than 13.0% by weight, even more preferably not more than 12.0% by weight, as not more than 11.5% by weight. Thus a preferred range is 1.0 to 14.0% by weight, more preferred 1.0 to 13.0% by weight, even more preferred 1.2 to 11.0% by weight.
    [00023] The random propylene copolymer (R-PP) can be unimodal or multimodal, as bimodal in view of the distribution of molecular weight and / or the distribution of comonomer content.
    [00024] When the random propylene copolymer (R-PP) is unimodal with respect to molecular weight distribution and / or comonomer content, it can be prepared in a single stage process, for example, as a gas phase process or paste in a gas phase reactor or paste. Preferably, the random, unimodal propylene copolymer (R-PP) is polymerized as a slurry polymerization. Alternatively, the unimodal random propylene copolymer (R-PP) can be produced in a multistage process using conditions that result in similar polymer properties at each process stage.
    [00025] The term multimodal or bimodal used here refers to the polymer modality, that is, the shape of its molecular weight distribution curve, which is the graph of the molecular weight fraction as a function of its molecular weight, or more preferably
    Petition 870190132049, of 12/12/2019, p. 14/55
    12/43 .the shape of its comonomer content distribution curve, which is the graph of the comonomer content as a function of the molecular weight of the polymer fractions.
    [00026] As will be explained below, the polymer components of the random propylene copolymer (R-PP) can be produced in a sequential step process, using reactors in series configuration and operating under different reaction conditions. As a consequence, each fraction prepared in a specific reactor will have its own molecular weight distribution and / or comonomer content distribution.
    [00027] When the distribution curves (molecular weight or comonomer content) from these fractions are superimposed to obtain the molecular weight distribution curve or the comonomer content distribution curve of the final polymer, these curves can show two or maximum or at least be distinctly amplified when compared to curves for individual fractions. Such a polymer, produced in two or more serial steps, is called bimodal or multimodal depending on the number of steps.
    [00028] In the same way, the random propylene copolymer (R-PP) can be multimodal, as bimodal, in view of the comonomer content and / or molecular weight. In particular it is appreciated that the random propylene copolymer (R-PP) is of multimodal character, as bimodal, in particular multimodal, as bimodal, in view of the comonomer content, it is appreciated that the individual fractions are present in quantities influencing the properties of material. Likewise, it is appreciated that each of these fractions is present at least in the amount of 10%, by weight, based on the random propylene copolymer (R-PP). Likewise, in the case of a bimodal system, particularly in view of the comonomer content, the division of the two fractions is roughly 50:50.
    Petition 870190132049, of 12/12/2019, p. 15/55
    13/43 [00029] Thus, in one embodiment, the random propylene copolymer (R-PP) comprises two fractions that differ in their comonomer content, such as ethylene content (preferably as the only comonomer in the random propylene copolymer (R-PP) )), where the first fraction is present from 40 to 60% by weight and the second fraction from 60 to 40% by weight. In such a case the random propylene copolymer (R-PP) comprises at least two fractions, more preferably it consists of two fractions, which have a comonomer content, such as ethylene content, which differ by at least 2.0%, in weight, more preferably they differ by at least 2.5% by weight. On the other hand, the difference in comonomer content in the two fractions should not be too high, that is, not greater than 6.0% by weight, preferably not greater than 5.0% by weight, to avoid any tendencies of separation. Thus it is appreciated that the random propylene copolymer (R-PP) comprises at least two fractions, more preferably consists of two fractions, which have comonomer contents that differ from 2.0 to 6.0% by weight, more preferably from 2.5 to 5.0% by weight. Likewise in one embodiment the random propylene copolymer (R-PP) consists of a first fraction being a propylene homopolymer and a second fraction being a random propylene copolymer having a comonomer content, preferably ethylene content, of at least 2.0% by weight, more preferably at least 3.0% by weight, as at least 3.5% by weight.
    [00030] As already apparent from words used in the present invention, the random propylene copolymer (R-PP) is not only (chemically) different from propylene (B), but also (chemically) different from polypropylene with high melt strength (HMS-PP). An essential difference is that the random propylene copolymer (R-PP) (compared to polypropylene with high melt strength
    Petition 870190132049, of 12/12/2019, p. 16/55
    14/43 (HMS-PP)) is unbranched. In other words, the random propylene copolymer (R-PP) preferably has a higher g 'branching index compared to the g' branching index of high melt strength polypropylene (HMS-PP), more preferably the g 'branching index of the random propylene copolymer (R-PP) is at least 0.95, such as 1.0. Still a distinguishing feature between the polypropylene with high melt strength (HMS-PP) and the random propylene copolymer (R-PP) is preferably the gel content expressed in the amount of the insoluble fraction in hot xylene (XHI). Likewise, the random propylene copolymer (R-PP) has a gel content below 0.15% by weight, more preferably it has no detectable gel content.
    [00031] Particularly suitable random propylene copolymers (R-PP) are those, for example, as described in EP 1 580 207 A1 and WO 2003/002639 A1.
    [00032] As stated above, the polypropylene composition being part of the inventive blow-extruded film comprises at least - as polymer components - a random propylene copolymer (R-PP), a polypropylene (B) and a polypropylene with high melt strength (HMS-PP). The three components must be chosen in such a way that inter alia the required MFR2 (230 o C) of at least 0.5 g / 10 minutes, such as at least 1.0 g / 10 minutes, for blown film and / or for the polypropylene composition to be satisfied. In principle, reducing the viscosity of feed (visbreaking) is an option to increase the melt flow rate of the polypropylene composition. However, although it has been found that reducing the feed viscosity of a polypropylene composition can improve the turbidity and brightness of blown extrusion films, it has now surprisingly been found that increasing the melt flow rate through
    Petition 870190132049, of 12/12/2019, p. 17/55
    15/43 incorporation of a viscous polypropylene, ie polypropylene (B), leads to much better properties. Without being bound by theory, it is believed that the addition of a polypropylene with a previously high melt flow rate to a mixture of non-reduced viscosity random propylene copolymer (R-PP) and a polypropylene with high melt strength (HMS-PP) leads to much better turbidity and gloss properties compared to low-viscosity polypropylene of random propylene copolymer (R-PP) and optionally polypropylene with high melt strength (HMS-PP), since polypropylene viscous can perfect the surface of the film extruded by blowing and with that the total transparency of the said film. Likewise, it is preferred that neither the polypropylene composition as a whole nor the random propylene copolymer (R-PP) have low viscosity feed. [00033] Likewise, it is appreciated that the random propylene copolymer (R-PP) has an MFR2 (230 o C) of at least 0.5 g / 10 minutes, more preferably in the range of 0.8 to 6, 0 g / 10 minutes, even more preferably from 1.2 to 4.5 g / 10 minutes, such as 1.5 to 4.0 g / 10 minutes.
    [00034] The preparation of the random propylene copolymer (R-PP) will be defined in more detail below.
    [00035] Still as an essential requirement of the present invention a polypropylene with high melt strength (HMS-PP) must be used. Such types of polymers are characterized by a certain degree of branching. Possible polypropylenes with high melt strength (HMS-PP) are so-called polypropylenes - Y / H and, for example, described in EP 0 787 750, that is, types of single branching polypropylene (polypropylenes Y having a main chain with a simple long side chain and a Y-like architecture) and types of polypropylene to which polymer chains are attached
    Petition 870190132049, of 12/12/2019, p. 18/55
    16/43 with a bridge formation group (an architecture resembling an H). Such polypropylenes are characterized by high melt resistance. A parameter of the degree of branching is the branching index g '. The g 'branch index correlates with the number of branches of a polymer. The branching index g 'is defined as g' = [IV] br / [IV] lin where g 'is the branching index, [IV] br is the intrinsic viscosity of the branched polypropylene and [IV] lin is the intrinsic viscosity of linear polypropylene having the same average molecular weight (within a range of +/- 10%) as branched polypropylene. Therefore, a low g 'value is an indicator for a highly branched polymer. In other words, if the g 'value decreases, the branching of the polypropylene increases. Reference is made in this context to B.H. Zimm and W.H. Stockmeyer, J. Chem. Phys. 17, 1301 (1949). This document is included here by reference. Thus it is preferred that the branching index g 'of the high melt strength polypropylene (HMS-PP) should be less than 1.0, more preferably, equal to or less than 0.9, such as less than 0.8. In another preferred embodiment the branching index g 'of the high melt strength polypropylene (HMSPP) should preferably be less than 0.7.
    [00036] The high degree of branching of polypropylene with high melt strength (HMS-PP) also contributes to its resistance to melting. In the same way, it is preferred that the polypropylene with high melt strength (HMS-PP) is still characterized by a deformation hardening behavior. Thus it is appreciated that the polypropylene with high melt strength (HMS-PP) has a strain hardening factor (SHF) of 3.5 to 30.0, more preferably from 5.0 to 20.0, measured at a rate deformation of 3.0 s -1 and a Hencky deformation of 3.0.
    [00037] Such a polypropylene with high melt strength (HMSPP) is preferably obtained through modification, that is, it modifies
    Petition 870190132049, of 12/12/2019, p. 19/55
    17/43 chemical tion, of a polypropylene. Such a modification is necessary to obtain the branching structure and / or the deformation hardening phenomena of the polypropylene with high melt strength (HMS-PP). Such a modification also has an influence on the gel content of polypropylene with high melt strength (HMS-PP). In the same way, it is justified to define polypropylene with high melt strength (HMS-PP) still and / or alternatively by its gel content. Thus, it is appreciated that polypropylene with high melt strength (HMS-PP) is characterized by a relatively moderate gel content, that is, not more than 1.00% by weight, even more preferred not more than 0.80 % by weight, even more preferred not exceeding 0.50%, by weight determined as the relative amount of boiling xylene insoluble polymer (hot xylene insoluble fraction, XHI). On the other hand, polypropylene with high melt strength (HMS-PP) can show a certain degree of branching and thus some amount of gel content, that is, at least 0.15% by weight, more preferably at least minus 0.27% by weight. Thus a preferred range for the gel content of the high melt strength polypropylene (HMS-PP) is 0.05 to 0.90% by weight, more preferred 0.26 to 0.8% by weight.
    [00038] Additionally, it is preferred that in the melt-resistant polypropylene (HMS-PP) it has an MFR2 (230 o C) in a range of 1.0 to 10.0 g / 10 minutes, more preferably from 4.0 to 8 , 5 g / 10 minutes, even more preferably from 6.0 to 8.0 g / 10 minutes.
    [00039] Preferably, high melt strength polypropylene (HMS-PP) has a density of at least 850 kg / m 3 , more preferably at least 875 kg / m 3 and more preferably at least 900 kg / m 3 .
    [00040] Also, preferably, the polypropylene with high melt strength (HMS-PP) has a density not exceeding 950
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    18/43 kg / m 3 , more preferably not more than 925 kg / m 3 and more preferably not more than 910 kg / m 3 .
    [00041] Preferably, the polypropylene with high melt strength (HMS-PP) has a melting point of at least 140 ° C, more preferably at least 150 ° C, more preferably at least 160 o C.
    [00042] As stated above, the high melt strength polypropylene (HMS-PP) is preferably a modified polypropylene. In the same way, polypropylene with high melt strength (HMS-PP) can still be defined using the method obtained. Thus the high melt strength (HMS-PP) is preferably the result of treating an unmodified polypropylene (A) with thermally decomposing agents and / or with ionizing radiation. However, in such a case there is a high risk that polypropylene (A) will be degraded, which is harmful. Thus it is preferred that the modification be carried out using the bifunctional unsaturated monomer (s) and / or multifunctional unsaturated low molecular weight polymer (s) as the chemically bonded bridging unit (s). An appropriate process for obtaining melt resistance polypropylene (HMS-PP) is, for example, shown in EP 0 787 750, EP 0 879 830 A1 and EP 0 890 612 A2. All documents are included here by reference. Therefore, the amount of peroxide is preferably in the beech of 0.05 to 3.00%, by weight, based on the unmodified polypropylene (A).
    [00043] Likewise in a preferred embodiment the high strength and melting polypropylene (HMS-PP) comprises units derived from (i) propylene and (ii) bifunctional unsaturated monomer (s) and / or low weight polymer (s) molecularly unsaturated molecular.
    Petition 870190132049, of 12/12/2019, p. 21/55
    19/43 [00044] Bifunctional unsaturated or multifunctional unsaturated as used above preferably means the presence of two or more non-aromatic double bonds, as in, for example, divinyl benzene or cyclopentadiene or polybutadiene. Only such bi- or multifunctional unsaturated compounds are used which can be preferably polymerized with the aid of free radicals. The unsaturated sites in the bi- or multifunctional unsaturated compounds are in their chemically bonded state not actually unsaturated, because the double bonds are each used for a covalent bond to the polypropylene (A) polymer chains.
    [00045] Reaction of the bifunctional unsaturated monomer (s) and / or multifunctional unsaturated low molecular weight polymer (s), preferably having an average numerical molecular weight (Mn) 10,000 g / mol, synthesized from one and / or more monomers unsaturated with the propylene polymer composition can be carried out in the presence of a thermally free radical forming agent, for example, decomposition free radical forming agent, with a peroxide that can be thermally decomposed and / or ionizing radiation or radiation from microwave.
    [00046] Bifunctional unsaturated monomers can be
    - divinyl compounds, such as divinyl aniline, m-divinyl benzene, p-divinyl benzene, divinyl pentane and divinyl propane;
    - allyl compounds, such as allyl acrylate, allyl metharylate, allyl methyl maletate and allyl vinyl ether;
    - dienes, such as, 1,3-butadiene, chloroprene, cyclohexadiene, cyclopentadiene, 2,3-dimethyl butadiene, heptadiene, hexadiene, isoprene and 1,4-pentadiene;
    - aromatic and / or aliphatic bis (maleimide), aliphatic (citraconimide) and mixtures of these unsaturated monomers.
    Petition 870190132049, of 12/12/2019, p. 22/55
    Especially preferred bifunctional unsaturated monomers are 1,3-butadiene, isoprene, dimethyl butadiene and divinyl benzene.
    [00048] The multifunctional unsaturated low molecular weight polymer, preferably having an average numerical molecular weight (Mn) 10,000 g / mol can be synthesized from one or more unsaturated monomers.
    [00049] Examples of such low molecular weight polymers are
    - polybutadienes, especially where the different microstructures in the polymer chain, that is, 1,4-cis, 1,4-trans and 1,2- (vinyl) are predominantly in the 1,2- (vinyl) configuration
    - copolymers of butadiene and styrene having 1,2- (vinyl) in the polymer chain.
    [00050] A preferred low molecular weight polymer is polybutadiene, in particular a polybutadiene having more than 50.0%, by weight of the butadiene in the 1,2- (vinyl) configuration.
    [00051] Polypropylene with high melt strength (HMS-PP) may contain more than one bifunctional unsaturated monomer and / or multifunctional unsaturated low molecular weight polymer. Even more preferred, the amount of bifunctional unsaturated monomer (s) and multifunctional unsaturated low molecular weight polymer (s) together in the high melt strength polypropylene (HMS-PP) is 0.01 to 10.0% by weight , based on said high melt strength polypropylene (HMS-PP).
    [00052] As stated above, it is preferred that the bifunctional unsaturated monomer (s) and / or multifunctional unsaturated low molecular weight polymer (s) are used in the presence of a thermal decomposition free radical forming agent.
    [00053] Peroxides are preferred thermal free decomposition agents. More preferably,
    Petition 870190132049, of 12/12/2019, p. 23/55
    21/43 Free radical formation of thermal decomposition is selected from the group consisting of acyl peroxide, alkyl peroxide, hydroperoxide, perester and peroxy carbonate.
    [00054] The following peroxides listed are particularly preferred:
    Acyl peroxides: benzoyl peroxide, benzoyl 4-chloride peroxide, benzoyl 3-methoxy peroxide and / or methyl benzoyl peroxide;
    Alkyl peroxides: t-butyl alkyl peroxide, 2,2-bis (t-butyl peroxy butane), 1,1-bis- (t-butyl peroxy) -3,3,5-trimethyl cyclohexane, 4, N-butyl 4-bis- (t-butyl peroxy), diisopropyl amino methyl t-amyl peroxide, amino methyl t-amyl dimethyl peroxide, amino methyl t-butyl diethyl peroxide, dimethyl amino methyl t-peroxide butyl, 1,1di- (t-amyl peroxy) cyclohexane, t-amyl peroxide, t-butyl cumyl peroxide, t-butyl peroxide and / or 1-hydroxy butyl n-butyl peroxide;
    Peresters and peroxy carbonates: butyl peracetate, cumila peracetate, cumila perpropionate, cyclohexyl peracetate, di-t-butyl peradipate, di-t-butyl perazelate, di-t-butyl perglutarate, di-t pertalate -butyl, di-t-butyl persebacate, 4-nitro cumyl perpropionate, 1-phenyl ethyl perbenzoate, phenyl ethyl perbenzoate, t-butyl bicyclo percarboxylate— (2,2,1) heptane, t perbutyrate -butyl-4-carbo methoxy, t-butyl cyclobutane percarboxylate, t-butyl cyclohexyl peroxy carboxylate, t-butyl cyclopentyl percarboxylate, t-butyl cyclopropane percarboxylate, t-butyl dimethyl percinamate, t-butyl perbenzoate butyl-2- (2,2-diphenyl vinyl), t-butyl-4-methoxy perbenzoate, t-butyl perbenzoate, t-butyl carboxy cyclohexane, t-butyl peptide, t-butyl peroxy isopropyl carbonate, pertoluate tbutyl, t-butyl-1-phenyl cyclopropyl percarboxylate, t-butyl 2-propyl per-penten2-oate, t-butyl-1-methylcyclopropyl percarboxylate la, t-butyl-4-nitrophenyl peracetate, t-butyl nitro phenyl peroxy carbamate, per
    Petition 870190132049, of 12/12/2019, p. 24/55
    22/43 t-butyl-N-succiimido carboxylate, t-butyl percrotonate, t-butyl permaleic acid, t-butyl permethacrylate, t-butyl peroctoate, t-butyl peroxy isopropyl carbonate, t-butyl perisobutyrate , t-butyl peracrylate and / or t-butyl perpropionate;
    or mixtures of these free radical forming agents listed above.
    [00055] The unmodified polypropylene (A) to prepare such a polypropylene with high melt strength (HMS-PP) preferably presents an MFR2 (230 o C) in a range of 0.05 to 45.00 g / 10 minutes . Most preferably MFR2 (230 o C) is in a range of 0.05 to 35.00 g / 10 minutes in the case that unmodified polypropylene (A) is a homopolymer. On the other hand, MFR2 (230 o C) is in a range of 0.05 to 45.00 g / 10 minutes in the case of non-modified polypropylene (A) being a copolymer.
    [00056] Preferably the unmodified polypropylene (A) is a homopolymer.
    [00057] The term unmodified homopolymer (A) as used throughout the present invention refers to a polypropylene that consists substantially, that is, more than 95% by weight, even more preferably at least 99.7%, in weight, such as at least 99.8% by weight of propylene units. In a preferred embodiment, only propylene units in the propylene homopolymer are detectable. The comonomer content can be determined with FT infrared spectroscopy, as described below in the examples.
    [00058] Preferably the polypropylene with high melt strength (HMS-PP) is produced from unmodified polypropylene (A) as defined above under process conditions as defined in details below.
    [00059] Also as a polymer component, viscous polypropylene is required. As stated above, this polypropylene (B)
    Petition 870190132049, of 12/12/2019, p. 25/55
    23/43 has to be chemically different from the random propylene copolymer (R-PP). Of course, propylene (B) is also chemically different from polypropylene with high melt strength (HMS-PP). [00060] An essential difference between polypropylene (B) and polypropylene with high melt strength (HMS-PP) is that polypropylene (B) is an unbranched polypropylene while polypropylene with high melt strength (HMS-PP) ) shows a branching structure. In other words, polypropylene (B) preferably has a higher g 'branching index compared to the g' branching index of high melt strength polypropylene (HMSPP), more preferably the g 'branching index of polypropylene (B) is at least minus 0.95, such as 1.0. A further distinguishing feature between polypropylene with high melt strength (HMS-PP) and polypropylene (B) is preferably the gel content expressed in the amount of the insoluble fraction in hot xylene (XHI). Likewise, polypropylene (B) has a gel content below 0.15% by weight, more preferably it has no detectable gel content. Yet a difference between polypropylene (B) and high melt strength polypropylene (HMS-PP) is preferably that they differ in the melting flow rate MFR2 (230 o C), that is, polypropylene (B) has a MFR2 (230 o C) higher than polypropylene with high melt strength (HMS-PP).
    [00061] The difference between the polypropylene (B) and the random propylene copolymer (R-PP) is preferably that they differ in the melting flow rate MFR2 (230 o C), that is, the polypropylene (B) has a MFR2 (230 o C) higher than the random propylene copolymer (R-PP). In the same way it is appreciated that the polypropylene (B) has an MFR2 (230 o C) of at least 400 g / 10 minutes, more preferably at least 430 g / 10 minutes, as at least 450 g / 10 minutes, even more preferably at least 800 g / 10
    Petition 870190132049, of 12/12/2019, p. 26/55
    24/43 minutes, such as about 1200 g / 10 minutes. On the other hand, polypropylene (B) should not be so viscous as to deteriorate the stiffness of the final film. Likewise, it is appreciated that polypropylene (B) has an MFR2 (230 o C) in the range of 400 to 3000 g / 10 minutes, more preferably in the range of 420 to 2000 g / 10 minutes, such as 440 to 1500 g / 10 minutes.
    [00062] The distribution of molecular weight (MWD) is rather desirably low. Likewise, it is preferred that the Mw / Mn (MWD) of the polypropylene (B) is below 4.5, such as 0.5 to 4.5, more preferably below 4.0, such as 0.5 to 4 , 0.
    [00063] Additionally, it is appreciated that polypropylene (B) has a fraction soluble in cold xylene (XCS) not exceeding 5.0% by weight, such as 0.5 to 4.5% by weight, more preferably not exceeding to 3.5% by weight, such as 0.5 to 3.0% by weight.
    [00064] Polypropylene (B) as defined throughout the present invention can be obtained by decreasing the feed viscosity as defined in details below or by propylene polymerization, for example, in the presence of a metallocene catalyst. An appropriate polypropylene obtained by metallocene polymerization technology is Basell's commercial product MF650W. However, it is appreciated in the present patent application that polypropylene is obtained in particular by decreasing the feed viscosity.
    [00065] Likewise, to obtain the desired MFR range, polypropylene (B) is typically prepared through polymerization of propylene and optional comonomers for a relatively high molecular weight, which is then treated with peroxide to reduce its molecular weight to a desired average (viscosity dilution). Similarly, polypropylene (B) is preferably a polypropylene of diluted viscosity.
    Petition 870190132049, of 12/12/2019, p. 27/55
    25/43 [00066] Most preferably the initial polypropylene used for the preparation of the polypropylene (B) is chosen in such a way that the viscosity dilution ratio (final MFR2 (230 o C) / initial MFR2 (230 o C)) is 3.5 to 40.0, more preferably 4.0 to 30.0, where MFR2 (230 o C) is MFR2 (230 o C) of the polypropylene before viscosity dilution and final MFR2 (230 o C) is the MFR2 (230 o C) of polypropylene (B).
    [00067] The preparation of polypropylene (B) will be defined in more detail below.
    [00068] Furthermore, polypropylene (B) can be a propylene copolymer, such as a random propylene copolymer (B ') or a propylene homopolymer (B), the latter being preferred. In the case where polypropylene (B) is a random propylene copolymer (B '), the copolymer (B') preferably comprises units derived from propylene and at least one other C2-20 alpha olefin, preferably at least one other C2-10 alpha olefin. Likewise, such a random propylene copolymer (B ') comprises units derived from propylene and at least one other alpha olefin selected from the group consisting of ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1octene, 1-nonene and 1-decene, where ethylene, 1-butene, 1-pentene and 1hexene are preferred. In particular, it is preferred that such a random propylene copolymer (B ') consists of units derived from propylene and ethylene. The number of units derived from C2-20 alpha olefins other than propylene in the random propylene copolymer (B ') is in the range of 1.0 to 7.0% by weight, more preferably 1.5 to 6.0% by weight, even more preferably 2.0 to 5.5% by weight.
    [00069] Preferably polypropylene (B) is isotactic. In the same way it is appreciated that polypropylene (B) has a high pentad concentration, that is, greater than 90 mol%, more preferably greater than 92 mol%, even more preferably greater than 93 mol% and even more preferably greater than 95% by mol,
    Petition 870190132049, of 12/12/2019, p. 28/55
    26/43 as greater than 99 mol%.
    [00070] Additionally, it is preferred that the polypropylene composition being part of the inventive blow-extruded film comprises a bleach (C) comprising at least one alpha - nucleating agent (N). Just as beta - nucleation agents negatively influence the alpha - nucleation effect (of the alpha nucleation agent) it is preferred that the bleach (C), the polypropylene composition, and / or the final blow extruded film are (essentially) free of beta nucleating agents. Even more preferably, the bleach (C) consists of at least one alpha nucleating agent (N). Likewise, the bleach (C) may preferably comprise one, two or three alpha nucleating agents (N). However, it is appreciated that the bleaching agent (C) is an alpha nucleating agent (N).
    [00071] In principle any alpha nucleating agent (N) can be used.
    [00072] Examples of suitable alpha nucleating agents are selected from the group consisting of (i) salts of mono carboxylic acids and poly carboxylic acids, for example, sodium benzoate or aluminum t-butyl benzoate, and (ii) dibenzylidene sorbitol ( for example, 1,3: 2,4 dibenzylidene sorbitol) and derivatives of dibenzylidene sorbitol substituted with C1-8 alkyl, such as methyl dibenzylidene sorbitol, ethyl dibenzylidene sorbitol or dimethyl dibenzylidene sorbitol (eg 1.3: 2,4 di- (methyl benzylidene) sorbitol, nonitol, 1,2,3-tridesoxy-4,6: 5,7-bis-O - [(4-propyl phenyl) methylene] nonitol, and (iii) diesters of phosphoric acid, for example, 2,2'-methylene bis- (4,6-di-t-butyl phenyl) sodium phosphate or hydroxy-bis- [2,2'-methylene bis- (4,6-di-t-butyl phenyl) phosphate] of aluminum, and (iv) vinyl cycloalkane polymer and vinyl alkane polymer.
    Petition 870190132049, of 12/12/2019, p. 29/55
    27/43 [00073] Such additives are generally commercially available and are described, for example, in Gacheter / Muller, Plastics Additives Handbook, 4th Edition, Hanser Publishers, Munich, 1993.
    [00074] The content of nucleating agent in the polypropylene composition is preferably up to 5% by weight. In a preferred embodiment, the polypropylene composition of the present invention contains from 0.001 to 1.0%, by weight, preferably from 0.005 to 0.60%, by weight, of a nucleating alpha, in particular dibenzylidene sorbitol (for example,
    1.3: 2.4 dibenzylidene sorbitol) or a derivative of dibenzylidene sorbitol, preferably dimethyl dibenzylidene sorbidtol (eg 1.3:
    2.4 di (methyl benzylidene) sorbitol) and / or nonitol, 1,2,3-tridesoxy-4,6: 5,7bis-O - [(4-propyl phenyl) methylene] nonitol.
    [00075] The most preferred nucleating alpha is nonitol, 1,2,3-tridesoxy4,6: 5,7-bis-O - [(4-propyl phenyl) methylene] nonitol. Likewise in an especially preferred embodiment the bleach (C) comprises, even more preferred consists of, nonitol, 1,2,3-tridesoxy-4,6: 5,7-bisO - [(4-propyl phenyl) methylene] nonitol.
    [00076] In the event that alpha nucleating agents are polymeric alpha nucleating agents selected from the group consisting of vinyl cycloalkane polymers and vinyl alkane polymers, these polymeric nucleating agents are obtained using a special reactor technique, where the catalyst is prepolymerized as monomers similar to, for example, cyclohexane vinyl (HCV), or by combining a polypropylene composition with the vinyl cycloalkane polymer or vinyl alkane polymer. These processes are described in more detail in, for example, EP 0 316 187 A2 and WO 99/24479.
    [00077] To obtain especially good results, the required components as defined above can be present in specific amounts within the new polypropylene composition of the inventive blow extruded film. Thus it is preferred that the composition of
    Petition 870190132049, of 12/12/2019, p. 30/55
    28/43 polypropylene according to the present invention comprises:
    (a) 50.0 to 92.0% by weight, more preferably 60.0 to 90.0% by weight, even more preferably 65.0 to 90.0% by weight of the random propylene copolymer ( R-PP), (b) 5.0 to 26.0% by weight, more preferably 6.0 to 18.0% by weight, even more preferably 6.5 to 16.0% by weight. high melt strength polypropylene (HMS-PP), (c) 1.0 to 15.0, by weight, more preferably 1.5 to 17.0%, by weight, even more preferably 2.0 to 10.0 % by weight of the polypropylene (B), and (d) 0.01 to 5.0% by weight, more preferably 0.02 to 1.0% by weight, even more preferably 0.03 to 0 , 7%, by weight, of the bleach (C), based on the total polypropylene composition.
    [00078] The polypropylene composition of the inventive blow-extruded film can still comprise components. However, it is preferred that the polypropylene composition comprises as polymer components only the random propylene copolymer (R-PP), polypropylene (B) and high melt strength polypropylene (HMS-PP) as defined above. In the same way, the quantities of random propylene copolymer (R-PP), polypropylene (B), high melt strength polypropylene (HMS-PP) and bleach (C) may not result in 100% by weight, based on the total polypropylene composition. Thus, the remaining part up to 100%, by weight, can be obtained through additives known in the art. However, this remaining part should not be more than 10.0%, by weight, within the total composition. For example, the inventive polypropylene composition may additionally comprise small amounts of stabilizers, acid eliminators, lubricants, fillers, antistatic agents, plasticizers, dyes, pigments or retains
    Petition 870190132049, of 12/12/2019, p. 31/55
    29/43 flame donors. In general, these are incorporated during granulation of the powdery product obtained in the polymerization.
    [00079] Still as already established above, the blown film extruded comprises as a polymer composition only the polypropylene compositions as defined in the present invention. Thus, the blow-extruded film can still comprise additives, but no polymers such as those being part of the polypropylene composition.
    [00080] In a preferred embodiment the blow-extruded film comprises at least 80.0% by weight, more preferably at least 90.0% by weight, even more preferably at least 95.0% by weight, even more preferably consists of a polypropylene composition as defined in the present invention. Thus, it is especially preferred that the blow-extruded film comprises as polymer components only the random propylene copolymer (R-PP), polypropylene (B) and high melt strength polypropylene (HMS-PP) as defined in the present invention and additionally said extruded blow film contains the polypropylene composition as defined in the present invention by at least 80% by weight, more preferably at least 90.0% by weight, even more preferably at least 95.0% by weight , even more preferably, said blow-extruded film consists of the polypropylene composition as defined in the present invention.
    [00081] The present invention is also directed to the use of the polypropylene composition defined above. In the same way the polypropylene composition as defined in the present invention is used for the preparation of a blow-extruded film.
    [00082] Still the present invention is directed to a packaging material comprising the extruded blow film of the present invention.
    Petition 870190132049, of 12/12/2019, p. 32/55
    30/43 [00083] In what follows, the preparation of the inventive polypropylene composition is described in more detail.
    [00084] The individual components used for the polypropylene composition being part of the blow-extruded film are known to those skilled in the art and thus can be easily produced using the information provided here.
    [00085] For example, the random propylene copolymer (R-PP) as defined in the present invention can be prepared by polymerization, in a slurry reactor, for example, a loop reactor, optionally propylene together with at least one other C2 -20 alpha olefin (comonomers), in the presence of a polymerization catalyst to produce a part of the random propylene copolymer (R-PP). This part is then transferred to a subsequent gas phase reactor, where the propylene in the gas phase reactor is reacted in the presence of another appropriately selected C2-20 alpha olefin (s) (comonomers) in order to further produce a part in the presence reaction product of the first stage. This sequence of reactions provides a reactor combination of parts (i) and (ii) constituting a random propylene copolymer (R-PP). Of course, it is possible through the present invention that the first reaction is carried out in a gas phase reactor while the second polymerization reaction is carried out in a slurry reactor, for example, a loop reactor. In addition, it is also possible to reverse the order of production parts (i) and (ii), which were described above in order to first produce part (i) and then produce part (ii). The process discussed above, comprising at least two polymerization steps, is advantageous in view of the fact that it provides easily controllable reaction steps allowing the preparation of a desired reactor combination. The polymerization steps can be adjusted, for example, through appropriate selection of monomer feed, comonomer feed,
    Petition 870190132049, of 12/12/2019, p. 33/55
    31/43 hydrogen supply, temperature and pressure in order to properly adjust the properties of the obtained polymerization products. In particular, it is possible to obtain a multimodality, preferably bimodality, of the random propylene copolymer (R-PP), with respect to the comonomer, such as ethylene, distribution as well as with respect to the values of molecular weights and MFR2 (230 o C) during the said multistage polymerization procedures.
    [00086] Such a process can be carried out using any catalyst suitable for the preparation of the random propylene copolymer (R-PP). Preferably, the process as discussed above is carried out using a high performance Ziegler - Natta catalyst, in particular a high performance Ziegler - Natta catalyst (so called fourth and fifth generation types to differentiate from second generation Ziegler - Natta catalysts). An appropriate Ziegler - Natta catalyst to be employed in accordance with the present invention comprises a catalyst component, a cocatalyst component, and at least one electron donor (internal and / or external electron donor, preferably at least one external donor). Preferably, the catalyst component is a Ti-Mg based catalyst component and typically the cocatalyst is an Al-alkyl based compound. Suitable catalysts are shown in particular in US 5,234,879, WO 92/19653, WO 92/19658 and WO 99/33843. [00087] Preferred external donors are known donors based on silane, such as dicyclopentyl dimethoxy silane or cyclohexyl methyl dimethoxy silane.
    [00088] One embodiment of a process as discussed above is a gas - circuit phase process, as developed by Borealis, known as Borstar technology, described, for example, in EP 0 887 379 A1 and WO 92/12182.
    [00089] Regarding the gas phase process - preferred paste
    Petition 870190132049, of 12/12/2019, p. 34/55
    32/43 mentioned above, the following generic information can be provided with respect to process conditions.
    [00090] Temperature from 40 to 110 o C, preferably between 60 and 100 o C, in particular between 80 and 90 o C, with a pressure in the range of 2 to 8 MPa (20 to 80 bar), preferably 3 to 6 MPa (30 to 60 bar), with the option of adding hydrogen in order to control the molecular weight. The slurry reaction product, which is preferably carried out in a loop reactor, is then transferred to the subsequent gas phase reactor, where the temperature is preferably within the range of 50 to 130 o C, more preferably 80 to 100 o C, at a pressure in the range of 0.5 to 5 MPa (5 to 50 bar), preferably
    1.5 to 3.5 MPa (15 to 35 bar), again with the option of adding hydrogen in order to control the molecular weight.
    [00091] The residence time may vary in the reactor zones identified above. In modalities, the residence time in the slurry reaction, for example, the circuit reactor, is in the range of 0.5 to 5 hours, for example, 0.5 to 2 hours, while the residence time in the phase reactor gas will generally be 1 to 8 hours.
    [00092] The properties of the random propylene copolymer (RPP) produced with the process outlined above can be adjusted and controlled with the process conditions as known to those skilled in the art, for example, through one or more of the following process parameters : temperature, hydrogen feed, comonomer feed, propylene feed, catalyst, type and quantity of external donor, division between two or more components of a multimodal polymer.
    [00093] Polypropylene with high melt strength (HMS-PP) is preferably obtained through a process as described in EP 0 879 830 A1 and EP 0 890 612 A2. Both documents are included here by reference. Likewise, polypropylene with high resistance Petition 870190132049, of 12/12/2019, p. 35/55
    33/43 melt strength (HMS-PP) is produced through:
    (a) mixture of (i) an unmodified propylene homopolymer and / or copolymer (A) as defined above, preferably an unmodified propylene homopolymer with an average weight molecular weight (Mw) of 500,000 to 1,500,000 g / mol, (ii) from 0.05 to 3% by weight, based on the components of (i) and (ii), of a peroxide selected from the group consisting of acyl peroxide, alkyl peroxide, hydroperoxide, perester and peroxycarbonate, and (iii) optionally diluted with inert solvents, (b) heating to 30 to 100 o C, preferably 60 to 90 o C, (c) sorption of volatile bifunctional monomers, preferably multifunctional, ethylenically unsaturated monomers, such as C4- 10 dienes and / or C7-10 divinyl compound, through homopolymer and / or unmodified propylene copolymer (A), preferably unmodified propylene homopolymer (A), from the gas phase at a temperature of 20 to 120 o C , preferably from 60 to 100 o C, where the amount of the bifunctional unsaturated monomers is from 0.01 to 10.00% by weight, preferably from 0.05 to 2.00% by weight, based on the propylene homopolymer (A), (d) heating and melting the polypropylene composition in an atmosphere comprising inert gas and / or volatile bifunctional monomers, from a sorption temperature of 210 o C, with which the free radical generators are decomposed and then (e) melting heating to 280 ° C in order to remove non-monomers -reacts and decomposition products, and (f) fusion agglomeration.
    [00094] The process for producing high-strength polypropylene
    Petition 870190132049, of 12/12/2019, p. 36/55
    34/43 melt strength (HMS-PP) is preferably a continuous process, carried out in reactors, mixers, kneaders and continuous extruders. Batch production of polypropylene with high melt strength (HMS-PP), however, is also feasible.
    [00095] Practical t sorption times for volatile bifunctional monomers range from 10 to 1000 s, where t sorption times of 60 to 600 are preferred.
    [00096] As mentioned above, polypropylene (B) is preferably obtained by decreasing feed viscosity in a manner well known to those skilled in the art. It is preferably carried out as follows: a propylene polymer in the form of particles, for example, flake or pelletized as polymerized, has sprinkled on or combined with it, a pro-degradant or free radical generation source, for example, a peroxide in liquid or powdered form or absorbed on and / or in a carrier, for example, polypropylene / peroxide concentrate. Typical feed viscosity reducing agents are 2,5dimethyl-2,5-bis- (t-butyl peroxy) hexane (DHBP) (for example, sold under the trademarks Luperox 101 and Trigonox 101), 2,5-dimethyl2 , 5-bis- (t-butyl peroxy) hexino-3 (DYBP) (for example, sold under the trademarks Luperox 130 and Trigonox 145), dicumyl peroxide (DCUP) (for example, sold under the trademarks Luperox DC and Perkadox BC), di-t-butyl peroxide (DTBP) (for example, sold under the trademarks Trigonox B and Luperox Di), tbutil cumila peroxide (BCUP) (for example, sold under the trademarks Trigonox T and Luperox 801) and bis- (t-butyl peroxy isopropyl) benzene (DIPP) (for example, sold under the trademarks Perkadox 14S and Lupperox DC). Appropriate amounts of peroxide to be employed in accordance with the present invention are in principle known to those skilled in the art and can be easily calculated in
    Petition 870190132049, of 12/12/2019, p. 37/55
    35/43 bases of the amount of polypropylene to be subjected to feed viscosity dilution, the MFR2 value (230 o C) of the polypropylene to be subjected to feed viscosity reduction and the desired MFR2 (230 o C) target of the polypropylene (B) to be obtained. Likewise, typical amounts of peroxide feed viscosity reducing agent are from 0.005 to 0.5% by weight, more preferably from 0.01 to 0.2% by weight, based on the amount of propylene polymer employed . The propylene and peroxide polymer or polymer / peroxide concentrate is introduced into a medium for thermal plasticization or melting combination and transporting the mixture, for example, an extruder at an elevated temperature. Temperature residence times are controlled in relation to the particular peroxide selected (that is, based on the peroxide half-life at the extruder process temperature) in order to effect the desired degree of polymer chain degradation.
    [00097] In addition, the polymer composition according to the present invention can be prepared by composing components within appropriate melt mixing devices for the preparation of polymeric compounds, including in particular single screw extruders as well as extruders of double screw. Other suitable fusion mixing devices include planet extruders and single screw coamassers. Especially preferred are twin screw extruders including high intensity mixing and mixing sections. Suitable melting temperatures for preparing compositions are in the range of 170 to 300 o C, preferably in the range of 200 to 260 ° C and at a productivity of 10 to 500 kg / h and a screw speed of 50 to 200 rpm.
    [00098] For the preparation of the film an extrusion blowing process as known in the art is applied. The film of the present invention is preferably produced by the first extrusion of com
    Petition 870190132049, of 12/12/2019, p. 38/55
    36/43 polypropylene position through a circular die, followed by bubble-like expansion. The blown film according to this invention is, for example, produced on a single screw extruder with a 70 mm cylinder diameter and a 200 mm round section die with 1.2 mm die opening in combination with a single edge cooling ring and internal bubble cooling (IBC). Melting temperature is preferably 210 ° C in the die; the temperature of the cooling air is preferably maintained at 15 o C and the blow-up ratio (BUR) is preferably 1: 1.5 or less. More preferably, a typical blowing ratio (BUR) of the inventive blown film is 1: 1.5 to 1: 5, even more preferably the blowing ratio is 1: 2 to 1: 4.
    [00099] In addition, it is preferred that a film thickness is adjusted through the ratio between extruder production, withdrawal speed and blowing ratio (BUR). In the same way it is appreciated that the blow-extruded film of the present invention has a thickness not exceeding 200 micrometers, preferably it has a thickness in the range of 20 to 200 micrometers, such as 20 to 100 micrometers.
    [000100] The present invention will now be described in further detail by the examples provided below.
    Examples
    1. Measurement Definitions / Processes [000101] The following definitions of determination terms and procedures are applied to the above generic description of the invention as well as the examples below unless otherwise defined. [000102] Quantification of polypropylene isotacticity through 13 C MRI spectroscopy [000103] Isotacticity is determined by quantitative 13 C nuclear magnetic resonance spectroscopy after basic task such as,
    Petition 870190132049, of 12/12/2019, p. 39/55
    37/43 for example, in: V. Busico and R. Cipullo, Progress in Polymer Science, 2001, 26, 443-533. Experimental parameters are adjusted to ensure measurement of quantitative spectra for this specific task, for example, in: Berger and S. Braun, 200 and More RMN Experiments: A Practical Course, 2004, Wiley - VCH, Weiheim. Quantities are calculated using simple corrected ratios of the signal integrals of representative sites in a manner known in the art. Isotacticity is determined at the pentad level, that is, mmmm fraction of the pentad distribution.
    [000104] Average numerical molecular weight (Mn), average molecular weight (Mw) and molecular weight distribution (MWD) are determined by size exclusion chromatography (SEC) using a Waters Alliance GPCV 2000 instrument with an in-line viscometer. The oven temperature is 140 o C. Trichloro benzene is used as a solvent (ISO 16014).
    Randomness [000105] In FTIR instruments, films of 250 mm thickness were molded by compression at 225 ° C and investigated on a Perkin - Elmer System 2000 FTIR instrument. The peak ethylene area (760-700 cm -1 ) was used as a measure of total ethylene content. The absorption band for the structure -PEP- (an ethylene unit between propylene units), occurs at 733 cm -1 . This band characterizes the random ethylene content. For longer sequences of ethylene (more than two units), an absorption band occurs at 720 cm - 1 . Generally, a corresponding shoulder for longer ethylene runs is observed for random copolymers. Calibration for the total ethylene content based on the area and the random ethylene content (PEP) based on peak height at 733 cm -1 was performed using 13 C NMR. (Thermochimica Acta, 66 (1990) 53-68).
    Randomness = random ethylene content (-P-E-P -) / content
    Petition 870190132049, of 12/12/2019, p. 40/55
    38/43 total ethylene x 100% [000106] MFR2 (230 o C) is measured according to ISO 1133 (230 o C,
    2.16 kg of load).
    [000107] Melting temperature Tm and crystallization temperature Tc are measured with a Mettler TA820 differential scanning calorimetry (DSC) device on 3 +/- 0.5 mg samples according to ISO 11357-3: 1999. Crystallization and melting temperatures are obtained during cooling and heating explorations of 10 ° C / minute between 30 ° C and 225 o C. Melting and crystallization temperatures were taken as the peaks of endotherms and exotherms, while melting and crystallization enthalpies are taken as integrals under these peaks. The compositions according to the present invention will normally exhibit at least two distinct melting points with clearly different melting enthalpies, the smallest of them, Tm (1), normally constituting significantly more than 50% of the total melting enthalpy. The difference according to Formula (I) is then calculated as Tm (1) -Tc.
    [000108] Ethylene content is measured with Fourier transformation infrared spectroscopy (FTIR) calibrated with 13 C-NMR. When measuring the ethylene content in polypropylene, a thin film of the sample (thickness of about 250 mm) was prepared by hot pressing. The area of absorption peaks at 720 and 733 cm -1 was measured with a Perkin Elmer FTIR 1600 spectrometer. The process was calibrated using ethylene content data by 13 C-NMR.
    [000109] Content of any of the C4-20 alpha olefins is determined with 13 C-NMR; literature: IR-Spektroskopie für Anwender; WILEYVCH, 1997 and Validierung in der Analytik, WILEY-VCH, 1997.
    [000110] Density is measured according to ISO 1183-187. Sample preparation is done through compression molding according to ISO 1872-2: 2007.
    Petition 870190132049, of 12/12/2019, p. 41/55
    39/43 [000111] The content of soluble in cold xylene (XCS,% by weight): the content of soluble in cold xylene (XCS) is determined at 23 ° C according to ISO 6427.
    [000112] The gel content is assumed to be identical to the insoluble fraction in hot xylene (XHI), which is determined by extracting 1 g of a finely cut polymer sample with 350 ml of xylene in a Soxhlet extractor for 48 hours at temperature boiling. The amount of solid remaining is dried at 90 ° C and weighed to determine the amount of insoluble matter.
    [000113] Deformation hardening factor:
    [000114] The uniaxial extension viscosity was obtained from flow measurements of uniaxial extension, conducted on an Anton Paar MCR 501 coupled with the Sentmanat extension adaptation (SER-1). The temperature for uniaxial flow measurements was set at 180 ° C, applying extension rates ranging from 0.3 s 1 to 10 s -1 in a Hencky strain range from 0.5 to 3.5. Particular care was taken in preparing the samples for extension flow. Samples having a thickness of 0.6 mm were prepared by compression molding at 230 ° C followed by slow cooling at about 2 ° C / minute to room temperature (cooling with water or forced air was not used). This procedure allowed obtaining well-formed samples free of residual stresses. The sample was left for a few minutes at the test temperature of 180 ° C to ensure thermal stability, before uniaxial flow measurements.
    [000115] The deformation hardening factor is defined by Formula (II) SHF = VE (t, é) = η * Ε (ί, έ) n + Lve W 3η + (ί)
    Petition 870190132049, of 12/12/2019, p. 42/55
    40/43 where, it is the uniaxial extensional viscosity; and
    Vlive ^ is three times the time-dependent shear viscosity (n + (t)) in the linear strain range.
    [000116] The determination of the linear viscoelastic envelope using IRIS Rheo Hub 2008, required the calculation of the discrete relaxation time spectrum from loss and storage module data (G ', G (ω)). Linear viscoelastic data (G ', G (ω)) were obtained by frequency sweep measurements carried out at 180 ° C, on an Anton Paar MCR 300 coupled with 25 mm parallel plates. The underlying calculation principles used to determine the discrete relaxation spectrum are described in Baumgãrtel M, Winter HH, Determination of the discrete relaxation and retardation time spectra from dynamic mechanical data, Rheol Acta 28: 511519 (1989).
    [000117] IRIS RheoHub 2008 expresses the relaxation time spectrum as a sum of Maxwell N ο W _ f modes
    G (t) = G e . ^ G, -e λ 'where g, and λί are material parameters resulting from the spectrum calculation and G and is the equilibrium module for isotactic polymer. [000118] The choice for the maximum number of modes, N used for determining the discrete relaxation spectrum, was made through the use of the optimal option from IRIS RheoHub 2008. The balance module G e was set to zero. The nonlinear adaptation used to obtain the linear viscoelastic envelope in extension (&&)) was performed on IRIS Rheo Hub 2008, using the Doi-Edwards model.
    [000119] Turbidity was determined according to ASTM D 1003-00 on extruded blown films having a thickness of 40 microPetition 870190132049, from 12/12/2019, p. 43/55
    41/43 meters [000120] Brightness was determined according to DIN 67530 on blown extrusion films having a thickness of 40 micrometers at an angle of 20 o .
    2. Preparation of Examples [000121] The components were combined according to Table 2. For stabilization of the materials a conventional additive package was used such as Irganox B225 0.2% by weight (antioxidant master batch supplied by Ciba Specialty Chemicals, Switzerland) and 0.05% by weight of Ca stearate (CAS-No . 1592-23-0). Combination took place in a twin screw extruder (PRISM TSE24 L / D ratio 40) with two high intensity mixing segments at temperatures between 190 and 240 ° C at a productivity of 10 kg / h and a screw speed of 50 rpm. The material was extruded into two circular dies of 3 mm in diameter in a water bath for tape solidification and then pelleted and dried. The films were made on a W&H Monolayer blown film line (a 70 mm extruder, productivity (total) 60 kg / h, 200 mm die diameter, 1.2 mm die opening, 1: 2 blowing ratio , 5) with the following processing parameters:
    Tablei: Processing Parameters
    T (fusion ° C 240 V (screw rpm 70 V (line m / minute 15 d (FL) * mm 600
    Table 2: Polypropylene compositions
    R-PP HMS PP α-1[g] [g] [g] [pm] CE 1 100.00 - - 4000
    Petition 870190132049, of 12/12/2019, p. 44/55
    42/43
    CE 2 95.00 - 5.00 4000 IE 1 87.50 7.50 5.00 4000 R- PP: is the random propylene ethylene copolymer
    Borealis RB709CF with an ethylene content of 4.5% by weight, an MFR2 (230 o C) of 1.5 g / 10 minutes, a density of 901 kg / m 3 and a fraction soluble in cold xylene (XCS ) of 8.5% by weight.
    HMS: is the high strength polypropylene of the commercial cast Daploy WB180HMS from Borealis based on a propylene homopolymer, where the high strength polypropylene of the cast Daploy WB180HMS has a density of 905 kg / m 3 , a melting point of 165 o C , MFR2 (230 o C) of 6.0 g / 10 minutes, a melting resistance of 11.5 cN at a maximum speed of 242 mm / s, a fraction soluble in cold xylene (XCS) of 2.5%, by weight, and a g 'branch index of 0.64.
    PP: is the commercial low viscosity polypropylene HL504FB from Borealis with an MFR2 (230 o C) of 450 g / 10 minutes
    Α-1: it is the commercial alpha nucleating agent Millad NX8000 (Nonitol, 1,2,3-tridesoxy-4,6: 5,7-bis-O - [(propyl phenyl) methylene] nonitol)
    Table 3: Properties of polypropylene compositions.
    CE 1 CE 2 E 1 MFR [g / 10 minutes] 1.5 4.0 3.2 Tm (1) [° C] 136 137 136 Hm (1) [J / g] 94 96 86 Tm (2) [° C] - - 156 Hm (2) [J / g] - - 10 Tc [° C] 122 120 124 SHF ** [-] 0.9 0.8 1.5 XCS [wt .-%] 7.0 6.8 6.6
    * MFR is MFR2 (230 ° C) ** SHIF is the strain hardening factor (SHF)
    Petition 870190132049, of 12/12/2019, p. 45/55
    43/43 measured at a strain rate of 3.0 s -1 and a strain
    Hencky of 3.0
    Table 4: Properties of the blown film.
    CE 1 CE 2 E 1 MFR [g / 10 minutes] 1.5 4.0 3.2 SHF ** [-] 0.9 0.8 1.5 Turbidity [%] 4.6 6.7 4.5 Brightness inside [%] 60 79 76 Brightness out [%] 59 81 79 Tensile Test (MD) Modulus [MPa] 923 793 847 Load Limit [MPa] 27.7 25.7 25.7 Limit extension [%] 9.6 10.4 9.9 Extension at break [%] 680 620 650 Tensile Test (TD) Modulus [MPa] 910 799 838 Load Limit [MPa] 25.2 23.0 23.5 Limit extension [%] 8.2 8.5 8.0 Extension at break [%] 680 700 720
    * MFR is MFR2 (230 ° C) ** SHIF is the strain hardening factor (SHF) measured at a strain rate of 3.0 s -1 and a strain
    Hencky of 3.0
    权利要求:
    Claims (13)
    [1]
    1. Extruded blow film, characterized by the fact that it comprises a polypropylene composition, said polypropylene composition comprises a random propylene copolymer (RPP), a polypropylene with high melt strength (HMS-PP), a polypropylene (B ), and optionally a bleach (C), where:
    (a) the random propylene copolymer (R-PP) comprises units derived from propylene and at least one other C2 to C20 alpha olefin.
    (b) polypropylene with high melt strength (HMSPP) has a g 'branching index below 1.0, (c) polypropylene (B) has an MFR2 (230 o C) measured according to ISO 1133 at least minus 400 g / 10 minutes, (d) the bleach (C) comprises at least one alpha nucleating agent (N), and further (i) the ramification index g 'of the random propylene copolymer (R-PP) and the g 'branching index of polypropylene (B) are higher than the g' branching index of polypropylene with high melt strength (HMS-PP), (ii) the random propylene copolymer (R-PP) shows flow rate melting point MFR2 (230 o C) measured according to ISO 1133 lower than polypropylene (B), (iii) the extruded film by a molten blow and / or the polypropylene composition (α) satisfies equation (I)
    Tm - Tc <30 (I) in which
    Tm is the melting temperature [ o C] constituting more than 50% of the total melting enthalpy Hm of the molten blow extruded film or of the DSC-measured polypropylene composition according to
    Petition 870190132049, of 12/12/2019, p. 47/55
    [2]
    2/4
    ISO 11357-3;
    Tc is the crystallization temperature [ o C] of the blown extruded film or of the polypropylene composition measured by DSC according to ISO 11357-3 and
    (β) has a melt flow rate MFR2 (230 o C) measured according to ISO 1133 from 1.0 to 5.5 g / 10 minutes.
    2. Extruded blow film, according to claim 1, characterized by the fact that the polypropylene film and / or composition has:
    (a) a strain hardening factor (SHF) of 1.2 to 3.0, measured at a strain rate of 3.0 s -1 and a Hencky strain of 3.0, and / or (b) a gel content determined as the insoluble fraction in hot xylene (XHI) equal to or below 1.0%, by weight, and / or (c) a fraction soluble in cold xylene (XCS) not exceeding 15.0%, in Weight.
    [3]
    3. Blow-extruded film according to claim 1 or 2, characterized by the fact that the number of units derived from C2 to C20 alpha olefins other than propylene is not more than 7.0% by weight in the film extruded by blowing and / or in the polypropylene composition.
    [4]
    4. Blow-extruded film according to any one of claims 1 to 3, characterized by the fact that the number of units derived from C2 to C20 alpha olefins other than propylene is in the range of 1.0 to 7.0% by weight in the random propylene copolymer (R-PP).
    [5]
    5. Extruded blow film, according to any
    Petition 870190132049, of 12/12/2019, p. 48/55
    3/4 of claims 1 to 4, characterized by the fact that the random propylene copolymer (R-PP) features:
    (a) a fraction soluble in cold xylene (XCS) determined in accordance with ISO 6427 not exceeding 15.0% by weight, and / or (b) an MFR2 (230 o C) measured in accordance with ISO 1133 not exceeding at 4.5 g / 10 minutes.
    [6]
    6. Extruded blow film according to any one of claims 1 to 5, characterized by the fact that polypropylene with high melt strength (HMS-PP) has a strain hardening factor (SHF) of 3.5 to 30.0 measured at a strain rate of 3.0 s -1 and a Hencky strain of 3.0.
    [7]
    7. Blow-extruded film according to any one of claims 1 to 6, characterized in that the polypropylene with high melt strength (HMS-PP) comprises units derived from:
    (i) propylene, and (ii) bifunctional unsaturated monomer (s) and / or multifunctional unsaturated low molecular weight polymer (s).
    [8]
    8. Blow-extruded film according to any one of claims 1 to 7, characterized by the fact that the polypropylene with high melt strength (HMS-PP) features:
    (a) a fraction insoluble in hot xylene (XHI) not exceeding 1.0% by weight, and / or (b) an MFR2 (230 o C) measured according to ISO 1133 from 1.0 to 10.0 g / 10 minutes.
    [9]
    Blow-extruded film according to any one of claims 1 to 8, characterized by the fact that polypropylene (B) is a propylene homopolymer (H-PP).
    [10]
    10. Film extruded by blow, according to any
    Petition 870190132049, of 12/12/2019, p. 49/55
    4/4 one of claims 1 to 9, characterized by the fact that the nucleating agent (s) alpha (N) is selected from the group consisting of:
    (i) salts of monocarboxylic acids and polycarboxylic acids, (ii) dibenzylidene sorbitol and dibenzylidene sorbitol derivatives substituted with C1-8 alkyl, (iii) salts of phosphoric acid diesters, and (iv) cycloalkane vinyl polymer and vinyl alkane polymer.
    [11]
    11. Blow-extruded film according to any one of claims 1 to 10, characterized in that the polypropylene composition comprises:
    (a) 50.0 to 92.0%, by weight, of the random propylene copolymer (R-PP), (b) 5.0 to 26.0%, by weight, of the polypropylene with high melt strength (HMS -PP), (c) 1.0 to 15.0%, by weight, of polypropylene (B), and (d) 0.01 to 5.0%, by weight, of bleach (C), based on total polypropylene composition.
    [12]
    Blow-extruded film according to any one of claims 1 to 11, characterized in that it comprises at least 80% by weight of, preferably consists of said polypropylene composition.
    [13]
    13. Packaging material, characterized by the fact that it comprises a blow-extruded film, as defined in any one of claims 1 to 12.
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-04-24| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-09-17| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2020-03-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-05-12| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 15/12/2010, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP09180609.1|2009-12-23|
    EP09180609A|EP2338930A1|2009-12-23|2009-12-23|Blownfilm grade showing superior stiffness, transparency and processing behaviour|
    PCT/EP2010/069788|WO2011076636A1|2009-12-23|2010-12-15|Blownfilm grade showing superior stiffness, transparency and processing behaviour|
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