Polymeric composition and sealant layer with same

Description

BASIS

[0001] Plastic films find use in a wide variety of packaging applications, such as bags, containers, cups, pouches, tubes, and trays. Laminates, monolayer films and multilayer films with a heat sealable layer are often used in form-fill-seal (FFS) machines. The FFS equipment produces a continuous stream of packages from the film that can be closed by a film-to-film seal.

[0002] Film-to-film sealing closures are made by placing a film between opposing sealing jaws that apply pressure and provide heat above the film start temperature. The sealed closures are often stronger after the seal has cooled down to ambient temperature. In order to increase production capacity, the packages are filled with the product before the seal has cooled down completely. Thus, in the case of heat-sealed closures, it is necessary to provide sufficient strength very quickly without the need to cool the package to ambient temperature. Otherwise, the heat seal closure will be of reduced value as it will lead to product rejection, waste and additional costs.

[0003] In addition, in the case of films used for sterilization packages, there is a need to provide seals that can withstand the elevated temperatures required for sterilization. Sterilization packages typically are exposed to temperatures greater than 121 ° C or greater than 130 ° C for extended periods of time to sterilize their contents.

[0004] There is therefore a continuing need in the art to develop improved films for FFS applications. In particular, there is a need for films which have a low seal initiation temperature and high hot tack strength over a wide temperature range to increase production efficiency in packaging procedures such as FFS procedures. There is a further need for films which, in addition to the above-mentioned properties, have a strong high-temperature seal.

SUMMARY

[0005] The present disclosure provides a polymeric composition and films made therefrom. When the present polymeric composition is formed into a film (or film layer), it exhibits (i) a low seal initiation temperature, (ii) high heat seal strength over a wide temperature window, and (iii) high heat seal strength. Furthermore, the film composed of the present polymeric composition has a high temperature seal strength suitable for use as a film for sterile packaging.

[0006] The present disclosure provides a polymeric composition.

[0007] The present disclosure provides a film and includes a first layer made from a polymeric composition comprising:

(A) propylene / α-olefin interpolymer;

(B) an ethylene-based polymer;

(C) a block composite comprising:

i) a propylene-based crystalline polymer;

ii) an ethylene / α-olefin polymer; and iii) a block copolymer comprising a crystalline propylene based block and an ethylene / α-olefin block, and a second layer composed of an olefin based polymer.

EP-2622014B1PL

[0008] The present disclosure provides a bag for sterilization and includes a first layer, a second layer, and optionally a third layer. The first layer is composed of a polymeric composition containing:

(A) propylene / α-olefin interpolymer;

(B) an ethylene-based polymer;

(C) a block composite comprising:

i) a propylene-based crystalline polymer;

ii) an ethylene / α-olefin polymer; and iii) a block copolymer comprising a propylene based crystal block and an ethylene / α-olefin block. The second layer is composed of an olefin-based polymer.

[0009] An advantage of the present disclosure is an improved polymeric composition that provides improved seal properties when formed into a film or film layer, such as low seal initiation temperature and / or high heat seal strength over a wide temperature window, and / or high heat seal strength. hot seal.

[0010] An advantage of the present disclosure is an improved film for heat seal applications.

BRIEF DESCRIPTION OF THE DRAWINGS

[0011] 'FIG. 1 is a top view of a sterilization bag according to an embodiment of the present disclosure.

FIG. 2 is a top view of a multi-layer film according to an embodiment of the present disclosure.

FIG. 3 is a top view of a multi-layer film according to an embodiment of the present disclosure.

FIG. 4 is a plot of the hot tack strength and temperature for comparative samples and embodiments according to the present disclosure.

FIG. 5 is a graph showing the heat seal temperature window for comparative samples and embodiments according to the present disclosure.

FIG. 6 is a plot of the heat seal strength and the seal temperature for the comparative samples and embodiments of the present disclosure.

FIG. 7 is a graph showing the coefficients of friction for comparative samples and embodiments according to the present disclosure.

FIG. 8 is a graph showing transparency for comparative samples and embodiments according to the present disclosure.

FIG. 9 is a graph showing the heat seal strength at 150 ° C for comparative samples and embodiments according to the present disclosure.

DETAILED DESCRIPTION

1. Composition

[0012] The present disclosure provides a polymeric composition.

In one embodiment, a polymeric composition is provided which includes:

(A) propylene / α-olefin interpolymer;

(B) an ethylene-based polymer; and (C) a block composite comprising:

(i) a propylene-based crystalline polymer;

(ii) an ethylene / α-olefin polymer; and (iii) a block copolymer comprising a propylene based crystal block and an ethylene / α-olefin block.

EP-2622014B1PL

[0013] The polymeric composition may optionally contain (D) an olefin-based polymer and / or (E) additives. In one embodiment, the polymeric composition comprises 50 wt. up to 95 wt.% % of component (A), 1 wt. up to 30 wt.% % of component (B) and 1 wt. up to 30 wt.% component (C). The weight percentage is based on the total weight of the composition. It is understood that the amount of each component (A) - (E) may be adjusted to obtain 100 wt%. the polymeric composition.

(A) Propylene / α-olefin interpolymer

[0014] The present composition comprises component (A) propylene / α-olefin interpolymer. The propylene / α-olefin interpolymer is a propylene based polymer. For the purposes of this disclosure, ethylene is considered an α-olefin. Non-limiting examples of suitable comonomers include ethylene, C4-20 α-olefins such as 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene; C4-20 diolefins such as 1,3-butadiene, 1,3-pentadiene, norbornadiene, 5-ethylidene-2-norbornene (ENB) and dicyclopentadiene; Cs-4o vinyl aromatics including styrene, O-, m-, and p-methylstyrene, divinylbenzene, vinylbiphenyl, vinylnaphthalene, and halogen substituted Cs-4o vinyl aromatics such as chlorostyrene and fluorostyrene. The α-olefins may also contain a cyclic structure such as cyclohexane or cyclopentane in which case it is an α-olefin such as 3-cyclohexyl-1-propene (allylcyclohexane) and vinylcyclohexane.

[0015] In an embodiment, the propylene / α-olefin interpolymer is a propylene / ethylene copolymer. The propylene / ethylene copolymer contains from 1 wt. % up to 40 wt.% units derived from ethylene (based on the total weight of the propylene / ethylene copolymer). In a further embodiment the propylene / ethylene copolymer has a density of 0.86 g / cm³ up to 0.90 g / cm³ and / or a melt flow rate (MFR) from 0.5 g / 10 min to 10 g / min, and / or a total crystallinity from 10% to 40%, and / or a melting point (Tm) from 70 ° C or 80 ° C to 90 ° C or 95 ° C. Non-limiting examples of a suitable propylene / ethylene copolymer are the propylene / ethylene copolymers sold under the tradename VERSIFY (such as VERSIFY 2200 and VERSIFY 3200) available from The Dow Chemical Company, Midland, Michigan and the propylene / ethylene copolymer sold under the tradename VISTAMAXX available from ExxonMobil Corporation , Irving, Texas.

[0016] In an embodiment, the propylene / ethylene copolymer has a density of 0.86 g / cm³ up to 0.89 g / cm³ % and / or MFR from 1 g / 10 min to 3 g / 10 min, and / or total crystallinity from 20 wt.%. % to 25 wt.%, and / or a Tm from 80 ° C to 85 ° C.

[0017] In an embodiment, the propylene / ethylene copolymer has a density of 0.86 g / cm³ up to 0.88 g / cm³ and / or MFR from 5 g / 10 min to 10 g / 10 min, and / or total crystallinity from 25% to 35%, and / or a Tm from 80 ° C to 90 ° C.

[0018] In an embodiment, the propylene / ethylene copolymer is a monophasic propylene / ethylene copolymer. In other words, the propylene / ethylene copolymer excludes heterophasic copolymers such as propylene impact copolymer. [0019] In an embodiment, the propylene / α-olefin interpolymer has a molecular weight distribution (MWD) of from 2.0 or 2.5 to 4.0 to 3.5. In a further embodiment the propylene / α-olefin interpolymer is a propylene / ethylene copolymer with a MWD of from 2.0 or 2.5 to 4.0 to 3.5.

[0020] The propylene-based polymer may include two or more embodiments disclosed herein.

(B) Ethylene-based polymer

[0021] The present polymeric composition comprises component (B) an ethylene-based polymer. The ethylene-based polymer may be an ethylene homopolymer or an ethylene copolymer. The comonomer may be an α-olefin, such as a C3-20 linear, branched or cyclic α-olefin. Non-limiting examples of suitable C3-20 aolefins include propene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene. The α-olefins may also contain a cyclic structure such as cyclohexane or cyclopentane in which case it is an α-olefin such as 3-cyclohexyl-1-propene (allylcyclohexane) and vinylcyclohexane. Although they are not α-olefins in the classical sense of the term, for the purposes of this disclosure certain cyclic olefins are

EP-2622014B1PL such as norbornene and related olefins, especially 5-ethylidene-2-norbornene, are α-olefins and may be used in place of some or all of the α-olefins described above. Likewise, styrene and its related olefins (e.g., α-methylstyrene, etc.) are α-olefins for the purposes of this disclosure. Illustrative ethylene polymers include ethylene / propylene, ethylene / butene, ethylene / 1-hexene, ethylene / 1-octene, ethylene / styrene, and the like. Illustrative ethylene terpolymers include ethylene / propylene / 1-octene, ethylene / propylene / butene, ethylene / butene / 1-octene, ethylene / propylene / diene monomer (EPDM), and ethylene / butene / styrene. The copolymers can be random or block.

[0022] In an embodiment, the ethylene-based polymer is high density polyethylene. The term "high-density polyethylene" (or HDPE) as used herein is an ethylene-based polymer with a density equal to or greater than 0.941 g / cm 2.³. A non-limiting example of a suitable HDPE is 12450N available from The Dow Chemical Company, Midland, Michigan.

[0023] In an embodiment, the HDPE has a density of 0.941 g / cm³ up to 0.970 g / cm³ and / or a crystallinity of at least 55%, and / or a melting point of at least 125 ° C, and / or a melt index (Ml) from 1.0 g / 10 min to 20.0 g / 10 min.

[0024] In an embodiment, the HDPE has a density of 0.950 g / cm³ and a melt index of 12.0 g / 10 min.

[0025] As used herein, total weight is the total weight of component (A) plus the weight of component (B). The cumulative weight is the parameter by which to evaluate component (A) versus component (B) and vice versa. In other words, the total weight excludes component (C) and optional components (D) and (E). In an embodiment, the total weight comprises greater than 50 wt.%, Greater than 60 wt.%, Or greater than 70 wt.%. component (A).

[0026] The ethylene-based polymer may include two or more embodiments disclosed herein.

(C) Block composite

[0027] The present polymeric composition comprises a block composite. Block composite includes:

(i) a propylene-based crystalline polymer;

(ii) an ethylene / α-olefin polymer; and iii) a block copolymer comprising a propylene-based crystal block and an ethylene / α-olefin block. [0028] The term block copolymer or segmented copolymer refers to a polymer comprising two or more chemically different regions or segments (referred to as "blocks") preferably linearly connected, that is, a polymer containing chemically diverse units which are connected end-to-end with respect to polymerized ethylene functionality, not for side or graft. In an embodiment, the blocks differ in the amount or type of comonomer incorporated therein, the density, the amount of crystallinity, the size of the crystallite attributable to the polymer in the composition, the type or degree of tacticity (isotactic or syndiotactic), regio-regularity or regio-irregularity, the amount of branching, including branching long-chain or hyperbranching, homogeneity, or other chemical or physical property. The block copolymers of the present disclosure are characterized by a unique distribution of both polydispersity (PDI or Mw / Mn) and block length distribution and / or block number distribution due, in a preferred embodiment, to the influence of the chain transfer agent (s). (shuttling agent) in combination with the catalyst (s).

[0029] The block copolymer is a new polymer comprising a soft copolymer, a hard polymer and a block copolymer that has a soft segment and a hard segment, the hard segment of the block copolymer having the same composition as the hard polymer in the block composite, and the soft segment of the block copolymer having the same composition as the soft polymer in the block composite. The block copolymer can be linear or branched. More specifically, when the block composite is manufactured in a continuous process, it is desirable to have a PDI

ΕΡ-2622014Β1 Fetus 1.7 to 15, or 1.8 to 3.5, or 1.8 to 2.2, or 1.8 to 2.1. When the block composite is produced in a batch or semi-batch process, it has a PDI of 1.0 to 2.9, or 1.3 to 2.5, or 1.4 to 2.0, or 1.4 to 1.8 .

[0030] The "hard" segments refer to highly crystalline blocks of polymerized units in which the monomer is present in an amount greater than 95 percent by weight, and preferably greater than 98 percent by weight. In other words, the comonomer content of the hard segments is less than 5 weight percent, preferably less than 2 weight percent. In some embodiments, the hard segments include all or substantially all of the propylene units. The "soft" segments, on the other hand, refer to amorphous, substantially amorphous or elastomeric blocks of polymerized units in which the comonomer content is greater than 10 mol%.

(i) Block Composite Index

[0031] The present examples (Table 3, 4) show that the insoluble fractions contain a significant amount of ethylene which would not be present if the polymer were simply a blend of an iPP homopolymer and an EP copolymer. To quantify this extra ethylene, a mass balance calculation can be performed to estimate the block composite index from the amount of xylene insoluble and soluble fractions and the wt% ethylene present in each fraction.

[0032] Summing the wt% ethylene of each fraction as equation 1 gives the total wt% ethylene (in polymer). This mass balance equation can also be used to calculate the amount of each component in a double blend or it can be extended to a ternary or n-component blend.

wt.% C._2ogblas = W._{stainless steel body}and_on (wt% C2_{niero2pus2c2a}and_on) + ^ soluble (wt% C_{2ro2pus2c2alna})

Eq. 1

[0033] Using Equations 2 to 4, the amount of soft block (providing a source of extra ethylene) present in the insoluble fraction is calculated. Substituting the C2 wt% insoluble fraction on the left hand side of Equation 2, you can calculate wt% hard iPP and wt% soft EP using Equations 3 and 4. Note that the wt% ethylene in soft EP is set to be equal to the wt% ethylene in the xylene soluble fraction. The wt% ethylene in the iPP block is set to zero or, if known from its melting point from DSC or other composition measurement, this value may be inserted in its place.

% By weight C2_{generallyorro2pu52chalnk5len} — ⁱⁿiPPtwardyC °^wa9 ^ 2iPP) + ⁱⁿEPoft (° /^oWag ^ 2EPoft)

Eq. 2% by weight C.₂ ... . . . ,,, · -% waq. C.₂„_n . ,,.

⁰⁷ generally or xylene insoluble & lt; E & gt;_iPPtWards = wt% C._{2ppi d} - wt% C._2pp . _{of the Penal Code}.

^ iPPhard ^ EPoft

Eq. 3 ^ EPoft 1 ^ IPPhard

Eq. 4

[0034] Once the "additional" ethylene present in the insoluble fraction has been calculated, the only way to obtain the EP copolymer present in the insoluble fraction is to bind the EP polymer chain to the iPP polymer block (or else it could be extracted into the xylene soluble fraction). Thus, when the iPP block crystallizes, it prevents solubilization of the EP block.

EP-2622014B1PL

[0035] For the evaluation of the composite block index, the relative amount of each block must be considered. The ratio between soft EP and hard iPP is used to estimate it. The ratio of EPP soft polymer and hard iPP polymer can be calculated using Equation 2 from the mass balance of total ethylene measured in the polymer. Alternatively, it can also be estimated from the mass balance of monomer and comonomer consumption during polymerization. Refer to Table 3 for the estimated ratio of iPP and EP present in the diblock copolymer for all runs. The hard iPP weight fraction and the soft weight fraction are calculated using Equation 2 and assume that the hard iPP is ethylene-free. The weight% ethylene in soft EP is the amount of ethylene present in the xylene soluble fraction.

[0036] For example, if the inventive block composite (C) of iPP (C) (i), EP (C) (ii) and the iPPEP diblock (C) (iii), it generally comprises 47 wt. % C2 and is made under the conditions for the production of soft EP polymer with 67 wt. % Of C2 and zero ethylene iPP homopolymer, the amount of soft EP and hard iPP is 70 wt.%. and 30 wt.%, respectively (as calculated using Equations 3 and 4). If the percentage of EP is 70 wt% and the iPP is 30 wt%, the relative ratio of EP: iPP blocks could be expressed as 2.33: 1.

[0037] Thus, if the skilled person would extract the polymer with xylene and recover 40 wt. % insoluble and 60 wt. soluble, this would be an unexpected result and would lead to the conclusion that the block copolymer fraction of the invention was present. If the ethylene content of the insoluble fraction is then measured to be 25 wt.%. % Of C2, one can solve Equations 2 through 4 to calculate this additional ethylene and get 37.3 wt. % EP soft polymer and 62.7 wt. hard iPP polymer.

[0038] Since the insoluble fraction contains 37.3 wt. % of EP copolymer, it must be added to an additional 16 wt. of the iPP polymer, based on an EP: iPP block ratio of 2.33: 1. This gives an estimated amount of diblock in the insoluble fraction of 53.3 wt%. For all polymer (unfractionated) the composition is reported to be 21.3 wt.%. % iPP-EP diblock, 18.7 wt. % of the iPP polymer and 60 wt. EP polymer. As the compositions of these polymers are novel, the term block composite index (or BCI) is defined herein as equal to the weight percent of the diblock divided by 100% (ie weight fraction). The block composite index value can range from 0 to 1, with 1 being 100% of the inventive diblock, and zero would be for a material such as a conventional blend or a random copolymer. In the example described above, the block composite index for the block composite is 0.213. The insoluble BCI fraction is 0.533 and the soluble BCI fraction is assigned a value of zero.

[0039] Depending on the estimate for the total polymer composition and the error in the analytical measurements that is used to estimate the composition of the hard and soft blocks, an error of 5 to 10% is possible in the calculated block composite index value. Such an estimate includes the wt.%. C2 in iPP hard block as measured by DSC melting point, NMR analysis or process conditions; average wt.% C2 in soft block as estimated from xylene soluble solids composition, or by NMR, or from soft block DSC melting point (if detected). But in general, the calculation of the composite block index explains the presence of "extra" ethylene in the insoluble fraction and the only way to obtain the EP copolymer in the insoluble fraction is to link the EP polymer chain to the iPP polymer block (or else to extract it into a xylene soluble fraction).

[0040] The block composite polymers of the present disclosure are prepared by a method comprising contacting the addition polymerizable monomer or mixture with a composition comprising at least one addition polymerization catalyst, a cocatalyst, and a chain shuttling agent, the process being characterized by producing at least some

The growing polymer chains under varying process conditions in two or more reactors operating under steady state polymerization conditions or in two or more zones of a reactor operating under closed flow polymerization conditions.

[0041] In an embodiment, the composite block comprises a block polymer fraction that has the most likely block length distribution. Preferred polymers according to the present disclosure are block copolymers containing 2 or 3 blocks or segments. In a polymer containing three or more segments (i.e., blocks separated by different blocks), each block may be the same or different chemically and generally characterized by a distribution of properties. The method of producing polymers uses chain transfer ( chain shuttling as a method of extending the life of the polymer chain such that a substantial fraction of the polymer chains exits at least the first reactor in a series of multiple reactors or from the first reactor zone in a multi-zone reactor operating under substantially plug flow conditions in the form of a chain transfer agent terminated polymer, and The polymer chain is subject to different polymerization conditions in the next reactor or in the next polymerization zone. The different polymerization conditions in the respective reactors or zones include the use of different monomers, comonomers or monomer / comonomer (s) ratio, different polymerization temperatures, pressures or partial pressures of different monomers, different catalysts, different monomer gradients or any other difference leading to the production of different polymer segment. Thus, at least a portion of the polymer comprises two, three or more, preferably two or three, differentiated intramolecularly arranged polymer segments.

[0042] The following mathematical treatment of the prepared polymers is based on theoretically derived parameters which are believed to be relevant and demonstrate that, especially in two or more continuous steady state reactors or zones connected in series. Steady State) under which there are different polymerization conditions and to which the growing polymer is exposed, the lengths of the polymer blocks produced in each reactor or zone will follow the most likely distribution, derived as follows, where pi is the probability of the polymer propagating in the reactor in with respect to the block sequence from the catalyst and. The theoretical analysis is based on the standard assumption and methods known in the art and used to predict the effects of polymerization kinetics on molecular architecture, including reaction rate parameters from the mass law that are not influenced by chain or block length and the assumption that polymer chain growth is complete in very short time compared to the average residence time in the reactor. Such methods were previously disclosed in WH Ray, J. Macromol. Sci., Rev. Macromol. Chem., C8.1 (1972) and AE Hamielecand JF MacGregor, Polymer Reaction Engineering, KH Reichert and W. Geisler, Ed., Hanser, Munich, 1983. Furthermore, it is assumed that as a result of each chain transfer reaction event, The chain shuttling reaction in a given reactor produces a single polymer block, while the polymer transfer is terminated with a chain transfer agent (chain transfer agent). chain shuttling agent to another reactor or zone and exposure to different polymerization conditions produces a different block. For catalyst i, the proportion of sequence n produced in the reactor is given by Xi [n], where n is an integer from 1 to infinity representing the total number of monomer units in the block.

Xi [n] = (1-pi) pi (nl) most likely block length distribution

ΕΡ-2622014Β1 PL numeric average block length

[0043] If more than one catalyst is present in a reactor or zone, each catalyst has a probability of propagation (pi) and thus has a unique average block length and distribution for the polymer produced in that reactor or zone. In the most preferred embodiment, the propagation probability is defined as:

. ₌____________Rpfil____________ ^pi Rp [i] + Rt [i] + Rs [i] + [Ci] for each catalyst i = {1,2 ...}, where

Rp [i] = Local monomer consumption rate by catalyst i, (moles / l / time),

Rt [i] = Total chain transfer and termination rate for catalyst i, (moles / L / time) i

Rs [i] = Local chain shuttling rate with dormant polymer, (moles / L / time).

[0044] For a given reactor, the rate of polymer propagation, Rp [i], is determined using the apparent rate constant, kpi, multiplied by the total monomer concentration, [M], and multiplied by the local catalyst concentration i, [Ci] as follows:

Rp [i] = kpi [M] [Ci]

[0045] Chain transfer, termination and shuttling are defined as a function of chain transfer to hydrogen (H2), elimination of beta to hydride, and chain transfer to chain shuttling agent (CSA). ). The amounts of [H2] and [CSA] are in molar concentrations, and each k-value index is a rate constant for the reactor or zone:

Rt [i] = kH2i [H2] [Ci] + kpi [Ci] + kai [CSA] [Ci]

[0046] Sleeping polymer chains are formed when the polymeric moiety is transferred to the CSA and it is assumed that all CSA moieties that react are paired with the sleeping polymer chain. The dormant polymer chain shuttling rate to the catalyst i is given below, where [CSAf] is the feeding concentration of CSA and the amount ([CSAf] - [CSA]) represents the concentration of dormant polymer chains:

Rs [i] = kai [Ci] ([CSAf] - [CSA])

[0047] From the above theoretical considerations, it can be seen that the overall block length distribution for each block of block copolymer produced is the sum of the block length distribution previously given by Xi [n], weighted by the local polymer production rate for catalyst i. That is, a polymer produced under at least two different polymer production conditions will have at least two different blocks or segments, each having the most likely block length distribution.

[0048] Suitable catalysts and catalyst precursors for making block composite (C) include metal complexes such as those disclosed in WO2005 / 090426, especially those disclosed from page 20 line 30 to page 53 line 20, which is incorporated herein by reference. Suitable catalysts are also disclosed in US 2006/0199930, US 2007/0167578, US 2008/0311812, US 7,355,089 B2 or WO 2009/012215. Suitable cocatalysts are those disclosed in WO2005 / 090426, especially those disclosed on page 54, line 1 to page 60, line 12, which are hereby incorporated by reference. Suitable chain shuttling agents are those disclosed in WO2005 / 090426, especially those disclosed on page 19, line 21 to page 20, line 12, which are hereby incorporated by reference. Particularly preferred chain transfer agents are dialkyl zinc compounds.

EP-2622014B1PL

[0049] The block polymers in the block composition include, 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, and / or one or more C5-C20 α-olefin comonomers, and / or one or more additional copolymerizable comonomers. Additional suitable comonomers are selected from diolefins, cyclic olefins and cyclic diolefins, halogenated vinyl compounds and vinylidene aromatics.

[0050] The comonomer content of the resulting polymers that are block composites can be measured using any suitable technique, preferably techniques based on nuclear magnetic resonance (NMR) spectroscopy. It is highly desirable that some or all of the polymer blocks contain 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 remaining polymer blocks (hard segments), if any, mainly consisted of propylene, 1-butene or 4-methyl-1-pentene in polymerized form. Preferably, such segments are: highly crystalline or stereospecific polypropylene, polybutene or poly-4-methyl-1-pentene, especially isotactic homopolymers. [0051] Further preferably, the block copolymers of the present disclosure contain from 10 to 90 percent crystalline or relatively hard segments and 90 to 10 percent amorphous or relatively amorphous segments (soft segments), preferably 20 to 80 percent crystalline or relatively hard segments, and 80 up to 20 percent of amorphous or relatively amorphous segments (soft segments) most preferably from 30 to 70 percent crystalline or relatively hard segments and 70 to 30 percent amorphous or relatively amorphous segments (soft segments). Within the soft segments, the mole percent of the comonomer may range from 10 to 90 mole percent, preferably from 20 to 80 mole percent, and most preferably from 33 to 75 mole percent. In the case where the comonomer is ethylene, it is preferably present in an amount of 75 mole percent. Preferably, the copolymers contain hard segments which constitute 90 mole% to 100 mole% propylene. The hard segments may constitute more than 90 mole%, preferably more than 93 mole%, most preferably more than 95 mole% propylene and most preferably more than 98 mole% propylene. Such hard segments have suitable melting points which are 80 ° C and higher, preferably 100 ° C and higher, more preferably 115 ° C and higher, most preferably 120 ° C and higher. Preferably, the block copolymers of the present disclosure contain from 10 to 90 percent crystalline or relatively hard segments and 90 to 10 percent amorphous or relatively amorphous segments (soft segments). Within the soft segments, the mole percent of the comonomer may range from 5 to 90 mole percent, preferably from 10 to 60 mole percent. In the case where the comonomer is ethylene, it is preferably present in an amount of 10 wt.%. % to 75 wt.%, more preferably 30 wt.%. up to 70 wt.%

[0052] Preferably, the copolymers contain hard segments which constitute 80 wt. up to 100 wt.% propylene. The hard segments may constitute more than 90 wt%, preferably more than 95 wt%, and most preferably more than 98 mole% propylene.

[0053] The block composite polymers of the present disclosure can differ from conventional, random copolymers, physical blends of polymers, and block copolymers made by sequential addition of monomers. Block composites can differ from random copolymers in such characteristics as higher melting points for a comparable amount of comonomer, block index and composite index

EP-2622014B1PL as described below; from physical blends with features such as block index and block composite index, better tensile strength, improved fracture strength, finer morphology, improved optical properties and higher impact toughness at lower temperature; from block copolymers prepared by sequential addition of monomers by molecular weight distribution, rheology, shear densification, rheology index rheology ratio) and that there is a polydispersity of the blocks.

[0054] In some embodiments, the block composites of the present disclosure have a Block Composite Index (BCI) as defined below that is greater than zero but less than about 0.4, or from about 0.1 to about 0.3. In other embodiments, the BCI is greater than about 0.4 and is up to about 1.0. Additionally, the BCI may range from about 0.4 to about 0.7, from about 0.5 to about 0.7, or from about 0.6 to about 0.9. In some embodiments, the BCI ranges from about 0.3 to about 0.9, from about 0.3 to about 0.8, or from about 0.3 to about 0.7, from about 0.3 to about 0.6. , from about 0.3 to about 0.5, or from about 0.3 to about 0.4. In other embodiments, the BCI ranges from about 0.4 to about 1.0, from about 0.5 to about 1.0, or from about 0.6 to about 1.0, from about 0.7 to about 1.0. , from about 0.8 to about 1.0, or from about 0.9 to about 1.0.

[0055] Other desirable compositions of the present disclosure are elastomeric block copolymers of propylene, 1-butene or 4-methyl-1-pentene with ethylene and optionally with one or more α-olefinic or diene monomers. Preferred α-olefins for use in this embodiment of the present disclosure are represented by the formula CH2 = CHR *, wherein R * is a linear or branched alkyl group of 1 to 12 carbon atoms. Examples of suitable α-olefins include, but are not limited to, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene (when copolymerized with propylene), and 1-octene. Suitable dienes for use in the preparation of such polymers, especially multi-block polymers of the EPDM type, include conjugated or unconjugated, straight chain or branched, cyclic or polycyclic dienes containing from 4 to 20 carbons. Preferred dienes include 1,4-pentadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, cyclohexadiene and 5-butylidene-2-norbornene. A particularly preferred diene is 5-ethylidene-2-norbornene. The resulting product may contain isotactic homopolymer segments, alternating with elastomeric copolymer segments formed in situ during polymerization. Preferably, the product may contain only an elastomeric block copolymer of propylene, 1-butene or 4-methy-1-pentene with one or more comonomers, especially ethylene.

[0056] Since diene-containing polymers contain alternating segments or blocks containing greater or lesser amounts of diene (including none) and alpha-olefin (including none), the total amount of diene and alpha-olefin can be reduced without losing the obtained properties of the polymer. That is, because diene and alpha-olefin monomers are preferentially incorporated into one type of polymer block and not homogeneously or randomly throughout the polymer, they are more efficiently used and consequently the polymer crosslink density can be better controlled. Such crosslinkable elastomers and cured products have favorable properties, including higher tensile strength and better elastic recovery.

[0057] In an embodiment, the block composite has a weight average molecular weight (Mw) of from 10,000 to 2,500,000, preferably from 35,000 to 1,000,000, and more preferably from 50,000 to 300,000, preferably from 50,000 to 200,000. Block composite (C) is disclosed in co-pending US Application 2012/208946 (Patent Application No. 61 / 248,160 filed October 2, 2009).

(ii) Crystalline block composite

EP-2622014B1PL

[0058] The block composite (C) may be a crystalline block composite. The term "crystalline block composite" (CBC) refers to a polymer comprising a crystalline ethylene-based polymer (CEP), a crystalline propylene-based polymer (CAOP), and a block copolymer that has a crystalline ethylene block (CEB) and a crystalline propylene block (CAOB) wherein the CEB in the block copolymer has substantially the same composition as the CEP in the block copolymer and the CAOB in the block copolymer has substantially the same composition as the CAOP in the block composite. Block copolymers can be linear or branched. More specifically, each of the respective block segments may contain long-chain branches with a similar composition to the respective block, but the block copolymer segment is substantially linear as opposed to containing grafted or branched blocks. When the crystalline block composites are produced continuously, it is desirable that they have a PDI of 1.7 to 15, preferably 1.8 to 5, more preferably 1.8 to 3.5, and most preferably 1.8 to 2. 5.

[0059] Crystalline propylene-based block (CAOB) refers to highly crystalline blocks of polymerized alpha-olefin units in which the propylene monomer is present in an amount greater than 90 mole percent, preferably greater than 93 mole percent, more preferably greater than 95 percent. mole percent, and preferably greater than 96 mole percent. In other words, the comonomer content of the CAOB is less than 10 mole percent and preferably less than 7 mole percent, more preferably less than 5 mole percent and most preferably less than 4 mole percent. Such CAOBs have suitable melting points which are 80 ° C and higher, preferably 100 ° C and higher, more preferably 115 ° C and higher, and most preferably 120 ° C and higher. Whereas CEB refers to blocks of polymerized 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 mole%. molar. Such CEBs have suitable melting points which are preferably 75 ° C and higher, more preferably 90 ° C and 100 ° C and higher.

[0060] Preferably, the crystalline block composite polymers of the present disclosure comprise from 0.5 to 94 wt.%. CEP, 0.5 to 94 wt.% CAOP and 5 to 99 wt. block copolymer . More preferably, the block composite crystalline polymers comprise from 0.5 to 79 wt. % CEP, 0.5 to 79 wt.%. CAOP and from 20 to 99 wt. % of the block copolymer and more preferably from 0.5 to 49 wt. % CEP, 0.5 to 49 wt.% CAOP and 50 to 99 wt. block copolymer.

[0061] Preferably, the block copolymers of the present disclosure include from 5 to 95 percent by weight of crystalline ethylene blocks (CEBs) and 95 to 5 percent of crystalline propylene blocks (CAOBs). More preferably, the block copolymers comprise 25 to 75 wt. Of CEB and 75 to 25 wt.%. CAOB and even more preferably include 30 to 70% CEB and 70 to 30 wt.%. CAOB.

[0062] Further preferably, the crystalline block composites according to this embodiment of the present disclosure have a weight average molecular weight (Mw) of 1,000 to 2,500,000, preferably 35,000 to 1,000,000, and more preferably 50,000 to 500,000, 50,000 to 300,000. and preferably from 50,000 to 200,000.

[0063] In an embodiment, the block composite (C) comprises an isotactic crystalline propylene homopolymer, or iPP, (C) (i), an ethylene / propylene copolymer, or EP, (C) (ii), and a block copolymer (C) (iii) . The (C) (iii) block copolymer subcomponent includes a diblock of formula (1) below (EP) - (iPP) (1)

[0064] The term EP denotes a segment of polymerized monomeric ethylene and propylene units. The term iPP denotes an isotactic propylene homopolymer segment or a substantially isotactic propylene homopolymer segment with minimal (<1%) atactic or syndiotactic defects.

EP-2622014B1PL

[0065] In an embodiment, the block composite (C) has an ethylene content greater than 20 wt%. % or greater than 30 wt.%, or greater than 35 wt.%. The weight percentage of ethylene is based on the total weight of the block composite (C).

[0066] In an embodiment, component (C) (iii) is present in an amount of greater than 15 wt.%. % or greater than 20 wt.%, or greater than 25 wt.%, or greater than 30 wt.%, or greater than 50 wt.%. to about 80 wt.% based on the total weight of component (C).

[0067] In an embodiment, the block composite (Component C) has a density of 0.865 to 0.90 g / cm³ or 0.897 g / cm³ and / or a melt index (I2) from 1 to 50 g / 10 min.

[0068] In an embodiment, the block composite (C) has a melt index of from about 1 or about 2, or about 3, or about 4, or about 5, or about 6 to about 40, or about 35, or about 20, or about. 15 or about 13.

[0069] In an embodiment, the block composite (C) has 110/12 from about 6 or about 7, or about 8 to about 20, or about 19, or about 17, or about 15, or about 13, or about 12, or around 11.

D. Olefin based polymer

[0070] The present polymeric composition may optionally include an olefin-based polymer. Non-limiting examples of suitable olefin-based polymers include propylene-based polymer and ethylene-based polymer. Non-limiting examples of a suitable ethylene-based polymer include linear low density polyethylene (LLDPE), low density polyethylene (LDPE), HDPE, homogeneously branched polyethylene (non-limiting examples include polymers sold under the trade name EXXACT from Εχχοη Mobil and under the trade name TAFMER from Mitsui). a substantially linear ethylene polymer (non-limiting examples include polymers sold under the trade names AFFINTY and ENGAGE from The Dow Chemical Company), an olefin-based functionalized polymer and any combination thereof.

[0071] The substantially linear ethylene / α-olefin (ŚLEP) interpolymer is a homogeneously branched polymer and is described in US Patent Nos. 5,272,236,5,278,272, 6,054,544, 6,335,410, and 6,723,810. Substantially linear ethylene / α-olefin interpolymers have long chain branching. The long chain branches have the same comonomer distribution as the polymer backbone and may be approximately the same length as the polymer backbone length. Substantially linear, typically, refers to a polymer that is substituted, on average, 0.01 long chain branches per 1,000 carbons to 3 long chain branches per 1,000 carbons. The length of the long chain branch is greater than the length of the carbons in the short chain branch formed by the inclusion of one comonomer in the polymer backbone.

[0072] Some polymers may be substituted with 0.01 long chain branches per 1000 carbons to 3 long chain branches per 1000 carbons, more preferably from 0.05 long chain branches per 1000 carbons to 2 long chain branches per 1000 carbons, especially from 0.3 long chain branches per 1000 carbons, especially from 0.3 long chain branches per 1000 carbons. branches per 1,000 carbons to 1 long chain branch per 1,000 carbons.

[0073] The substantially linear ethylene / α-olefin interpolymers form a unique class of homogeneously branched ethylene polymers. They differ substantially from the well-known class of conventional homogeneously branched ethylene / α-olefin interpolymers and, furthermore, are not in the same class as conventional heterogeneous linear ethylene polymers "polymerized with a Ziegler-Natta catalyst (e.g., ultra-low density polyethylene ( ULDPE), rope low density polyethylene (LLDPE) or high density polyethylene (HDPE), made, for example, using the technique disclosed by Anderson et al. in US Patent 4,076,698); nor are they in the same class as highly branched high pressure free radical initiated polyethylenes such as, for example, low density polyethylene (LDPE), ethylene acrylic acid (EAA) copolymers, and ethylene vinyl acetate (EVA) copolymers.

EP-2622014B1PL

[0074] The homogeneously branched, substantially linear ethylene / α-olefin interpolymers useful in the present disclosure have excellent processability, even though they have a relatively narrow molecular weight distribution. Surprisingly, the melt index (110/12) according to ASTM D 1238 of substantially linear ethylene interpolymers can vary over a wide range and substantially independent of the molecular weight distribution (Mw / Mn or MWD). This unexpected behavior is in contrast to conventional homogeneously branched linear ethylene interpolymers such as those described, for example, by Elston in US 3,645,992, and heterogeneously branched, conventional linear ethylene polymerized interpolymers from Ziegler-Natta, such as those described, for example, , by Anderson et al., in US 4,076,698. Unlike substantially linear ethylene interpolymers, linear ethylene interpolymers (homogeneously or heterogeneously branched) have rheological properties such that as the molecular weight distribution increases, the 110/12 value also increases.

[0075] Long chain branching can be determined using 13C nuclear magnetic resonance (NMR) spectroscopy and can be quantified using the Randall method (Rev. Macromol. Chem. Phys., C29 (2 & 3), 1989, pp. 285-297), which this disclosure is herein incorporated by reference.

Two other methods include gel permeation chromatography coupled with a low-angle laser detector (GPCLALLS) and gel permeation chromatography coupled with a differential viscosity detector (GPCDV). The use of these techniques to detect long chain branching and the theories underlying them are well documented in the literature. See, for example, Zimm, BH, and Stockmayer, WH, J. Chem. Phys., 17.1301 (1949) and Rudin, A., Modern Methods of Polymer Characterization, John Wiley & Sons, New York (1991) pp. 103-112.

[0076] The olefin-based polymer may include a functionalized olefin-based polymer. Non-limiting examples of suitable olefin-based functionalized polymer include maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, ethylene acrylic acid copolymer, ethylene methacrylate copolymer, and any combinations thereof.

E. Accessories

[0077] The present polymeric composition may optionally contain one or more additives. Known additives can be incorporated into the resin composition so long as they do not detract from the purposes of this disclosure. Non-limiting examples of such additives include nucleating agents, antioxidants, acid scavengers, heat stabilizers, light stabilizers, ultraviolet light absorbers, lubricants, antistatic agents, pigments, dyes, dispersants. , inhibitors, neutralizing agents, foaming agents, plasticizers, fluidity agents, anti-blocking agents, slip additives and agents improving the strength of the weld.

[0078] The above-mentioned additives may be used in any combination and each may be present in the respective polymer composition in an amount of 0.0001 to 10 percent (or any given amount within or sub-range thereof) or in an amount of 0.001 to 1 percent. .0 percent.

[0079] The polymeric composition may include two or more embodiments disclosed herein.

2. Foil

[0080] The present disclosure provides films comprising the present polymeric composition. In other words, the present polymeric composition can be processed into a film. In execution, the foil is delivered and includes:

% (A) from 50 wt. up to 95 wt.% a propylene / α-olefin interpolymer;

(B) from 1 wt. up to 30 wt.% ethylene-based polymer and

% Of EP-2622014B1PL (C) from 1 wt. up to 30 wt.% block composite.

[0081] The film may optionally contain an olefin-based polymer (D) and / or additives (E). Components (A) - (E) may be any suitable component (A) - (E) as disclosed above for the polymer composition. In an embodiment, the foil comprises from 70 wt. up to 80 wt.% % Of component (A), 10 wt. up to 20 wt.% % Of component (B) i from 5 wt. up to 15 wt.% Ingredient (C). The weight percentage is based on the total weight of the film. The film has one, some, or all of the following properties as summarized in Table 1 below.

Table 1-Film properties

<td>Property</td><td>Unit</td><td>Range</td>

<td>Film thickness</td><td>milical</td><td>0.3 to 5</td>

<td>Kinetic Coefficient of Friction (FF)</td><td></td><td>0.15 to 1.2</td>

<td>Static coefficient of friction (FF)</td><td></td><td>0.15 to 1.2</td>

<td>Haze</td><td> %</td><td>0.5 to 15</td>

<td>Transparency</td><td> %</td><td>80 to 99.5</td>

<td>Hot seal strength peak</td><td>N / inch</td><td>3 to 18</td>

<td>Sealing initiation temperature (HTIT)</td><td>° C</td><td> 70-150</td>

<td>Sealing temperature peak</td><td>° C</td><td>60 to 140</td>

<td>Welding temperature window</td><td>° C</td><td>Wider than 50 ° C or wider than 55 ° C,</td>

<td>Hot seal strength at 150 ° C</td><td>N / inch</td><td>1 to 8</td>

[0082] A low coefficient of friction (COF) is desirable for improved processing and / or faster packaging. The coefficient of friction in Table 1 above is the film-to-foil coefficient of friction. A wide seal temperature window is advantageous for (i) lower seal initiation temperatures, (ii) improved seal durability at sterilization temperatures (120 ° C to 130 ° C), and (iii) faster processing rates. The heat seal strength at 150 ° C is favorable for sterilization applications.

[0083] The applicant has invented a film with the following desired combination of properties: low COF, wide seal temperature window, low seal initiation temperature and high heat seal strength at elevated temperature.

[0084] Moreover, the present film has the desired optical properties: low haze and high transparency.

[0085] In an embodiment, the film has a seal initiation temperature (HTIT) of less than 80 ° C or less than 75 ° C.

[0086] The present polymeric composition may be formed into a multi-layer film. The multilayer film structure can be laminated, extruded (cast / sheet), coextruded (cast / sheet), oriented (axially, biaxially, tenter frame, blow molding, two-stage blow, entrapped bladder) and combinations thereof.

[0087] In an embodiment, the present film is cross-link free. As used herein, a film is "cross-link free" when it has a gel content of less than 5% as measured by ASTM D-2765-84 Method A.

[0088] In an embodiment, the film has a thickness from about 0.3 mil to about 5.0 mil, or about 3.5 mil.

(A) Multilayer foil

[0089] The present disclosure provides a multi-layer film. In an embodiment, a multilayer film is provided that includes a first layer, a second layer and optionally a third layer. The first layer includes:

% Of EP-2622014B1PL (A) 50 wt. up to 95 wt.% % of a propylene / α-olefin interpolymer, (B) 1 wt. up to 30 wt.% of an ethylene-based polymer and (C) 1 wt% to 30 wt% of the block composite.

[0090] The weight percentage is related to the total weight of the first layer. Ingredients (A), (B), and (C) may be any suitable ingredient (A) - (C) as disclosed for the present polymeric composition. In an embodiment, component (A) in the first layer comprises a propylene / ethylene copolymer with a density of 0.89 g / cm 2³ up to 0.92 g / cm³ and / or from 1 mole% to 12 mole% of units derived from ethylene. The first layer may contain optional components (D) and (E).

[0091] In an embodiment, component (B) in the first layer is HDPE with a density greater than 0.941 g / cm3.³ and / or a melt index from 1.0 g / 10 min to 20.0 g / 10 min.

[0092] In an embodiment, component (C) in the first layer of the multilayer film comprises (i) an iPP, (ii) an ethylene / propylene copolymer and (iii) a diblock copolymer comprising an iPP block and an ethylene / propylene block. The density of the block composite (C) is 0.87 g / cm³ or 0.875 g / cm³ up to 0.915 g / m³ or 0.92 g / cm³.

[0093] In an embodiment, the second layer of the multilayer film is composed of an olefin-based polymer. Non-limiting examples of suitable olefin-based polymer include LLDPE, LDPE, homogeneously branched polyethylene, ŚLEP, HDPE, propylene-based polymer, and any combination thereof.

[0094] In an embodiment, the second layer comprises 70 wt. up to 99 wt.% of an olefin-based polymer and 30 wt% to 1 wt%. a functionalized olefin-based polymer. Non-limiting examples of suitable functionalized olefin-based polymer include maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, ethylene acrylic acid copolymer, ethylene methacrylate copolymer, and any combination thereof. The weight percentage is related to the total weight of the second layer.

[0095] An optional third layer comprises a material selected from nylon, polyethylene terephthalate (PET), polypropylene, and any combination thereof.

[0096] In an embodiment, the multi-layer film is a three-layer film. The first layer is a sealant layer (containing the present polymer composition), the second layer is a core layer (containing an olefin-based polymer), and the third layer is a backing layer (containing nylon, PET and / or polypropylene). The weldable layer is the innermost layer. The second layer is the core layer. The core layer is a layer between at least two other layers. In other words, the core layer is not the innermost layer or the outermost layer. The backing layer is the outermost layer.

[0097] In an embodiment, the three-layer film has a thickness of 0.3 mils or 0.5 mils to 3 mils or 5 mils. [0098] The present film may be in two or more of the embodiments disclosed herein.

3. GOODS

[0099] The present disclosure provides articles comprising at least one component formed from the present polymeric composition. In other words, the present polymeric composition can be formed into articles. The present polymeric composition and / or the present film can be formed into final products manufactured by any of several conventional processes and apparatus. Illustrative methods include, but are not limited to, extrusion, calendering, injection molding, and / or compression molding. For example, articles may be manufactured by injection molding, extrusion, extrusion followed by thermoforming, low pressure molding, compression molding, and the like. Non-limiting examples of suitable articles include extruded profiles (monolayer or multilayer films), foams, tapes

EP-2622014B1PL seals, strips, hoses, wires and cable sheaths, pipes, flooring, gaskets, molded articles, plates and extruded parts. Additional articles include automotive parts (e.g., dashboards and window seals), computer parts, building materials, household appliances, toys, shoe parts, label sheets, paper carton such as milk carton, sachets, bags, pouches, wrapping sausages and / or meat or heat sealed bags, dry food packaging such as flakes, sugar, flour etc., thermoformed multilayer films, thermoformed containers, blister packs and films for pharmaceutical packaging.

(A) Sterilization bag

[0100] In an embodiment, the article is a flexible container containing the present polymeric composition. Referring to the drawings and beginning FIG. 1, one form of product is a sterilization pouch, shown and indicated generally by reference number 10. The sterilization pouch is a flexible packaging that remains airtight and tight when exposed to temperatures from 120 ° C-135 ° C and pressures up to 500 kPa for 30-80 minutes. The sterilization bag 10 comprises two sheets 12A and 12B of the multilayer film, bonded and welded together along respective rims by a weld 14. The weld 14 may include the entire common rim of the sheets 12A, 12B. Alternatively, seam 14 may include a portion of the common periphery of the sheets 12A, 12B. The storage space 16 is defined by the area between the two sheets 12A, 12B and the seam 14. The storage space 16 is closed to the surrounding environment and contains the contents 18 of a sterilization bag for e.g. food products. While the package is described as including two sheets 12A, 12B, it is understood that one sheet may be used. A single sheet could be so folded that it forms two layers. Then the three unconnected edges will be welded after the contents have been placed between the stacked layers.

[0101] Sheets 12A, 12B of the sterilization pouch 10 may be made from a film with a 2-layer structure as shown in FIG. 2. The outer layer 20 is furthest from the contents of the package 18. In an embodiment, the outer layer corresponds to the second layer of the previously described film.

[0102] The heat seal layer 22 is directly adjacent the outer layer 20. The heat seal layer 22 (or the innermost layer or layer in contact with the contents of the sterilization bag) is composed of the present polymeric composition. The outer layer 20 and the heat seal layer 22 may be coextruded directly with each other. Alternatively, the adhesive layer 24 may bond the outer layer 20 to the heat seal layer 22 as shown in Figure 2. The foil-to-foil contact under the influence of heat and pressure of the opposing sealable layers 24 forms the seal 14.

[0103] In an embodiment, the sterilization bag 10 is not wrinkled or substantially wrinkled after sterilization.

[0104] In an embodiment, the sterilization bag 100 is made of a three-layer film, as shown in Figure 3. The sterilization bag 100 is similar to the sterilization bag 10 except that the sterilization bag 100 is made of a three-layer film and not two-layer foil. The heat seal layer 22 is in contact with the layer 20. The backing layer 26 is in contact with the layer 20. The contact between the layers can be direct (direct and / or close contact) or indirect (adhesive layer between and / or an intermediate structure between the film layers). In this configuration, layer 20 (corresponding to the second layer in the previously described film) becomes the core layer. Layer 26 is the outermost layer and corresponds to the third layer in the previously described film.

[0105] The thickness of layers 22, 20 and 26 may be the same or different.

EP-2622014B1PL

[0106] In an embodiment, heat seal layer 22 is coextruded with core layer 20. Backing layer 26 is coextruded with core layer 20. Each of the layers, heat seal layer 22 and backing layer 26 are in direct and close contact with layer 20. In other words, there are no intermediate layers between the heat sealable layer 22 and the core layer 20. Likewise, there are no intermediate layers between the backing layer 26 and the core layer 20.

[0107] In an embodiment, sterilization bag 10 or sterilization bag 100 comprises a barrier layer. [0108] The 10/100 sterilization bag is designed to withstand a maximum applied temperature of 120 to 135 ° C (or any specified value within or within this range) for 30 to 90 minutes without significant degradation.

[0109] The sterilization bag is used to hold, protect, or contain such products, but are not limited to foodstuffs, spices, medicaments, and sterile solutions. The sterilization bag may be a "pillow" shape or it may be a gusset or a stand-up bag. During "make and fill" packaging, sterilization pouches are made in line by forming the bottom and side seals of two films brought into contact with their surfaces, adding the material to be secured and creating a final seal to enclose the foodstuff or other substance to be packed, everything is carried out in one operation. The resulting sterilization bag is usually pillow-shaped. Alternatively, the manufacturer may use pre-made pouches, with one open end, which are then filled and closed or sealed after filling. This technique is better suited for sterilization pouches with a side gusset. In a final step, the sterilization bag and the contents are typically heated to pasteurize, sterilize or cook the contents, either by using an oven or by autoclaving pressurized steam.

[0110] The sterilization bag may have two or more embodiments as disclosed herein.

DEFINITIONS

[0111] All reference to the Periodic Table of the Elements is to the Periodic Table of the Elements, copyrighted and published by CRC Press, Inc., 2003. Also, any reference to a Group or Groups shall be to a Group or Groups in that Periodic Table of the Elements using the IUPAC system. for group numbering. Unless otherwise stated, not literally out of context or customarily not used in the art, all parts and percentages are by weight. For purposes of US patent practice, the contents of each patent, patent application, or publication referred to herein are hereby incorporated by reference in their entirety (or the US equivalent version thereof so incorporated by reference), especially regarding the disclosure of synthetic techniques, definitions (to the extent that is inconsistent with the definitions provided herein) and general knowledge in the field.

[0112] Numerical ranges cited herein include all values ​​from the low value to the high value, spaced by one unit, provided that the lower value and the higher value are separated by at least 2 units. For example, if an ingredient amount or value of a physical or compositional property, such as blend ingredient amount, softening point, melt index, etc., is found to be between 1 and 100, it is intended to mean that all individual values, such as like 1, 2, 3, etc., and all subranges such as 1 to 20, 55 to 70, 197 to 100, etc. are explicitly recited in this specification. For values ​​that are less than one, one unit is considered to be 0.0001.0.001.0.01 or 0.1, respectively. These are only specific examples and all possible combinations of numerical values ​​between the lowest value given and the highest value should be considered as explicitly stated in this application. In other words, quoted

Any numerical ranges herein encompass any value or sub-range within the range. Cited are numerical ranges, as discussed herein, of the reference melt flow rate, melt flow rate, and other properties.

[0113] The terms blende or polymer blend as used herein mean blend of two or more polymers. Such a blend may or may not be miscible (no phase separation at the molecular level). In such a blend, the phases may or may not be separated. Such a blend may or may not include one or more domain configurations as determined from transmission electron spectroscopy, photo scattering, x-ray scattering, and other methods known in the art.

[0114] The term composition, as used herein, includes the mixture of materials that constitute the composition as well as reaction products and decomposition products produced from the materials of the composition.

[0115] The term "comprising, comprising" and derived therefrom does not exclude the presence of another additional ingredient, step, or procedure, whether or not disclosed herein. For the avoidance of doubt, all compositions claimed herein in connection with the use of the term "comprising" may contain any additional additive, adjuvant, or polymeric or other compound, unless otherwise stated. By contrast, the term "consisting essentially of" excludes any other component, step, or procedure from the scope of the subsequent enumeration, except those that are not essential to the flow of the process. The term consisting of excludes any ingredient, step or procedure not designated or specifically mentioned. The term or, unless otherwise stated, refers to the specified individual elements as well as in any combination.

[0116] The term ethylene-based polymer, as used herein, means a polymer that comprises most of the polymerized ethylene in percent by weight (based on the weight of the polymer) and may optionally include at least one polymerized comonomer.

[0117] The "hot tack initiation temperature" (HTIT) is the temperature at which the seal reaches 4 N / inch as the seal temperature increases.

[0118] The seal temperature window "or Delta T" is the temperature range over which the heat seal strength is equal to or greater than 6 N / inch.

[0119] The term olefin-based polymer means a polymer containing, in polymerized form, a majority by weight of an olefin, for example ethylene or propylene, based on the weight of the polymer. Non-limiting examples of olefin-based polymers include ethylene-based polymers and propylene-based polymers.

[0120] The term polymer denotes a macromolecular compound formed by polymerizable monomers of the same or different types. The polymer includes homopolymers, copolymers, terpolymers, interpolymers, and so on. The term interpolymer denotes a polymer made by the polymerization of at least two types of monomers or comonomers. It includes, but is not limited to, copolymers (and refers to polymers made from two different types of monomers or comonomers), terpolymers (and refers to polymers made from three different types of monomers or comonomers), tetrapolymers (and refers to polymers made from four different types of monomers or comonomers) and the like.

[0121] The term propylene-based polymer, as used herein, refers to a polymer which comprises a majority percent by weight of polymerized propylene monomer (based on the weight of the polymer) and optionally may include at least one polymerized comonomer.

TEST METHODS

[0122] Transparency is measured according to ASTM D 1746.

EP-2622014B1PL

[0123] The coefficient of friction for coextruded films is measured between the films with the outer (sealable) layer sliding relative to the outer (sealable) layer of the blown film in accordance with ASTM D 1894 at room temperature (23 ° C). A piece of foil is held on a horizontal surface. Another piece of foil (approximately 2.5 by 3 inches) is attached to the bottom of the sled, which is placed on top of the flat substrate with foil. A TMI Monitor / Slip &amp; Friction Tester, Model 32-06-00 was used to measure COF. The drag speed is 6 inches per minute. The forces required to initiate relative motion and to maintain steady motion were recorded and used to obtain the static and kinetic coefficients of friction, respectively. Values ​​are averages of 5 readings.

[0124] Differential to crystallinity scanning calorimetry (DSC) was used to measure the crystallinity in the ethylene (PE) and propylene (PP) based samples. The sample is pressed into a thin film at a temperature of 190 ° C. About 5 to 8 mg of the film sample is weighed and placed in a DSC pan. The vessel is closed with a crimp cap to ensure a closed atmosphere. The sample dish is placed in the DSC cell and then heated at a rate of about 10 ° C / min to 180 ° C for PE (230 ° C for PP). The sample is kept at this temperature for three minutes. The sample is then cooled at a rate of 10 ° C / min to -60 ° C for PE (-40 ° C for PP) and kept isothermally at this temperature for three minutes. The sample is then heated at a rate of 10 ° C / min until it is completely melted (second heat). The percent crystallinity is calculated by dividing the heat of fusion (Ht), determined from the 2nd heating curve, by the theoretical heat of fusion of 292 J / g for PE (165 J / g for PP) and multiplying this by 100 (e.g.,% crystalline = (Ht / 292 J / g) x 100 (for PE)).

[0125] Density is measured according to ASTM D 792-08.

[0126] Haze is measured according to ASTM D 1003.

[0127] The film seal strength is measured using the Enepay MAGMA Hot Tack and Heat Seal test system. The films are sealed at specific temperatures and allowed to cool completely to room temperature (23 ° C). The samples are conditioned at 23 ° C and 50% relative humidity for a minimum of 24 hours prior to testing. Sample foils with seals are prepared in the following Examples section.

[0128] Heat seal test - Sample films (prepared in the following Examples section) are measured using the Enepay MAGMA Hot Tack and Heat Seal test system (available from Enepay Corporation, Raleigh, NC), based on ASTM F 1921, Method B according to with the following conditions:

Table 2. Test conditions for the heat seal of coextruded films

<td>Parameter</td><td>Unit</td><td>Value</td>

<td>Sample Width:</td><td>mm</td><td> 25,4</td>

<td>Sealing time:</td><td>Knot.</td><td> 1,0</td>

<td>Pressure during welding:</td><td>N / mm²</td><td> 0,275</td>

<td>Delay time:</td><td>Knot.</td><td> 0,1</td>

<td>Pulling speed:</td><td>Mm / s</td><td> 200</td>

[0129] Data for heat seal are collected at temperature intervals of 10 ° C.

[0130] The melt flow rate (MFR) is measured according to the ASTM D 1238 test method at 230 ° C with a load of 2.16 kg.

[0131] The melt flow index (Ml) is measured according to the ASTM D 1238 test method at 190 ° C with a load of 2.16 kg.

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[0132] The melting point (Tm) of the polymer samples is measured by Differential Scanning Calorimetry (DSC). The sample is pressed into a thin film at a temperature of 190 ° C. About 5 to 8 mg of the film sample is weighed and placed in a DSC pan. The vessel is closed with a crimp cap to ensure a closed atmosphere. The sample dish is placed in the DSC cell and then heated at a rate of about 10 ° C / min to 180 ° C for PE (230 ° C for PP). The sample is kept at this temperature for three minutes. The sample is then cooled at a rate of 10 ° C / min to -60 ° C for PE (-40 ° C for PP) and kept isothermally at this temperature for three minutes. The sample is then heated at a rate of 10 ° C / min until it is completely melted (second heat). The melting point of a substance is the temperature at which a material changes from a solid to a liquid. The melting point of the polymer is defined herein as the temperature at which the heat of fusion reaches its maximum.

[0133] By way of example, and non-limitingly, examples of the present disclosure will now be provided. EXAMPLES

1. Polymer composition

[0134] The block composite component (C) is prepared as described in 82-91 in parallel US Application 2012/208946 (Patent Application No. 61 / 248,160, filed October 2, 2009).

[0135] Examples of the polymerization conditions for making the block composites 02, 03 and 14 are provided in Table 3 below. The physical properties of the obtained block composites 02, 03 and 14 are provided in Table 4.

[0136] The catalyst system comprises a catalyst ([[rel-2 ', 2' - [(1 R, 2R) -1,2-cyclohexanediylbis (methyleneoxycO)] bis [3- (9H-carbazol-9-yl) -5 -methyl [1,1'-biphenyl] -2-olane-KO]] (2 -)] dimethyl-hafnium) and cocatalyst, mixture of methyldi (C 1-8 alkyl) ammonium tetrakis (pentafluorophenyl) borane salts, prepared by long chain reaction trialkylamine (Armeen ™ M2HT, available from Akzo-Nobel, Inc.), HCl and Li [B (CeF5) 4], essentially as disclosed in USP 5,919,9883, Ex. 2., purchased from Boulder Scientific and used without further purification.

[0137] The catalytic system also contains CSA (diethyl zinc or DEZ) and modified methylalumoxane (MMAO) purchased from Akzo Nobel and used without further purification.

The solvent for the polymerization reaction is a mixture of hydrocarbons (SBP 100/140), obtainable from Shell Chemical Company, and purified through 13-molecular sieve beds prior to use.

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Table SA Process conditions for the production of block composites, examples 02₍ 03

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<img file="PL2622014T3_D0002.tif" />

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Table 3B - Physical Properties — Block Composite, Examples 02, 03

<td>Example</td><td>wt.% from extraction</td><td>MFR @ 230 ° C</td><td>Mw Kg / mol</td><td>Mw / Mn</td><td>wt.% C.₂</td><td>Tm (° C)</td><td>Tc (° C)</td><td>Enthalpy Stop (J / g)</td><td>Tg (Ό) via DSC</td><td>wt.% PP from HTLC separation</td>

<td> 02</td><td> 62,3</td><td> 7,6</td><td> 132</td><td> 2,31</td><td> 42,4</td><td> 128</td><td> 74,5</td><td> 52</td><td> -46</td><td> 13,0</td>

<td> 03</td><td> 29,1</td><td> 1,7</td><td> 202</td><td> 2,53</td><td> 26,9</td><td> 134</td><td> 91</td><td> 67</td><td> -47</td><td> 32,5</td>

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Table 3D - Physical Properties — Block Composite, Example 14

<td>Example</td><td>MFR @ 230 ° C</td><td>Mw Kg / mol</td><td>Mw / Mn</td><td>wt.% C.₂</td><td>Tm (° C) Peak 1 (Peak 2)</td><td>Tc (° C)</td><td>Enthalpy Stop (J / g)</td><td>Tg (° C)</td><td>wt.% PP from HTLC separation</td>

<td> 14</td><td> 5,8</td><td> 151</td><td> 2,9</td><td> 37,5</td><td> 127 (110)</td><td> 95</td><td> 97</td><td> -24</td><td> 28</td>

[0138] Each example of a block composite, 02, 03, and 14 comprises (i) a crystalline isotactic propylene homopolymer (iPP), (ii) an ethylene / propylene polymer (EP), and (iii) a block copolymer composed of an iPP block. and EP block.

[0139] Table 4 provides an analytical listing of the block composite examples 02, 03 and 14. Unless otherwise indicated, the properties in Table 4 are for the block composite (C).

Table 4. Analytical listing of the block composite, Component (C) - Examples

<td>Ex</td><td>Density</td><td>MFR @ 230 ° C (g / 1 Skip)</td><td>Mw Kg / mol</td><td>Mw / Mn</td><td>% wt. 02</td><td>Estimated weight share iPP (hard) (C) (i)</td><td>Estimated weight share EP (Soft) (O) (ii)</td><td>Estimated Block Composite Index</td><td>Estimated diblock capacity (C) (iii), wt.%</td>

<td> 02</td><td> 0,8688</td><td> 7,6</td><td> 132</td><td> 2,31</td><td> 42,4</td><td> 0,30</td><td> 0,70</td><td> 0,19</td><td> 19</td>

<td> 03</td><td> 0,8804</td><td> 1,7</td><td> 202</td><td> 2,53</td><td> 26,9</td><td> 0,60</td><td> 0,40</td><td> 0,32</td><td> 32</td>

<td> 14</td><td> 0,8997</td><td> 5,8</td><td> 151</td><td> 2,9</td><td> 37,5</td><td> 0,60</td><td> 0,40</td><td> 0,55</td><td> 55</td>

2. Foils

[0140] A polymer composition composed of (A) a propylene / α-olefin interpolymer, (B) an ethylene-based polymer and (C) a block composite is coextruded into film structures. Ingredients (A), (B), and (C) are dry blended prior to addition to the extruder hopper.

[0141] Three-layer coextruded films were prepared using a Colin blown film extrusion line with three extruders. The film production conditions are shown in Table 5 below. Nylon Ultramid C33L01 (inside the bladder) is used as the backing layer. A 90% by weight blend is used as the core layer. % ATTANE 4201 (commercial ethylene / octene ultra low density copolymer available from The Dow Chemical Company) and 10 wt. AMPLIFY GR 205 (HDPE polymer grafted with maleic anhydride available from The Dow Chemical Company). The composition of the heat sealable layer and the corresponding properties of the three-layer film are shown in Table 6.

Table 5. Conditions for extrusion of the coextruded 3-layer film

<td>Parameter</td><td>Unit</td><td>Value</td><td></td><td></td>

<td>Nozzle slot</td><td>mm</td><td> 2,0</td><td></td><td></td>

<td>BUR</td><td></td><td> 2,5</td><td></td><td></td>

<td>Thickness</td><td>milicale</td><td> 3,5</td><td></td><td></td>

<td>Lying flatness width</td><td>cm</td><td> 23-24</td><td></td><td></td>

<td>Pulling speed</td><td>m / min</td><td> 5,0-5,2</td><td></td><td></td>

<td>Actual speed</td><td>kg / h</td><td> 10,4-13,1</td><td></td><td></td>

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<td></td><td></td><td>Prov. 25-A</td><td>Prov.30A</td><td>Prov. 25-B</td>

<td>Layer configuration</td><td></td><td>Foundation (inside the bladder)</td><td>Core</td><td>Weldable layer (outer layer)</td>

<td>Layer ratio</td><td> %</td><td> 25</td><td> 50</td><td> 25</td>

<td>Melting temperature</td><td>° C</td><td> 223-225</td><td> 191-196</td><td> 187-194</td>

<td>Engine load</td><td>amp</td><td> 1.3-2.1</td><td> 6,1-6,5</td><td> 1,7-4,0</td>

<td>The speed of the snail</td><td>rpm</td><td> 57-63</td><td> 70-74</td><td> 61-65</td>

Table 6. Sealing layer compositions and properties of the three-layer film

<td>Ingredient</td><td>Polymer MI / MFR</td><td>Polymer Density</td><td>Unit</td><td>CS1</td><td>CSV1</td><td>CS- V2</td><td>For- V1</td><td>For- V2</td>

<td></td><td></td><td></td><td></td><td> 1</td><td> 12</td><td> 13</td><td> 15</td><td> 14</td>

<td>(B) AFFINITY PL1880G</td><td> 1,0</td><td> 0,902</td><td></td><td> 100</td><td></td><td></td><td></td><td></td>

<td>(A) H110-02N</td><td> 2,0</td><td> 0,902</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>(A) DS6D81 ** (5.1% C2)</td><td> 5,0</td><td> 0,900</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>(A) VERSIFY 2200</td><td> 2,0</td><td> 0,876</td><td></td><td></td><td> 100</td><td></td><td> 75</td><td></td>

<td>(A) VERSIFY 3200</td><td> 8,0</td><td> 0,876</td><td></td><td></td><td></td><td> 100</td><td></td><td> 75</td>

<td>(C) Block composite (14 from Table 3, 4)</td><td> 5,8</td><td> 0,8997</td><td></td><td></td><td></td><td></td><td> 10</td><td> 10</td>

<td>(B) HDPE 12450N</td><td> 12</td><td> 0.950</td><td></td><td></td><td></td><td></td><td> 15</td><td> 15</td>

<td>Kinetic COF (FM)</td><td></td><td></td><td></td><td> 1,20</td><td> 1,37</td><td> 1,11</td><td> 1,00</td><td> 0,983</td>

<td>Static COF (FM)</td><td></td><td></td><td></td><td> 1,37</td><td> 1,54</td><td> 1,30</td><td> 1,15</td><td> 1,12</td>

<td>Haze</td><td></td><td></td><td> (%)</td><td> 0,63</td><td> 0,756</td><td> 1,66</td><td> 2,38</td><td> 1,83</td>

<td>Transparency</td><td></td><td></td><td> (%)</td><td> 98,2</td><td> 98,14</td><td> 97,1</td><td> 96,0</td><td> 97,3</td>

<td>Hot seal peak</td><td></td><td></td><td>(N / inch)</td><td> 8,14</td><td> 7,11</td><td> 9,72</td><td> 8,73</td><td> 9,52</td>

<td>HTIT (° C 4N / inch)</td><td></td><td></td><td>(° C)</td><td> 97</td><td> 67</td><td> 72</td><td> 67</td><td> 69</td>

<td>HT peak Temperature</td><td></td><td></td><td>(° C)</td><td> 120</td><td> 120</td><td> 100</td><td> 80</td><td> 110</td>

<td>Delta T (HT&gt; 6N / in)</td><td></td><td></td><td>(° C)</td><td> 29</td><td> 47</td><td> 48</td><td> 77</td><td> 68</td>

<td>HT at 150 ° C</td><td></td><td></td><td>(n / in)</td><td> 4,3</td><td> 4,9</td><td> 4,1</td><td> 5,9</td><td> 5,0</td>

<td colspan="9">** MFR measured @ 230 ° CCS = Comparative samples Ex = Examples of the present disclosure</td>

Hot seal temperature window

[0142] The structured coextruded films made with the present polymeric composition exhibit a heat seal strength greater than 6 N / inch over a temperature range of at least about 50 ° C, or at least about 55 ° C, or at least about 60 ° C. C (Table 5) according to ASTM F 1921, Method B with a dwell time of 1.0 seconds and a cooling time of 0.1 seconds. Data for the heat seal temperature window are shown in Figure 5.

Sealing initiation temperature (HTIT)

[0143] The coextruded films prepared with the present polymeric composition in the heat sealable layer exhibited a seal initiation temperature comparable or lower to the comparative samples. Generally, a lower temperature is desirable to improve processing and production speed in the packaging operation

Sealing initiation. Coextruded films containing the present polymeric composition in the heat seal layer exhibit a lower HTIT than films containing ŚLEP in the heat seal layer. HTIT data is listed in Table 6.

Coefficient of friction (COF)

[0144] Generally, a lower COF is desirable to improve processing and / or increase packing speed. The COF data is shown in Table 6 and Figure 7. Coextruded films with a heat sealable layer made with the present polymeric composition exhibit a lower COF compared to comparative samples made from ŚLEP and polypropylene based polymers.

Strength of hot welding at elevated temperatures

[0145] Another very useful aspect in these examples is the heat seal strength at elevated temperatures, such as 150 ° C. The higher heat seal strength at high temperatures allows the contents to be packaged and / or processed at elevated temperatures, such as sterilization with boiling water or other heating mechanisms, for use in sterilization processes. As shown in Figures 4 and 6 and in Table 6, the values ​​of the heat seal strength of the present examples at 150 ° C are higher than the values ​​of the respective comparative samples.

Optical properties

[0146] The present examples show very good optical properties as shown in Table 6 and Figures 8 and 9. All the haze values ​​of the film containing the heat seal layers in the comparative samples and in the present examples are less than 2.5, and the transparency of these films is greater than 96. %.

[0147] The present disclosure is not limited to the embodiments and illustrations contained herein, but covers portions of the embodiments and feature combinations of different embodiments falling within the scope of the following claims.