BREATHABLE FILM, LAMINATED AND ARTICLE

专利摘要:
breathable films and articles incorporating them. breathable films formed from polyethylene are provided and may have desirable properties. in one aspect, a breathable film comprises a first composition, wherein the first composition comprises at least one ethylene-based polymer and wherein the first composition comprises a mwcdi value greater than 0.9 and a melt index ratio (i10/i2) which meets the following equation: i10/i2 = 7.0 - 1.2 x log (i2).
公开号:BR112016029614B1
申请号:R112016029614-1
申请日:2015-06-26
公开日:2021-08-17
发明作者:Jian Wang；Pradeep Jain；Mehmet Demirors；Rajen M. Patel；Joseph L. Deavenport；Jacquelyn A. Degroot；Suzanne M. Guerra；Viraj Shah；Selim Bensason；Satyajeet Ojha
申请人:Dow Global Technologies Llc；
IPC主号:

专利说明:

FIELD
[0001] The present invention generally relates to breathable films and to articles incorporating breathable films. INTRODUCTION
[0002] Breathable films are widely used in hygiene applications such as diaper backsheets. Persons skilled in the art generally understand breathable films as having a microporous morphology with some ability to allow the passage of moisture vapors. See, for example, Wu et al., “Novel Microporous Films and Their Composites,” Journal of Engineered Fibers and Fabrics, Vol. 2, Issue 1, at 49-59 (2007).
[0003] Breathable films are normally made by incorporating 40 to 60% of a mineral filler, such as calcium carbonate (CaCO3), into polyolefin resin such as polyethylene or polypropylene or combinations of these materials, causing a molten film or blown, and stretching or orienting the molten or blown film by means of machine direction orientation rollers ("MDO"), by means of stretching or by means of interlocking gears, through which the film is looped or incrementally stretched , in one or both of the machine direction or the transverse direction below the melting point of the polyolefin resin. The water vapor transmission rate or breathability (WVTR) of the film is important for some applications such as diaper backsheet films, protective clothing, surgical suits, and thermal and acoustic coatings. In these applications, the films can act as a liquid barrier, while allowing the transmission of water vapor to provide advantages such as protection and comfort for the end user, in the case of hygiene and medical applications and protection from the elements, no moisture build-up in case of thermal coating.
[0004] For fabric underlay applications, breathable films need a good balance of processability, stiffness and toughness. Processability, in terms of drawing capacity, is required during the semi-solid state stretching and extrusion steps of the process to ensure smooth, uniform drawing without breakage. Stiffness, often measured as film modulus, allows for good dimension stability to films as they go through high speed film printing processes to prepare diaper. This ultimately provides basic print repeat lengths and predictable screen widths. Hardness is necessary to prevent film perforation due to the presence of superabsorbent polymer particles (SAP) in the absorbent core next to the film and to prevent leaks formed by hydraulic head pressure due to a saturated absorbent core and the weight of the end user.
[0005] While ethylene-based polymers have been used for breathable films, there continues to be a need for ethylene-based compositions that can be used in the manufacture of breathable films with desirable properties and related articles. SUMMARY
[0006] The present invention uses ethylene-based polymers that exhibit certain characteristics in the formation of breathable films with desirable properties. For example, in some embodiments, breathable films provide desirable processability, stiffness, hardness and/or WVTR values for hygiene and other applications.
[0007] In one aspect, the present invention provides a breathable film, comprising a first composition, wherein the first composition comprises at least one ethylene-based polymer and wherein the first composition comprises a MWCDI value greater than 0, 9 and a melt index ratio (I10/I2) that meets the following equation: I10/I2 > 7.0 - 1.2 x log (I2).
[0008] These and other modalities are described in more detail in the Detailed Description. BRIEF DESCRIPTION OF THE DRAWINGS
[0009] Figure 1 illustrates the graph of "SCBf versus Area Ratio of IR5" over ten SCB Standards.
[0010] Figure 2 illustrates the various GPC profiles for determining the IR5 Height Ratio for the first composition 2.
[0011] Figure 3 illustrates the graph of "SCBf in relation to the equivalent molecular Log Mwi of polyethylene (GPC)" for the first inventive composition 2 .
[0012] Figure 4 illustrates a graph of the "Percentage in moles of comonomer against the equivalent Log Mwi of polyethylene (GPC)" for the first inventive composition 2 .
[0013] Figure 5 illustrates some GPC MWD profiles and corresponding comonomer distribution overlaps for some inventive and comparative compositions (density 0.916-0.919 g/cc).
[0014] Figure 6 illustrates some GPC MWD profiles and corresponding comonomer distribution overlaps for some inventive and comparative compositions (density 0.924-0.926 g/cc).
[0015] Figure 7 illustrates some GPC MWD profiles and corresponding comonomer distribution overlays for some inventive and comparative compositions (Cast stretch). DETAILED DESCRIPTION
[0016] It has been found that the compositions of the invention can be used to form inventive breathable films and related products. Such compositions contain an ethylene-based polymer that has a superior comonomer distribution, which is significantly higher in the comonomer concentration, and a good comonomer distribution, in the high molecular weight polymer molecules, and is significantly lower in the comonomer concentration in the low molecular weight polymer molecules, compared to conventional polymers in the art with the same total density. It was also found that the ethylene-based polymer has low LCBs (long chain branches), as indicated by low ZSVR, compared to conventional polymers. As a result of this optimized comonomer distribution, as well as from the inherent nature of low LCBs, the inventive compositions have multiple loop currents, and thus improved film tenacity. The inventive compositions may be useful in forming the inventive breathable films and related products of the present invention.
[0017] The invention provides a composition comprising a first composition, which comprises at least one ethylene-based polymer, wherein the first composition comprises a MWCDI value greater than 0.9, and a melt index ratio (I10 /I2) which meets the following equation: I10/I2 > 7.0-1.2 x log (I2).
[0018] The inventive composition may comprise a combination of two or more modalities described herein.
[0019] The first composition may comprise a combination of two or more modalities as described herein.
[0020] The ethylene-based polymer may comprise a combination of two or more modalities as described herein.
[0021] In one modality, the first composition has a MWCDI value less than or equal to 10.0, still less than or equal to 8.0, still less than or equal to 6.0.
[0022] In one modality, the first composition has a MWCDI value less than or equal to 10.0, still less than or equal to 8.0, still less than or equal to 6.0.
[0023] In one modality, the first composition has a MWCDI value greater than or equal to 1.0, even greater than or equal to 1.1, even greater than or equal to 1.2.
[0024] In one modality, the first composition has a MWCDI value greater than or equal to 1.3, even greater than or equal to 1.4, still greater than or equal to 1.5.
[0025] In one embodiment, the first composition has a melt index ratio of I10/I2 greater than or equal to 7.0, yet greater than or equal to 7.1, yet greater than or equal to a, 7.2, still greater than or equal to 7.3.
[0026] In one embodiment, the first composition has a melt index ratio of I10/I2 less than or equal to 9.2, yet less than or equal to 9.0, still less than or equal to a, 8.8, still less than or equal to 8.5.
[0027] In one modality, the first composition has a ZSVR value of 1.2 to 3.0, plus 1.2 to 2.5, plus 1.2 to 2.0.
[0028] In one embodiment, the first composition has a vinyl unsaturation level greater than 10 vinyls per 1,000,000 total carbons. For example, greater than 20 vinyls per 1,000,000 total carbon atoms, or greater than 50 vinyls per 1,000,000 total carbon atoms, or greater than 70 vinyls per 1,000,000 total carbon atoms, or greater than than 100 vinyls per 1,000,000 total carbons.
[0029] In one modality, the first composition has a density in the range of 0.910 to 0.940 g/cm3, for example, from 0.910 to 0.935 g/cm3, or from 0.910 to 0.930 g/cm3, or from 0.910 to 0.925 g/ cm3. For example, the density can be from a lower limit of 0.910, 0.912, or 0.914 g/cm3 to an upper limit of 0.925, 0.927, 0.930, or 0.935 g/cm3 (1 cm3 = 1 cc).
[0030] In one embodiment, the first composition has a melt index (I2 or I2; at 190°C/2.16 kg) of 0.1 to 50 g/10 minutes, for example, from 0.1 to 30 g/10 minutes, or 0.1 to 20 g/10 minutes, or 0.1 to 10 g/10 minutes. For example, the melt index (I2 or I2; at 190°C / 2.16 kg) can be from a lower limit of 0.1, 0.2, or 0.5 g/10 minutes, at a upper limit of 1.0, 2.0, 3.0, 4.0, 5.0, 10, 15, 20, 25, 30, 40, or 50 g/10 minutes.
[0031] In one embodiment, the first composition has a molecular weight distribution expressed as the ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn; as determined by GPC conv.) in the range of 2, 2 to 5.0. For example, the molecular weight distribution (Mw/Mn) can be from a lower limit of 2.2, 2.3, 2.4, 2.5, 3.0, 3.2, or 3.4 , to an upper limit of 3.9, 4.0, 4.1, 4.2, 4.5, or 5.0.
[0032] In one embodiment, the first composition has a number average molecular weight (Mn; as determined by GPC conv.) in the range of 10,000 to 50,000 g/mol. For example, number average molecular weight can be from a lower limit of 10,000, 20,000, or 25,000 g/mol, to an upper limit of 35,000, 40,000, 45,000, or 50,000 g/mol.
[0033] In one embodiment, the first composition has a weight average molecular weight (Mw; as determined by GPC conv.) in the range of 70,000 to 200,000 g/mol. For example, the number average number molecular weight can be from a lower limit of 70,000, 75,000, or 78,000 g/mol, to an upper limit of 120,000, 140,000, 160,000, 180,000, or 200,000 g/mol.
[0034] In one embodiment, the first composition has a melt viscosity ratio, Eta*0.1/Eta*100, in the range of 2.2 to 7.0. For example, the number average molecular weight can be from a lower limit of 2.2, 2.3, 2.4 or 2.5, to an upper limit of 6.0, 6.2, 6.5, or 7.0.
[0035] In one embodiment, the ethylene-based polymer is an ethylene/α-olefin interpolymer and further an ethylene/α-olefin copolymer.
[0036] In one embodiment, the first ethylene-based polymer is an ethylene/α-olefin interpolymer and further an ethylene/α-olefin copolymer.
[0037] In one embodiment, the α-olefin has less than or equal to 20 carbon atoms. For example, α-olefin comonomers can preferably have from 3 to 10 carbon atoms and more preferably from 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1 -pentene. The one or more α-olefin comonomers can, for example, be selected from the group consisting of propylene, -butene, 1-hexene, and 1-octene; or, alternatively, from the group consisting of 1-butene, 1-hexene and 1-octene, and furthermore 1-hexene and 1-octene.
[0038] In one embodiment, the ethylene-based polymer, or the first ethylene-based polymer, has a molecular weight distribution (Mw/Mn; as determined by GPC conv.) in the range of 1.5 to 4, 0, for example from 1.5 to 3.5, or from 2.0 to 3.0. For example, the molecular weight distribution (Mw/Mn) can be from a lower limit of 1.5, 1.7, 2.0, 2.1, or 2.2 to an upper limit of 2, 5, 2.6, 2.8, 3.0, 3.5 or 4.0.
[0039] In one embodiment, the first composition further comprises a second ethylene-based polymer. In yet an embodiment, the second ethylene-based polymer is an ethylene/α-olefin interpolymer, and further an ethylene/α-olefin copolymer or an LDPE.
[0040] In one embodiment, the α-olefin has less than or equal to 20 carbon atoms. For example, α-olefin comonomers can preferably have from 3 to 10 carbon atoms and more preferably from 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1 -pentene. The one or more α-olefin comonomers can, for example, be selected from the group consisting of propylene, -butene, 1-hexene, and 1-octene; or, alternatively, from the group consisting of 1-butene, 1-hexene and 1-octene, and furthermore 1-hexene and 1-octene.
[0041] In one embodiment, the second ethylene-based polymer is a heterogeneously branched ethylene/α-olefin interpolymer and further a heterogeneously branched ethylene/α-olefin copolymer. Heterogeneously branched ethylene/α-olefin interpolymers are typically produced using the Ziegler/Natta type catalyst system and have more comonomers distributed in the lower molecular weight molecules of the polymer.
[0042] In one embodiment, the second ethylene-based polymer has a molecular weight distribution (Mw/Mn) in the range from 3.0 to 5.0, for example from 3.2 to 4.6. For example, the molecular weight distribution (Mw/Mn) can be from a lower limit of 3.2, 3.3, 3.5, 3.7, or 3.9, to an upper limit of 4, 6, 4.7, 4.8, 4.9, or 5.0.
[0043] In one embodiment, the composition comprises from 50 to 80% by weight, or from 50 to 85% by weight, or from 50 to 90% by weight, or from 50 to 95% by weight of the first composition, based on in the weight of the composition.
[0044] In one embodiment, the composition comprises more than or equal to 80% by weight, or more than or equal to 85% by weight, or more than or equal to 90% by weight, or more than or equal to 95% by weight, or greater than or equal to 98% by weight of the first composition, based on the weight of the composition.
[0045] In one embodiment, the composition comprises yet another polymer. In yet another embodiment, the polymer is selected from the following: an LLDPE, a VLDPE (very low density polyethylene), an MDPE, an LDPE, an HDPE, an HMWHDPE (a high molecular weight HDPE), a polymer to propylene base, a polyolefin plastomer, a polyolefin elastomer, an olefin block copolymer, an ethylene vinyl acetate, an ethylene acrylic acid, an ethylene methacrylic acid, a methyl ethylene acrylate, an ethyl acrylate of ethylene, an ethylene butyl acrylate, a polyisobutylene, a maleic anhydride grafted polyolefin, an ionomer of any of the above, or a combination thereof.
[0046] In one embodiment, the composition further comprises an LDPE. In another embodiment, LDPE is present in an amount of 5 to 50% by weight, more than 10 to 40% by weight, more than 15 to 30% by weight, based on the weight of the composition. In another embodiment, LDPE has a density of 0.915 to 0.930 g/cc and a melt index (I2) of 0.15 to 30 g/10 min, even more than 0.25 to 20 g/10 min.
[0047] In one embodiment, the composition further comprises one or more additives.
[0048] The invention also provides an article comprising at least one component formed from an inventive composition as described herein. In another embodiment, the article is a film.
[0049] In some embodiments, the present invention relates to a breathable film formed from any of the inventive compositions as described herein. In some embodiments, a first composition (formed from an inventive composition described herein) in the breathable film may have a MWCDI value of less than or equal to 10.0. In some embodiments, the first composition used in the breathable film has a density of 0.910-0.950 g/cm3 and/or a melt index (I2) of 0.5 to 30 g/10 minutes. The first composition used in the breathable film, in some embodiments, has a density of 0.915 g to 0.940/cm3. In some embodiments where the permeable film is a cast film, the melt index can be 0.8 to 15 g/10 minutes or 1.5 to 5 g/10 minutes. In some embodiments where the breathable film is a blown film, the melt index can be 0.7 to 1.5 g/10 minutes.
[0050] In some embodiments, the breathable film further comprises 40 to 65 percent by weight of a mineral filler (eg, CaCO3).
[0051] A breathable film, in some embodiments, has a basis weight of 10 to 20 g/m2 or 12 to 20 g/m2 or 8 to 18 g/m2.
[0052] In some embodiments, the breathable film is a monolayer film. The breathable film, in some embodiments, is a multilayer film. In some embodiments, the breathable film comprises up to 7 layers or, in the case of microlayer films, it may comprise more than 15 or 25 layers.
[0053] In some embodiments, a first breathable film layer may comprise, in addition to an inventive composition, a second polymer, wherein the second polymer is selected from the following: an LLDPE, a VLDPE, an LDPE, an MDPE, an HDPE, an HMWHDPE, a propylene-based polymer, a polyolefin plastomer, a polyolefin elastomer, an olefin block copolymer, an ethylene vinyl acetate, an ethylene acrylic acid, an ethylene methacrylic acid, an acrylate of methyl ethylene, an ethyl ethylene acrylate, a butyl ethylene acrylate, a polyisobutylene, a maleic anhydride grafted polyolefin, an ionomer of any of the above, or a combination thereof.
[0054] In some embodiments, where the breathable film is a multilayer film, the film may further comprise a second layer, wherein the second layer comprises a polymer selected from the following: an inventive composition, a LLDPE, a VLDPE ( very low density polyethylene), an MDPE, an LDPE, an HDPE, an HMWHDPE (a high molecular weight HDPE), a propylene-based polymer, a polyolefin plastomer, a polyolefin elastomer, an olefin block copolymer , an ethylene vinyl acetate, an ethylene acrylic acid, an ethylene methacrylic acid, an ethylene methyl acrylate, an ethylene ethyl acrylate, a ethylene butyl acrylate, a polyisobutylene, a maleic anhydride grafted polyolefin, a ionomer of any of the above or a combination thereof.
[0055] The air permeable film in some embodiments comprises at least 30 percent by weight of any of the inventive compositions described herein. In some embodiments, the breathable film comprises up to 60 percent by weight of any of the inventive compositions described herein. The breathable film, in some embodiments, comprises 40 to 60 percent by weight of an inventive composition, or 45 to 55 percent by weight of an inventive composition.
[0056] In some embodiments, a breathable film has a water vapor transmission rate of at least 100 g/m2-day-atm and up to 10,000 g/m2-day-atm, preferably 500 g/m2-day-atm- atm to 10,000 g/m2-day-atm or from 1,000 to 6,000 g/m2-day-atm or from 1,500 to 6,000 g/m2-day-atm.
[0057] The breathable film, in some embodiments, has a hydraulic head of at least 60 cm as measured by the EN 20811 standard.
[0058] In some embodiments, the breathable film is oriented at least in the machine direction.
[0059] Some embodiments of the present invention relate to laminates comprising a breathable film as disclosed herein. In some such embodiments, the laminate may additionally comprise a non-woven material. Some embodiments of the present invention pertain to an article comprising a laminate as disclosed herein.
[0060] Some embodiments of the present invention pertain to an article comprising a breathable film as disclosed herein. Non-limiting examples of such articles may include baby diaper backsheets, workout pants, adult incontinent products, surgical gowns with a breathable barrier, thermal and acoustic coating, and filtration products. Polymerization
[0061] Polymerization processes include, but are not limited to, solution polymerization processes using one or more conventional reactors, for example, closed loop reactors, isothermal reactors, adiabatic reactors, stirred tank reactors, autoclave reactors in parallel, series and/or any combinations thereof. Ethylene-based polymer compositions can, for example, be produced through solution phase polymerization processes, using one or more closed loop reactors, adiabatic reactors and combinations thereof.
[0062] In general, the solution phase polymerization process takes place in one or more well-mixed reactors, such as one or more closed loop reactors and/or one or more adiabatic reactors, at a temperature in the range of 115 to 250 °C; for example, from 135 to 200°C and at pressures in the range of 300 to 1,000 psig, for example, from 450 to 750 psig.
[0063] In one embodiment, the ethylene-based polymer composition (for example, the first composition referred to in claim 1 or the first composition referred to in claim 1) can be produced in two closed loop reactors in series configuration, the the first reactor temperature is in the range 115 and 200°C, for example 135 to 165°C, and the second reactor temperature is in the range 150 to 210°C, for example 185 to 200°C. In another embodiment, the ethylene-based polymer composition can be produced in a single reactor, the reactor temperature is in the range of 115 to 200°C, for example 130 to 190°C. Residence time in a solution phase polymerization process is typically in the range of 2 to 40 minutes, for example 5 to 20 minutes. Ethylene, solvent, one or more catalyst systems, optionally one or more cocatalysts, and optionally one or more comonomers, are continuously fed to one or more reactors. Examples of solvents include, but are not limited to, isoparaffins. For example, such solvents are commercially available under the name Isopar E ExxonMobil Chemical. The resulting mixture of ethylene-based polymer composition and solvent is then removed from the reactor or reactors and the ethylene-based polymer composition is isolated. Solvent is typically recovered through a solvent recovery unit, i.e. heat exchangers and separation vessel, and the solvent is then recycled back to the polymerization system.
[0064] In one embodiment, the ethylene-based polymer composition can be produced through a solution polymerization process, in a double reactor system, for example, a double loop reactor system, in which the ethylene , and optionally one or more α-olefins, are polymerized in the presence of one or more catalyst systems, in a reactor, to produce a first polymer based on ethylene and ethylene, and optionally one or more α-olefins, are polymerized in the presence of one or more catalyst systems, in a second reactor, to produce a second ethylene-based polymer. Additionally, one or more cocatalysts may be present.
[0065] In another embodiment, the ethylene polymer-based composition can be produced through a solution polymerization process, in a single reactor system, for example, a single closed loop reaction system, in which the ethylene, and optionally one or more α-olefins, are polymerized in the presence of one or more catalyst systems. Additionally, one or more cocatalysts may be present.
[0066] As discussed above, the invention provides a process for forming a composition comprising at least two ethylene-based polymers, said process comprising the following: the polymerization of ethylene, and optionally at least one comonomer, in solution, in the presence of a catalyst system comprising a metal-ligand complex of Structure I,
M is titanium, zirconium, or hafnium, each independently being in a formal oxidation state of +2, +3, or +4; en is an integer from 0 to 3, and where when n is 0, X is absent; and each X, independently, is a monodentate ligand that is neutral, monoanionic, or dianionic; or two X's are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic; and X and en are chosen such that the metal-ligand complex of formula (I) is generally neutral; and
R1 through R16 are each independently selected from the group consisting of the following: a substituted or unsubstituted hydrocarbyl (C1-C40), a substituted or unsubstituted heterohydrocarbyl (C1-C40), Si(RC)3, Ge(RC)3, PP N CC CC (R)2, N(R)2, OR, SR, NO2, CN, CF3, RS(O)-, RS(O)2-, (RC)2C=N-, RCC(O) O-, RCOC(O)-, RCC(O)N(R)-, (RC)2NC(O)-, halogen atom, hydrogen atom; and wherein each RC is independently a hydrocarbyl (C1-C30); RP is a hydrocarbyl (C1-C30); and RN is a hydrocarbyl (C1-C30); and wherein, optionally, two or more R groups (from R1 through R16) may combine together into one or more ring structures, with such ring structures each independently having from 3 to 50 ring atoms, excluding of any hydrogen atom.
[0067] An inventive process may comprise a combination of two or more modalities as described herein.
[0068] In one embodiment, said process comprises polymerizing ethylene, and optionally at least one α-olefin, in solution, in the presence of a catalyst system comprising a metal-ligand complex of Structure I, to form a first ethylene-based polymer; and polymerizing ethylene, and optionally at least one α-olefin, in the presence of a catalyst system comprising a Ziegler/Natta catalyst, to form a second ethylene-based polymer. In another embodiment, each α-olefin is independently a C1-C8 α-olefin.
[0069] In one embodiment, optionally, two or more R groups of R9 through R13 or R4 through R8 may combine together into one or more ring structures, with such ring structures each independently having from 3 to 50 atoms in the ring, excluding any hydrogen atom.
[0070] In one modality, M is hafnium.
[0071] In one embodiment, R3 and R14 are each, independently, an alkyl and further a C1-C3 alkyl group and even more methyl.
[0072] In an embodiment, R1 and R16 are each as follows: I .
[0073] In one embodiment, each of the groups aryl, heteroaryl, hydrocarbyl, heterohydrocarbyl, Si(RC)3, Ge(RC)3, PNC CC CCP(R)2, N(R)2, OR, SR, RS (O)-, RS(O)2-, (R)2C=N-, RCC(O)O-, RCOC(O)-, RCC(O)N(R)-, (RC)2NC(O) -, hydrocarbylene and heterohydrocarbylene, independently, is unsubstituted or substituted with one or more RS substituents; and each RS is independently a halogen atom, polyfluoro substitution, perfluoro substitution, unsubstituted alkyl (C1-C18), F3C-, FCH2O-, F2HCO-, F3CO-, R3Si-, R3Ge-, RO-, RS, RS (O)-, RS(O)2-, R2P-, R2N-, R2C=N-, NC-, RC(O)O-, ROC(O)-, RC(O)N(R)-, or R2NC(O)-, or two of RS are taken together to form an unsubstituted (C1-C18) alkylene, where each R independently is an unsubstituted (C1-C18) alkyl.
[0074] In one embodiment, two or more of R1 through R16 do not combine to form one or more ring structures.
[0075] In one embodiment, the catalyst system suitable for producing the first ethylene/α-olefin interpolymer is a catalyst system comprising bis((2-oxoyl-3-(dibenzo-1H-pyrrol-1-yl)- 5-(methyl)phenyl)-2-

Ziegler/Natta catalysts suitable for use in the invention are typically supported Ziegler-type catalysts, which are particularly useful at high polymerization temperatures of the solution process. Examples of such compositions are those derived from organomagnesium compounds, alkyl halides or aluminum halides or hydrogen chloride and a transition metal compound. Examples of such catalysts are described in US Patents 4,612,300; 4,314,912; and 4,547,475; whose teachings are hereby incorporated by reference.
Particularly suitable organomagnesium compounds include, for example, hydrocarbon-soluble dihydrocarbylmagnesium such as magnesium dialkyls and magnesium diarys. Exemplary suitable magnesium dialkyls include, in particular, n-butyl-sec-butylmagnesium, diisopropylmagnesium, di-n-hexylmagnesium, isopropyl-n-butyl-magnesium, ethyl-n-hexyl-magnesium, ethyl-n-butylmagnesium, di- n-octylmagnesium, and others, where the alkyl has 1 to 20 carbon atoms. Suitable exemplary magnesium diaris include phenylmagnesium, dibenzylmagnesium and tolylmagnesium. Suitable organomagnesium compounds include alkyl and aryl magnesium alkoxides and aryl and aryl oxides and alkyl magnesium halides, with the halogen-free organomagnesium compounds being more desirable.
[0078] Halide sources include non-metal active halides, metal halides and hydrogen chloride. Suitable non-metallic halides are represented by the formula R'X, where R' is hydrogen or an active monovalent organic radical and X is a halogen. Particularly suitable non-metallic halides include, for example, hydrogen halides and active organic halides, such as t-alkyl halides, allyl halides, benzyl halides and other active hydrocarbyl halides. By an active organic halide is meant a hydrocarbyl halide which contains a labile halogen at least as active, i.e. as easily lost to another compound, such as the halogen of sec-butyl chloride, preferably as active as the t chloride -butyl. In addition to organic monohalides, it is understood that organic trihalide dihalides, and others which are active polyhalides, as defined hereinbefore, are also suitably employed. Examples of preferred active non-metallic halides include hydrogen chloride, hydrogen bromide, t-butyl chloride, t-amyl bromide, allyl chloride, benzyl chloride, crotyl chloride, carbinyl methylvinyl chloride, a phenylethyl bromide , diphenyl methyl chloride and the like. Most preferred are hydrogen chloride, t-butyl chloride, allyl chloride and benzyl chloride.
Suitable metal halides include those represented by the formula MRy-a Xa, wherein: M is a metal of Groups IIB, IIIA or IVA of the Mendeleev Periodic Table of Elements; R is a monovalent organic radical; X is a halogen; y has a value that corresponds to the valence of M; and "a" has a value from 1 to y. Preferred metal halides are aluminum halides of the formula AlR3-a Xa, where R is independently hydrocarbyl such as alkyl; X is halogen and is a number from 1 to 3. Most preferred are alkylaluminum halides, such as ethylaluminum sesquichloride, diethylaluminum chloride, ethylaluminum dichloride and diethylaluminum bromide, ethylaluminum dichloride with being especially preferred. Alternatively, a metal halide, such as aluminum trichloride, or a combination of aluminum trichloride with an alkyl aluminum halide, or an aluminum trialkyl compound can be suitably employed.
[0080] Any of the conventional Ziegler-Natta transition metal compounds can be usefully employed as the transition metal component in preparing the supported catalyst component. Typically, the transition metal component is a compound of a Group IVB, VB or VIB metal. The transition metal component is usually represented by the formulas: TRX'4-q (OR1)q, TrX'4-q (R2)q, VOX'3 and VO(OR)3.
[0081] Tr is a Group IVB, VB, or VIB of metal, preferably a Group IVB or VB of metal, preferably titanium, vanadium or zirconium; q is 0 or a number equal to or less than 4; X' is halogen, and R1 is an alkyl group, aryl group or cycloalkyl group having from 1 to 20 carbon atoms; and R2 is an alkyl group, aryl group, aralkyl group, substituted aralkyls and the like.
Aryl, aralkyls and substituted aralkyls contain 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. When the transition metal compound contains a hydrocarbyl group, R2 being an alkyl, cycloalkyl, aryl or aralkyl group, the hydrocarbyl group will preferably not contain an H atom in the beta position with respect to the metal bonding carbon. Illustrative, but not limiting, examples of aralkyl groups are methyl, neopentyl, 2,2-dimethylbutyl, 2,2-dimethylhexyl; aryl groups such as benzyl; cycloalkyl groups such as 1-norbornyl. Mixtures of these transition metal compounds can be employed, if desired.
[0083] Illustrative examples of transition metal compounds include TiCl4, TiBr4, Ti(OC2H5)3Cl, Ti(OC2H5)Cl3, Ti(OC4H9)3Cl, Ti(OC3H7)2Cl2, Ti(OC6H13)2Cl2, Ti(OC8H17 )2Br2e Ti(OC12H25)Cl3, Ti(O-iC3H7)4 and Ti(O-nC4H9)4. Illustrative examples of vanadium compounds include VCl4, VOCl3, VO(OC2H5)3, and VO(OC4H9)3. Illustrative examples of zirconium compounds include ZrCl4, ZrCl3(OC2H5), ZrCl2(OC2H5)2, ZrCl(OC2H5)3, Zr(OC2H5)4, ZrCl3(OC4H9), ZrCl2(OC4H9)2 and ZrCl(OC4H9)3.
[0084] An inorganic oxide support can be used in preparing the catalyst and the support can be any particulate oxide or mixed oxide that has been thermally or chemically dehydrated such that it is substantially free of adsorbed moisture. See US Patent 4,612,300; 4,314,912; and 4,547,475; whose teachings are hereby incorporated by reference.
[0085] In one modality, the composition comprises a MWCDI value greater than 0.9.
[0086] In one embodiment, the composition comprises a melt index ratio (I10/I2) that satisfies the following equation: I10/I2 ^ 7.0-1.2 x log (I2).
[0087] The composition may comprise one modality, or a combination of two or more modalities, as listed above, for the "first composition."
[0088] An inventive process may comprise a combination of two or more modalities as described herein. Cocatalyst component
[0089] The catalytic systems described above can be made catalytically active by contacting or combining it with the activation cocatalyst, or using an activation technique, such as those known in the art, for use with olefin polymerization reactions metal-based. Suitable activation cocatalysts, for use herein, include alkyl aluminums; polymeric or oligomeric alumoxanes (also known as aluminoxanes); neutral Lewis acids; and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions). A suitable activation technique is mass electrolysis. Combinations of one or more of the above activation cocatalysts and techniques are also contemplated. The term "alkyl aluminum" means a monoalkylaluminum dihydride or a monoalkylaluminum dihalide, a dialkylaluminum hydride or a dialkylaluminum halide or a trialkylaluminum. Aluminoxanes and their preparations are known, for example, in US Patent 6,103,657. Examples of preferred polymeric or oligomeric alumoxanes are methylalumoxane, methylalumoxane modified with tri-isobutylaluminum, and isobutylalumoxane.
Lewis acid activating cocatalysts are Group 13 metal compounds containing 1 to 3 hydrocarbyl substituents, as described herein. In some embodiments, exemplary Group 13 metal compounds are tri(hydrocarbyl)-substituted aluminum or tri(hydrocarbyl)-boron compounds. In some other embodiments, the exemplary Group 13 metal compounds are substituted tri(hydrocarbyl)aluminum compounds or the tri(hydrocarbyl) boron compounds are tri((C1-C10)alkyl)aluminum compounds or tri((C6-C18) aluminum compounds )aryl)boron and halogenated derivatives thereof (including perhalogenated). In some other embodiments, exemplary Group 13 metal compounds are tris(fluoro-substituted-phenyl)boranes, in other embodiments, tris(pentafluorophenyl)borane. In some embodiments, the activation cocatalyst is a tris((C1-C20)hydrocarbyl) borate (eg, trityl tetrafluoroborate) or a tri((C1-C20)hydrocarbyl)ammonium tetra((C1-C20)hydrocarbyl)borane ( for example, methylammonium tetrakis (pentafluorophenyl)borane)). As used herein, the term "ammonium" means a cation that is a ((C1-C20)hydrocarbyl)4N+, a ((C1-C20)hydrocarbyl)3N(H)+, u ((C1-C20)hydrocarbyl) 2N(H)2+, (C1-C20)hydrocarbylN(H)3+ or N(H)4+, wherein each (C1-C20)hydrocarbyl may be the same or different.
[0091] Examples of combinations of neutral Lewis acid activating cocatalysts include mixtures comprising a combination of a tri((1-C4)alkyl)aluminum and a halogenated tri((C6-C18)aryl)boron compound, especially a tris(pentafluorophenyl)borane. Other exemplary embodiments are combinations of such mixtures of neutral Lewis acid with a polymeric or oligomeric alumoxane and combinations of a single neutral Lewis acid, particularly of tris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxane. Mol number ratios of exemplary embodiments (metal-ligand complex):(tris(pentafluoro-phenylborane):(alumoxane) [e.g. (Group 4 metal-ligand complex):(tris(pentafluoro-phenylborane): (alumoxane)] are 1:1:1 and 1:10:30, other exemplary embodiments are 1:1:1.5 to 1:5:10.
[0092] Many activation techniques and activation cocatalysts have been previously taught, with respect to different metal-ligand complexes, in the following patents US 5,064,802; US 5,153,157; US 5,296,433; US 5,321,106; US 5,350,723; US 5,425,872; US 5,625,087; US 5,721,185; US 5,783,512; US 5,883,204; US 5,919,983; US 6.696,379; and US 7,163,907. Examples of suitable hydrocarbyloxides are described in US 5,296,433. Examples of suitable Bronsted acid salts for addition polymerization catalysts are disclosed in US 5,064,802; US 5,919,983; US 5,783,512. Examples of suitable salts of a cationic oxidizing agent and a compatible, non-coordinating anion as activation cocatalysts for addition polymerization catalysts are disclosed in US 5,321,106. Examples of carbonic salts suitable as activation cocatalysts for addition polymerization catalysts are disclosed in US 5,350,723. Examples of suitable silyl salts as activating cocatalysts for addition polymerization catalysts are disclosed in US 5,625,087. Examples of suitable complexes of alcohols, mercaptans, silanols and oximes with tris(pentafluorophenyl)borane are disclosed in US 5,296,433. Some of these catalysts are also described in a portion of US 6515155 B1 starting at column 50 at line 39 and going through column 56 at line 55, only the part of which is incorporated herein by reference.
[0093] In some embodiments, the catalyst systems described above can be activated to form an active catalyst composition by combining with one or more cocatalysts, such as a cocatalyst forming cation, a strong Lewis acid, or a combination thereof. Suitable cocatalysts for use include polymeric or oligomeric aluminoxanes, especially methyl aluminoxane, as well as inert, compatible, non-coordinating, ion-forming compounds. Exemplary suitable cocatalysts include, but are not limited to, methyl modified aluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-) amine, triethylaluminum (TEA) and any combinations thereof.
[0094] In some embodiments, one or more of the above activation cocatalysts are used in In one embodiment, a combination of a mixture of a tri((C1-C4)hydrocarbyl)aluminum, borane tri((C1-C4)hydrocarbyl) or an ammonium borate with an oligomeric or polymeric alumoxane compound can be used. Additives, additional polymers and applications
[0095] An inventive composition may comprise one or more additives. Additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, fillers (eg, TiO 2 or CaCO3), opacifiers, nucleants, adjuvants, pigments, primary antioxidants, secondary antioxidants, UV stabilizers , anti-blocking agents, slip agents, viscosity agents, fire retardants, antimicrobial agents, odor reducing agents, antifungal agents and combinations thereof. In some embodiments, an inventive composition can comprise from about 0.001 to about 10 percent by weight combined of such additives, based on the weight of the composition including such additives.
[0096] In breathable film applications (eg diapers, training pants and back films for adult incontinence, surgical gowns, protective clothing, thermal or acoustic coating, etc.), large amounts of CaCO3, or other mineral fillers , can be incorporated as a bulking agent to increase WVTR and other breathability related properties. For example, in some embodiments, a breathable film may comprise at least 20% by weight CaCO3 or at least 30% by weight CaCO3 or at least 40% by weight CaCO3 based on the total weight of the film. In some embodiments, a breathable film may comprise up to 70 wt% CaCO3 or up to 65 wt% CaCO3 or up to 60 wt% CaCO3 based on the total weight of the film. A breathable film in some embodiments may comprise from 20% to 70% by weight of CaCO3 or from 30% to 70% by weight of CaCO3 or from 40% to 65% by weight of CaCO3 or from 40% to 60% % by weight of CaCO3 based on the total weight of the film.
[0097] An inventive composition may further comprise one or more other polymers. For example, one or more other ethylene-based polymers (such polymers differ in one or more properties of the ethylene-based polymer of the first composition and the second ethylene-based polymer, i.e., density, melt index, comonomer , Mn, Mw and/or MWD) or one or more propylene-based polymers or combinations thereof.
[0098] The inventive compositions can be blended with other polymers to provide a resin in some embodiments. Non-limiting examples of other polymers that can be blended with one or more inventive compositions include an LLDPE, a VLDPE, an LDPE, an MDPE, an HDPE, an HMWHDPE, a propylene-based polymer, a polyolefin plastomer, a polyolefin elastomer. polyolefin, an olefin block copolymer, an ethylene vinyl acetate, an ethylene acrylic acid, an ethylene methacrylic acid, an ethylene methyl acrylate, an ethylene ethyl acrylate, an ethylene butyl acrylate, a polyisobutylene, a polyolefin grafted with maleic anhydride, an ionomer of any of the above, or a combination thereof. Such compositions may be blended by any method known to a person of ordinary skill in the art, including, but not limited to, dry blending and melt blending by any suitable equipment, for example, an extruder. The resin further comprises a mineral filler, such as CaCO3, to allow for the microporous morphology and breathability that result from stretching the film comprising the resin. As noted in “The Role of Calcium Carbonate in Microporous Film Applications” by Deeba Ansara, Allison Calhoun and Paul Merriman, PMA124PL, November 2001: “[Typically] CaCO3 coated with stearic acid is used to allow free flow of CaCO3, which is easier to handle, compound and disperse in the polymer. This coating results in a hydrophobic particle. The orientation process creates microvoids where the polymer separates from the calcium carbonate particles.” Thus, in some embodiments using CaCO3 as a mineral filler, the CaCO3 can be coated with stearic acid. In some embodiments, the resin can comprise 45-80% CaCO 3 by weight, based on the weight of the compound. In some such embodiments, the resin can provide good dispersion of the CaCO 3 and can then be placed with other resins to provide a breathable film that has a concentration of Desired CaCO 3 (eg 45-60% by weight of CaCO 3 ).
[0099] In some embodiments, the present invention relates to a breathable film formed from any of the inventive compositions as described herein. In some embodiments, the breathable film is a monolayer film. The breathable film, in some embodiments, is a multilayer film. Breathable films can be formed from the inventive compositions using methods and equipment well known to those skilled in the art. For example, breathable films can be produced through a blown or cast film extrusion process and then stretched/oriented in a semi-solid state below the melting point of the polymer or polymer blend.
[0100] The amount of the inventive composition to use in breathable films of the present invention may depend on a number of factors including, for example, whether the film is a monolayer or multilayer film, the other layers in the film, if it is a film. of multilayers, the desired film properties, the end use application of the film, the desired film properties, the equipment available for making the film, and others. A breathable film of the present invention, in some embodiments, comprises at least 20 percent by weight of the inventive composition, preferably at least 30 percent by weight of the inventive composition, and more preferably at least 40 percent by weight. weight of the inventive composition.
[0101] In embodiments where the breathable film comprises a multilayer film, the number of layers of the film may depend on a number of factors including, for example, the desired properties of the film, the desired thickness of the film, the content of the other layers of the film, if any of the layers in the film are to be foamed, the final use application of the film, the equipment available for making the film, and others. A multilayer breathable film can comprise up to 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 layers in various embodiments.
[0102] The inventive composition, in some embodiments, can be used in more than one layer of the film. Other layers within a multilayer film of the present invention may comprise, in various embodiments, a polymer selected from the following: an LLDPE, a VLDPE (very low density polyethylene), an MDPE, an LDPE, an HDPE, an HMWHDPE ( a high molecular weight HDPE), a propylene-based polymer, a polyolefin plastomer, a polyolefin elastomer, an olefin block copolymer, an ethylene vinyl acetate, an ethylene acrylic acid, an ethylene methacrylic acid, a methyl ethylene acrylate, an ethylene ethyl acrylate, a butyl ethylene acrylate, a polyisobutylene, a maleic anhydride grafted polyolefin, an ionomer of any of the above or a combination thereof. In some embodiments, a multilayer film of the present invention can comprise one or more loop layers known to those of skill in the art.
[0103] Breathable films may be co-extrusions comprising two or more layers in some embodiments. Common film structures include, for example, a/b/a structures, a/b/c structures and others. The individual layers within a film structure can be 1% to 99% of the multilayer film based on the total weight of the film. Exemplary settings include 10%/80%/10%, 20%/60%/20%, 1%/98%/1% and others. Breathable films that are co-extruded may be advantageous in some applications as it can, in some embodiments, achieve a better bond (eg, thermal, adhesive, or ultrasonic) between the breathable film and another substrate, provide stiffness and/or provide different haptics. In such multilayer films, one or more of the additional layers (in addition to the layer comprising an inventive composition) may comprise a polymer selected from the following: an inventive composition, a LLDPE, a VLDPE, an LDPE, an MDPE, an HDPE, a HMWHDPE, a propylene-based polymer, a polyolefin plastomer, a polyolefin elastomer, a block polyolefin copolymer, an ethylene vinyl acetate, an ethylene acrylic acid, an ethylene methacrylic acid, a methyl ethylene acrylate, an ethyl ethylene acrylate, a butyl ethylene acrylate, a polyisobutylene, a maleic anhydride grafted polyolefin, an ionomer of any of the above, or combinations thereof.
[0104] As noted above, after film formation (eg through blown or cast film extrusion processes), the film is then stretched or oriented. Often, the film is heated prior to the stretching step to a temperature above its glass transition temperature, but below its melting temperature, such that it is stretched in a semi-solid state. Drawing methods include orientation in the machine direction or the use of ring winding or interlocking gears. In machine direction orientation (MDO), the film can then be heated through contact with heated rollers before being stretched between the sets of rollers, as is known to those skilled in the art. See, for example, Wu et al., “Novel Microporous Films and Their Composites,” Journal of Engineered Fibers and Fabrics, Vol. 2, Issue 1, at 49-59 (2007). The film is typically stretched between driven rollers whereby pairs of consecutive rollers are driven at progressively higher speeds to induce stretching (see, for example, Wu et al., p. 53 in FIGURE 7). Films are typically stretched between 1.5 and 5 times their original length, depending on desired properties. Higher levels of stretch convey larger pore sizes and greater levels of breathability in the film. Higher stretch can also impart low tear or separability properties to the film. Processability or stretch window is measured in terms of the minimum amount of stretch needed to create an evenly stretched film without haze variations, often referred to as tiger stripes, to the maximum amount of stretch a film can withstand, without the creation of small holes or breaks in the weft. Films with a larger stretch window can allow for a wide range of performance properties and can be more resistant to puncture and web breakage.
[0105] In ring-wound or interlocking gear (BMI) orientation, the film can be heated to a temperature below its melting point through contact with heated rollers. The film is stretched between the interlocking rings or gears. The degree of stretch is controlled by the depth of engagement of an individual ring gear or ring gear relative to the adjacent ring(s) or gear(s). Such techniques are generally known to those skilled in the art. For example, US Patents 4,116,892 and 4,153,751, which are incorporated herein by reference, provide additional information on ring winding processes.
[0106] In both the MDO and IMG processes, the films can be annealed after the stretching process. In some embodiments, the films can be stretched in one direction, for example, with MDO or a single-stage IMG, either machine direction stretching or transverse direction stretching. Films can be stretched in two directions in series, such as MDO followed by an IMG step to stretch in the transverse direction. Another alternative is stretching in the machine direction by means of IMG followed by stretching in the transverse direction by means of IMG. However, another means of multi-direction stretching is through a stretching process.
[0107] Breathable films can have basis weights ranging from 8 to 24 grams per square meter, or alternatively from 10 to 20 g/m2 or alternatively 1218 g/m2. The basis weight of the breathable film can depend on a number of factors including the film's desired properties, the film's end use application, the equipment available to manufacture the film, the allowable cost of the application, and other factors.
[0108] In some embodiments, a breathable film of the present invention may exhibit a water vapor transmission rate of at least 100 g/m2-day-atm, measured in accordance with ASTM D-6701. A breathable film of the present invention, in some embodiments, can exhibit a water vapor transmission rate of at least 100 g/m2-day-atm and up to 10,000 g/m2-day-atm, measured in accordance with ASTM D- 6701. In some embodiments, a breathable film of the present invention can exhibit a water vapor transmission rate of at least 500 g/m 2 -day-atm and up to 10,000 g/m 2 -day-atm, in accordance with ASTM D-6701. A breathable film of the present invention, in some embodiments, can exhibit a water vapor transmission rate of at least 1000 g/m 2 -day-atm and up to 6,000 g/m 2 -day-atm, measured in accordance with ASTM D- 6701. A breathable film of the present invention, in some embodiments, can exhibit a water vapor transmission rate of at least 1500 g/m2-day-atm and up to 6,000 g/m2-day-atm, measured in accordance with ASTM D- 6701.
[0109] In some embodiments, a breathable film of the present invention may exhibit a water head of at least 60 cm as measured by EN 20811.
[0110] It is also contemplated that a breathable film may comprise additional layers, either co-extruded or as a laminate. These layers can be selected to provide additional functionality, for example, layers to provide extra strength, adhesion to another substrate, such as properties of a non-woven fabric, and/or aesthetics, such as feel or appearance.
[0111] Some embodiments of the present invention relate to laminates comprising one or more breathable films of the present invention. For example, breathable films of the present invention can be used in film/non-woven laminates. Typical nonwovens for use in such laminates may be spin deposited, air deposited, carded wefts or composites thereof. Typical nonwoven composites for use in laminates with a breathable film of the present invention include three layers of spunbonded material, (e.g., S/S/S), a spunbonded/melt blown/spunbond composite) ( for example, S/M/S) and others. Common methods for bonding the film to nonwovens include, for example, hot melt bonded adhesive lamination, ultrasonic bonding, and thermal bonding via a calendar or pinch roller.
[0112] The present invention also relates to articles comprising at least one component formed from an inventive composition. The component can be, for example, a film laminate or a breathable film. Such components can be used in disposable medical or hygiene products as breathable but liquid impervious layers. Examples of articles comprising such breathable film laminates include diapers, workout pants, feminine hygiene products, adult incontinence products, medical drapes, medical gowns, surgical suits, and others. In items such as diapers, workout pants, feminine care products and adult incontinence products, a breathable film or film laminate is also often referred to as a backsheet. In medical products, a breathable film or film laminate is often referred to as the "barrier layer", since the breathable film or film laminate can prevent contamination from a healthcare professional to a patient and vice-versa. versa. Breathable films can be incorporated into such articles using techniques known to those of skill in the art based on the teachings presented herein. DEFINITIONS
[0113] Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages are based on weight and all test methods are as current as of the filing date of the present disclosure.
[0114] The term "composition," as used herein, includes material(s) that comprise(s) the composition, as well as reaction products and decomposition products formed from the materials of the composition.
[0115] The term "comprising" and its derivatives is not intended to exclude the presence of any additional component, step or process, whether or not it is disclosed herein. For the avoidance of doubt, all compositions claimed herein using the term "comprising" may include any additional additive, adjuvant or compound, whether polymeric or otherwise, unless otherwise indicated. In contrast, the term "consisting essentially of" excludes from its scope of any further reference any other component, step or process, except those which are not essential for operability. The term "consisting of" excludes any component, step or procedure not specifically delineated or listed.
[0116] The term "polymer", as used herein, refers to a polymeric compound prepared by polymerization of monomers, either of the same type or of a different type. The generic term polymer thus encompasses the term homopolymer (used to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure) and the term interpolymer as defined in follow. Trace amounts of impurities can be incorporated into and/or into the polymer.
[0117] The term "interpolymer", as used herein, refers to a polymer prepared by polymerization of at least two different types of monomers. The generic term interpolymer thus includes copolymers (used to refer to polymers made from two different types of monomers) and polymers made from more than two different types of monomers.
[0118] The term "olefin-based polymer", as used herein, refers to a polymer that comprises, in polymerized form, a greater amount of olefin monomer, for example ethylene or propylene (based on the weight of the polymer ) and optionally may comprise at least one polymerized comonomer.
[0119] The term "ethylene-based polymer" as used herein, refers to a polymer that comprises a greater amount of polymerized ethylene monomer (based on the total weight of the polymer) and optionally may comprise at least less, a polymerized comonomer.
[0120] The term "ethylene/α-olefin interpolymer", as used herein, refers to an interpolymer comprising, in polymerized form, a greater amount of ethylene monomer (based on the weight of the interpolymer) and, at less, an α-olefin.
[0121] The term "ethylene/α-olefin copolymer", as used herein, refers to a copolymer that comprises, in polymerized form, a greater amount of ethylene monomer (based on the weight of the copolymer) and an α -olefin, such as the only two types of monomer.
[0122] The term "propylene-based polymer" as used herein, refers to a polymer that comprises, in polymerized form, a greater amount of propylene monomer (based on the total weight of the polymer) and, optionally, it can comprise at least one polymerized comonomer. TEST METHODS Melting Index
[0123] Melt indices I2 (or I2) and I10 (or I10) were measured according to ASTM D-1238 (method B) at 190°C and at 2.16 kg and 10 kg load, respectively. Their values are shown in g/10 min. Density
[0124] Samples for density measurement were prepared in accordance with ASTM D4703. Measurements were taken, in accordance with ASTM D792, Method B, within one hour of sample pressing. Dynamic Shear Rheology
[0125] Each sample was compression molded on a circular plate "3 mm thick x 25 mm in diameter" at 177oC for five minutes under a pressure of 10 MPa in air. The sample was then removed from the press and placed on a bench to cool.
[0126] At constant temperature, frequency sweep measurements were performed on a voltage-controlled rheometer ARES (TA Instruments), equipped with 25 mm parallel plates, under a nitrogen purge. For each measurement, the rheometer was thermally balanced for at least 30 minutes before zeroing the gap. The sample disc was placed on the plate and allowed to melt for five minutes at 190°C. The plates were then closed at 2 mm, the sample cut and then the test started. The method had an additional five minute delay built in to allow for temperature equilibrium. The experiments were carried out at 190oC over a frequency range of 0.1 to 100 rad/s, at an interval of five points per decade. The voltage amplitude was constant at 10%. The stress response was analyzed in terms of amplitude and phase, from which the storage modulus (G'), the loss modulus (G"), the complex modulus (G*), the dynamic viscosity (n *or Eta*) and tan δ (or tan delta) were calculated. Conventional gel permeation chromatography (GPC conv.)
[0127] A PolymerChar (Valencia, Spain) GPC-IR high temperature chromatography system was equipped with a Precision Detector (Amherst, MA), a Model 2040 2-angle laser light scattering detector, a IR5 infrared detector and a 4-capillary viscometer, both from PolymerChar. Data collection was performed using PolymerChar instrument control software and data collection interface. The system was equipped with an online solvent degassing device and pumping system from Agilent Technologies (Santa Clara, CA).
[0128] The injection temperature was controlled at 150 degrees Celsius. The columns used were three 10 micron "Mixed-B" columns from Polymer Laboratories (Shropshire, UK). The solvent used was 1,2,4-trichlorobenzene. Samples were prepared at a concentration of "0.1 grams of polymer in 50 ml of solvent." The chromatographic solvent and solvent sample preparation each contained "200 ppm butylated hydroxytoluene (BHT)." Both solvent sources were nitrogen sparged. Samples of ethylene-based polymers were gently shaken at 160 degrees Celsius for three hours. The injection volume was “200 microliters” and the flow rate was “1 ml/minute.” The GPC column set was calibrated by running 21 “narrow molecular weight distribution” polystyrene standards. MW) of the standards ranges from 580 to 8,400,000 g/mol and the standards were contained in six “cocktail” type blends. Each standard blend had at least a decade of separation between the individual molecular weights. Polymer Laboratories. Polystyrene standards were prepared at "0.025 g in 50 mL solvent" for molecular weights equal to or greater than 1,000,000 g/mol and at "0.050 g in 50 mL solvent" for weights molecular weights of less than 1,000,000 g/mol.
[0129] The polystyrene standards were dissolved at 80°C, with gentle agitation, for 30 minutes. Narrow standard blends were run first, and in descending order of "highest molecular weight component" to minimize degradation. The standard peak molecular weights of polystyrene were converted to the molecular weight of polyethylene using Equation 1 (as described in Williams and
[0130] Ward, J. Polym. Sci., Polym. Letters, 6, 621 (1968)):
[0131] Mpolyethylene = A x (Mpolystyrene)B (Eq. 1),
[0132] where M is the molecular weight, A is 0.4316 and B is 1.0.
[0133] The number average molecular weight (Mn(gpc conv)), the weight average molecular weight (Mw-gpc conv) and the z average molecular weight (Mz(gpc conv)) were calculated according to Equations 2- 4 below.

[0134] In Equations 2-4, the RV is the volume of the retention column (linearly spaced), collected at "1 point per second", the IR is the IR detector signal subtracted from the baseline, in Volts, at from the IR5 measurement channel of the GPC instrument and the MPE is the MW equivalent to polyethylene, determined from Equation 1. Data calculation was performed using PolymerChar's "GPC One Software (version 2013H)". Zero shear viscosity creep measurement method
[0135] The zero-shear viscosities were obtained by means of creep tests, which were performed in an AR-G2 tension-controlled rheometer (TA Instruments; New Castle, Del), using parallel plates "25 mm in diameter"a 190°C. The rheometer oven was set to test the temperature for at least 30 minutes before zeroing the accessories. At the test temperature, a compression molded sample disc was inserted between the plates and allowed to equilibrate for five minutes. The top plate was then reduced to 50 µm (instrument configuration) above the desired test gap (1.5 mm). Any superfluous material was trimmed off and the top plate was reduced to the desired range. Measurements were taken under nitrogen purge at a flow rate of 5L/min. The default fluency time was set to two hours. Each sample was compression molded on a circular plate "2 mm thick x 25 mm in diameter", 177oC, for five minutes, under a pressure of 10 MPa, in air. The sample was then removed from the press and placed on a bench to cool.
[0136] A constant low shear stress of 20 Pa was applied to all samples, to ensure that the steady state shear rate was low enough to be in the Newtonian region. The resulting steady-state shear rates were in the range of 10-3 to 10-4 s-1 for the samples in this study. Steady state was determined by a linear regression for all data, in the last 10% time window of the graph of "log(J(t)) vs. log(t)", where J(t) was the fulfillment of fluency et was the time of fluency. If the slope of the linear regression was greater than 0.97, the steady state was considered reached, then the creep test was stopped. In all cases in this study, the slope meets the criterion within one hour. The steady-state shear rate was determined from the slope of the linear regression of all data points, in the last 10% time window of the "ε vs. t" graph, where ε was the stress. Zero shear viscosity was determined from the ratio of applied stress to steady state shear rate.
[0137] In order to determine if the sample was degraded during the creep test, a small amplitude oscillatory shear test was performed before and after the creep test, on the same sample from 0.1 to 100 rad / s . The complex viscosity values of the two tests were compared. If the difference in viscosity values at 0.1 rad/s was greater than 5%, the sample was considered degraded during the creep test and the result was discarded.
[0138] The zero shear viscosity ratio (ZSVR) is defined as the ratio of the zero shear viscosity (ZSV) of the branched polyethylene material to the ZSV of a linear polyethylene material (see ANTEC procedure below) in molecular weight equivalent mean (Mw (gpc conv)), according to the following Equation 5:

[0139] The ZSV value was obtained from a creep test at 190ºC, through the method as described below. The value of Mw (gpc conv) was determined by the conventional GPC method (Equation 3), as discussed above. The correlation between linear polyethylene ZSV and its Mw (gpc conv) was established based on a series of linear polyethylene reference materials. A description of the ZSV-Mw relationship can be found in the ANTEC process: Karjala et al., Detection of Low Levels of Long-chain Branching in Polyolefins, Annual Technical Conference - Society of Plastics Engineers (2008), 66 887-891. 1H NMR Method
[0140] A stock solution (3.26 g) was added to "0.133 g of polymer sample" in a 10 mm NMR tube. The mother liquor was a mixture of tetrachloroethane-d2 (TCE) and perchlorethylene (50:50, w:w) with 0.001M Cr3+. The solution in the tube was purged with N2 for 5 minutes to reduce the amount of oxygen. The capped sample tube was left at room temperature overnight to swell the polymer sample. The sample was dissolved at 110°C with periodic vortex mixing. The samples were free of additives that can contribute to unsaturation, for example, glidants such as erucamide. Each 1 H NMR analysis was performed with a 10 mm cryoprobe at 120°C on the Bruker Avance 400 MHz spectrometer.
[0141] Two experiments were carried out to obtain the unsaturation: the control and the double pre-saturation experiments. For the control experiment, data was processed with an exponential window function with LB=1 Hz and the baseline was corrected from 7 to -2 ppm. The 1H residual TCE signal was set to 100 and the Itotal of -0.5 to 3 ppm was used as the polymer signal throughout the control experiment. The "CH2 group number, NCH2," in the polymer was calculated as follows in Equation 1A:

[0142] For the double presaturation experiment, the data was processed with an exponential window function with LB=1 Hz and the baseline was corrected from about 6.6 to 4.5 ppm. The residual 1H signal of TCE was set to 100, and the corresponding integrals for (Itrisubstituted, Ivinyl and Ivinylidene) unsaturations were integrated. The use of NMR spectroscopic methods for the determination of polyethylene unsaturation is well known, for example, see Busico, V., et al., Macromolecules, 2005, 38, 6988. The unit number of unsaturation by vinylene, trisubstituted, vinyl and vinylidene were calculated as follows:

[0143] The unsaturation units per 1,000 carbons, all polymer carbons including base carbons and branch carbons, were calculated as follows:


[0144] The chemical shift reference was set at 6.0 ppm for the 1H signal of the residual TCE-d2 proton. The control was performed with pulse ZG, NS=4, DS=12, SWH=10,000 Hz, AQ=1.64s, D1=14s. The double presaturation experiment was performed with a modified pulse sequence, with O1P=1,354 ppm, O2P=0.960 ppm, PL9=57db, PL21=70db, NS=100, DS=4, SWH=10,000 Hz, AQ =1.64s, D1=1 s (where D1 is the presaturation time), D13=13s. Only vinyl levels are reported in Table 2 below. 13C NMR Method
[0145] Samples are prepared by adding approximately 3g of a 50/50 mixture of tetra-chloroethane-d2/orthodichlorobenzene, containing 0.025M Cr(AcAc)3 to a "0.25g polymer sample" into an NMR tube 10 mm. Oxygen is removed from the sample by purging the tube space with nitrogen. The samples are then dissolved, and homogenized by heating the tube and its contents to 150°C using a heat block and heat gun. Each dissolved sample is visually inspected to ensure homogeneity.
[0146] All data is collected by means of a Bruker 400 MHz spectrometer. Data is acquired using a 6-second pulse repetition delay, 90 degree flip angles and closed reverse dissociation with a sample temperature of 120° Ç. All measurements are made on unwired samples in locked mode. Samples are allowed to thermally equilibrate for 7 minutes prior to data acquisition. The 13 C NMR chemical shifts were referenced internally to the EEE triad at 30.0 ppm.
[0147] 13C NMR comonomer content: It is well known to use NMR spectroscopic methods to determine polymer composition. ASTM D 5017-96; J.C. Randall et al., in "NMR and Macromolecules" ACS Symposium series 247; J.C. Randall, Ed., Am. Chem. Soc., Washington, DC, 1984, Ch. 9; and J.C. Randall in "Polymer Sequence Determination", Academic Press, New York (1977) provide general methods of polymer analysis by NMR spectroscopy. Comonomer Weighted Molecular Distribution Index (MWCDI)
[0148] A PolymerChar (Valencia, Spain) GPC-IR high temperature chromatography system was equipped with a Precision Detector (Amherst, MA), a Model 2040 2-angle laser light scattering detector, a IR5 infrared detector and a 4-capillary viscometer, both from PolymerChar. The "15 degree angle" of the light scattering detector was used for calculation purposes. Data collection was performed using PolymerChar instrument control software and data collection interface. The system was equipped with an online solvent degassing device and pumping system from Agilent Technologies (Santa Clara, CA).
[0149] The injection temperature was controlled at 150 degrees Celsius. The columns used were four, 20 micron "Mixed-A" light scattering columns from Polymer Laboratories (Shropshire, UK). The solvent was 1,2,4-trichlorobenzene. Samples were prepared at a concentration of "0.1 gram polymer in 50 ml solvent." The chromatographic solvent and solvent sample preparation each contained "200 ppm butylated hydroxytoluene (BHT)." Both solvent sources were nitrogen sparged. Samples of ethylene-based polymers were gently shaken at 160 degrees Celsius for three hours. The injection volume was "200 microliters' and the flow rate was "1 milliliter/minute."
[0150] Calibration of the GPC column set was performed with 21 "narrow molecular weight distribution" polystyrene standards with molecular weights ranging from 580 to 8400000 g/mole. These standards were arranged in six "cocktail" type mixtures, with at least a decade of separation between the individual molecular weights. Standards were purchased from Polymer Laboratories (UK Shropshire). Polystyrene standards were prepared at "0.025g in 50 ml solvent" for molecular weights equal to or greater than 1,000,000 g/mol and at "0.050 grams in 50 ml solvent" for molecular weights less than 1,000,000 g/mol. Polystyrene standards were dissolved at 80°C, with gentle agitation, for 30 minutes. Narrow standard blends were run first, and in descending order of "highest molecular weight component" to minimize degradation. Standard peak polystyrene molecular weights were converted to polyethylene molecular weights using equation 1B (as described in Williams and Ward, J. Polym. Sci., Polym. Let, 6, 621 (1968)): Polyethylene = A x (Polystyrene)B (Eq. 1B),
[0151] where M is the molecular weight, A has a value of approximately 0.40 and B equals 1.0. The A value was adjusted between 0.385 and 0.425 (depending on the specific efficiency of the column set), such that the linear polyethylene of weight average molecular weight NBS 1475A (NIST) corresponded to 52,000 g/mol, as calculated by the Equation 3B, below:

[0152] In Equations 2B and 3B, RV is column retention volume (linearly spaced), collected at “1 point per second.” The IR is the IR detector signal subtracted from the baseline, in Volts, from of the measurement channel of the GPC instrument and the MPE is the equivalent MW of polyethylene, determined from Equation 1B. Data calculation was performed using PolymerChar's "GPC One Software (version 2013H)".
[0153] A calibration for the IR5 detector ratios was performed using at least ten ethylene-based polymer standards (polyethylene homopolymers and ethylene/octene copolymers; narrow molecular weight distribution and homogeneous comonomer distribution) from known short chain branching frequency (SCB) (measured by the 13C NMR method, as discussed above), ranging from homopolymer (0 SCB/100 total C) to approximately 50 SCB/100 total C, where total C = carbons in base + carbons in branches. Each standard had a weight average molecular weight of 36,000 g/mol to 126,000 g/mol, as determined by the GPC-LALS processing method described above. Each standard had a molecular weight distribution (Mw/Mn) of 2.0 to 2.5, as determined by the GPC-LALS processing method described above. Polymer properties for SCB standards are shown in Table A. Table A: "SCB" Standards

[0154] The "IR5 Area Ratio (or "IR5 Methyl Channel Area / IR5 Measurement Channel Area")" of the "IR5 methyl channel sensor line subtracted area response" to the "response area subtracted from the baseline of the IR5 measurement channel sensor" (standard filters and filter wheel as supplied by PolymerChar: IR5_FWM01 number included as part of the GPC-IR instrument) was calculated for each of the "SCB standards ". A linear adjustment of the SCB frequency in relation to the "IR5 Area Ratio" was constructed in the form of the following Equation 4B: SCB/total C 1000 = A0 + [A1 x (IR5 Methyl Channel Area / IR5 Methyl Channel Area Measurement)] (Eqn. 4B), where A0 is the intercept of "SCB/100 total C" at an "Area Ratio IR5" of zero and A1 is the slope of "SCB/1000 total C with respect to the "Area Ratio IR5" and represents the increase in "SCB/100 total C as a function of "Area Ratio IR5".
[0155] A series of "linear chromatographic heights subtracted from baseline" for the chromatogram generated by the "IR5 methyl channel sensor" was established as a function of column elution volume, to generate a line-corrected chromatogram base (methyl channel). A series of "linear chromatographic heights subtracted from baseline" for the chromatogram generated by the "IR5 measurement channel" was established as a function of column elution volume to generate a baseline corrected chromatogram (measurement channel ).
[0156] The "IR5 Height Ratio" from "baseline corrected chromatogram (methyl channel)" to "baseline corrected chromatogram (measurement channel)" was calculated at each elution volume index in column (each index equally spaced, representing one data point per second at 1 ml/min) via the sample integration link. The "IR5 Height Ratio" was multiplied by the A1 coefficient and the A0 coefficient was added to this result to produce the sample's predicted SCB frequency. The result was converted into mole percent comonomer, as follows in Equation 5B: Comonomer percent in moles = {SCBf / [SCBf + ((1000 - SCBf * Length of comonomer) / 2)]} * 100 (Eq. 5B), where “SCBf” is the "SCB per 1000 total C", and the "comonomer length" = 8 for octene, 6 for hexene, and so on.
[0157] Each elution volume index was converted to a molecular weight value (Mwi) using the method of Williams and Ward (described above; Eq. 1B). The "mole percent comonomer (y-axis)" was plotted as a function of Log(Mwi) and the slope was calculated between 15,000 Mwi and 150,000 g/mol Mwi (end-group corrections at the chain ends were omitted for this calculation.) An EXCEL linear regression was used to calculate the slope between and including Mwi from 15,000 to 150,000 g/mol. This slope is defined as the comonomer weighted molecular distribution index (MWCDI = molecular distribution index weighted comonomers). Representative determination of MWCDI (First inventive composition 2)
[0158] A plot of "SCB per 1000 total C" measured (=SCBf)” against the Area Ratio of IR5"
[0159] of the SCB patterns was generated (see Figure 1) and the intercept (A0) and slope (A1) were determined. Here, A0 = -90.246 SCB/100 total C; and A1 = 499.32 SCB/100 total C.
[0160] The "Height Ratio of IR5" was determined for Inventive Example 2 (see integration shown in Figure 2). This height ratio (Height Ratio IR5 from Inventive Example 2) was multiplied by the coefficient A1 and the coefficient A0 was added to this result to produce the predicted SCB frequency in this example at each elution volume index as described above (A0 = -90,246 SCB/100 total C; and A1 = 499.32 SCB/100 total C). SCBf was plotted as a function of the equivalent molecular weight of polyethylene, as determined using Equation 1B, as discussed above. See Figure 3 (Log Mwi used as the x-axis).
[0161] The SCBf was converted to "mole percent comonomer" through Equation 5B. The "mole percent comonomer" was plotted as a function of the equivalent molecular weight of polyethylene, as determined using Equation 1B, as discussed above. See Figure 4 (Log Mwi used as the x-axis). A linear fit was from 15,000 g/mol Mwi to 150,000 g/mol Mwi, giving a slope of "2.27 percent in moles of comonomer x mol/g." Thus, MWCDI = 2.27. An EXCEL linear regression was used to calculate the slope between and including Mwi from 15,000 to 150,000 g/mol. Film Test Conditions
[0162] The following physical properties were measured on the produced films (see experimental section). • 45° Brightness: ASTM D-2457. • Clarity: ASTM D-1746. ASTM D1003 Total Mist
[0163] Samples measured by internal haze and general (total) haze were sampled and prepared in accordance with ASTM D1003. The inner haze was obtained by matching the refractive index using mineral oil on both sides of the films. A Hazeguard Plus (BYK-Gardner USA; Columbia, MD) was used for the test. Surface haze was determined as the difference between total haze and internal haze. Total haze was reported as the mean of five measurements. Elmendorf Slot Type B ASTM D1922 MD (machine direction) and CD (cross direction)
[0164] The Elmendorf tear test determines the average force to propagate the tear over a specified length of plastic film or soft sheets, after the tear has been initiated, using an Elmendorf-type tear tester.
[0165] After producing the film from the sample to be tested, the film was conditioned for at least 40 hours at 23°C (+/- 2°C) and 50% relative humidity (+/- 5), per ASTM standards. The standard test conditions were 23°C (+/- 2°C) and 50% RH (+/- 5) per ASTM standards.
[0166] The force, in grams, required to propagate the tear through a film or sheet sample was measured using an accurately calibrated pendulum device. In the test, acting by gravity, the pendulum swung through an arc, tearing the specimen from a pre-cut slit. The sample was maintained on one side by a pendulum and on the other side by a stationary element. The loss of energy by the pendulum was indicated by a pointer or an electronic scale. The scale indication was a function of the force required to tear the specimen.
[0167] The sample body geometry used in the Elmendorf tear test was 'constant radius geometry' as specified in ASTM D1922. The test is typically performed on samples that have been cut from MD and CD film directions. Before testing, the film sample thickness was measured at the center of the sample. A total of 15 samples per film direction were tested and the average tear strength and average thickness reported. The average tear strength was normalized to the medium thickness MD and CD ASTM D882, 1% and 2% Secant Modulus, Tensile strength and Tensile strength.
[0168] The secant modulus and tensile breaking strength of MD (machine direction) and CD (cross direction) film (or tensile strength) were measured with an Instron universal tester in accordance with ASTM D882-10. The reported secant modulus value was the average of five measurements. Tensile breaking strength was determined using five film samples in each direction, with each sample being "1 inch x 6 inches" in size. Breaking strength is the tensile load or force required to break or break a given material. It is measured as pounds of force for every square inch (psi). The breaking stress is the stress at which the material breaks and is measured as length at break divided by the original length multiplied by 100 (%). Puncture resistance
[0169] Perforation test determines the resistance of a film to probe penetration at a low pattern rate, a single test speed. The drill test method is based on ASTM D5748. After film production, the film was conditioned for at least 40 hours at 23°C (+/- 2°C) and 50% R.H (+/- 5), according to ASTM standards. The standard test conditions were 23°C (+/2°C) and 50% RH (+/- 5), per ASTM standards. Perforation was measured on a tensile testing machine. Square samples were cut from a sheet to a size of "6 inches by 6 inches." The sample was clamped onto a circular "4 inch diameter" sample holder and a drill probe was pushed into the center of the clamped film at a crosshead speed of 10 inches/minute. The internal test method follows ASTM D5748, with one modification. It is deviated from the ASTM D5748 method, where the probe used was a "0.5 inch diameter" polished steel ball on a "0.25 inch" support rod (instead of the 0.75 probe inches in pear-shaped diameter specified in D5748).
[0170] There was a maximum travel length of "7.7 inches" to prevent damage to test fixtures. There was no measuring length; before testing, the probe is as close as possible, but does not touch the sample.
[0171] A single thickness measurement was taken at the center of the sample. For each sample, the maximum force, the force at rupture, the penetration distance and the energy to rupture were determined. A total of five samples are tested to determine an average perforation value. The drill probe was made using "Kim-Wipe" after each sample. ASTM D1709 Dart Drop
[0172] The Film Drop Dart test determines the energy that causes a plastic film to fail under specific impact conditions of a free falling dart. The test result is the energy, expressed in terms of the missile's weight falling from a given height, which would result in 50% of the tested samples failing.
[0173] After film production, the film was conditioned for at least 40 hours at 23°C (+/- 2°C) and 50% R.H (+/- 5), according to ASTM standards. The standard test conditions were 23°C (+/- 2°C) and 50% RH (+/- 5) per ASTM standards.
[0174] The test result was reported by both Method A, which uses a "1.5" diameter dart head and a drop height of 26", and Method B, which uses a "Dart head of 2" diameter and a drop height of 60". The thickness of the sample was measured at the center of the sample, and the sample was then secured by an annular sample holder with an inside diameter of 5 inches. The dart was loaded above the center of the sample and released by a pneumatic or electromagnetic mechanism.
[0175] The test was performed according to the "ladder" method. If the sample failed, a new sample was tested with the dart weight reduced by a known and fixed amount. If the sample did not fail, a new sample was tested with the dart weight increased by a known amount. After 20 samples were tested, the number of failures was determined. If that number was 10, then the test is complete. If the number was less than 10, then testing continued until 10 failures had been recorded. If the number was greater than 10, testing continued until the total of non-fails was 10. Dart Drop Resistance was determined from these data, in accordance with ASTM D1709, and expressed in grams, as Impact Drop Javelin Type A or B. In some cases, Javelin drop resistance may be between A and B. In these cases, it was not possible to obtain a quantitative dart value. Water Vapor Transmission Rate (WVTR)
[0176] The Water Vapor Transmission Rate (or WVTR) is the absolute transmission rate. WVTR was determined in accordance with ASTM D-6701 and is reported in units of g/m2/day. EXAMPLES
[0177] The following examples illustrate the present invention, but are not intended to limit the scope of the invention. EXAMPLE 1: First inventive compositions 1, 2 and 3
[0178] The first inventive compositions 1, 2 and 3 each contain two ethylene-octene copolymers. Each composition was prepared, through solution polymerization, in a double series closed loop reactor system in accordance with US Patent 5,977,251 (see Figure 2 of this patent), in the presence of a first catalyst system, as described. below, in the first reactor and a second catalyst system, as described below, in the second reactor.
[0179] The first catalyst system comprises a bis((2-oxoyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene-1,2- cyclohexanediylhafnium (IV) dimethyl, represented by the following formula (CAT 1):

[0180] The molar ratios of CAT 1 metal, added to the polymerization reactor, in situ, for Cocat1 (modified methyl aluminoxane) or Cocat2 (bis(hydrogenated tallow alkyl)methyl, amine tetrakis(pentafluorophenyl)borate(1- )), are shown in Table 1.
[0181] The second catalyst system comprising a Ziegler-Natta type catalyst (CAT 2). The Ziegler-Natta type heterogeneous catalyst premix was prepared substantially in accordance with U.S. Pat. U.S. No. 4,612,300, by sequentially adding to one volume of ISOPAR E, a slurry of anhydrous magnesium chloride in ISOPAR E, a solution of EtAlCl2 in heptane, and a solution of Ti(O-iPr)4 in heptane, to obtain a composition containing a magnesium concentration of 0.20 M and a Mg/Al/Ti ratio of 40/12.5/3. An aliquot of this composition was further diluted with ISOPAR-E to obtain a final concentration of 500 ppm Ti in the slurry. While being fed to, and prior to entering the polymerization reactor, the catalyst premix was contacted with a dilute Et3Al solution in the Al to Ti molar ratio specified in Table 1 to generate the active catalyst.
[0182] The polymerization conditions for the first inventive compositions 1, 2 and 3 are shown in Table 1. As can be seen in Table 1, Cocat. 1 (modified methylaluminoxane (MMAO)); and Cocat. 2 (bis(hydrogenated tallow alkyl)methyl, amine tetrakis(pentafluorophenyl)borate(1- ) ) were each used as a cocatalyst for CAT 1. Additional properties of inventive compositions 1, 2 and 3 were measured and shown in Table 2. The MWD GPC profiles and corresponding comonomer distribution overlays are shown in Figures 5-7. Each polymer composition was stabilized with small (ppm) amounts of stabilizers. First comparative compositions A and B
[0183] Comparative compositions A and B each contain two ethylene-octene copolymers and each was prepared, through solution polymerization, in a double-loop reactor system, in the presence of a first catalyst system, as described below, in the first reactor, and a second catalyst system, as described below, in the second reactor. The first catalyst system comprises titanium, [N-(1,1-dimethylethyl)-1,1-dimethyl-1-[(1,2,3,3a-n)-1,5,6,7-tetra- hydro-2-methyl-indacen-1-yl]silanaminate(2-)-KN] [(1,2,3,4-n)-1,3-pentadiene]- (CAT 3, a restricted geometry catalyst) . The second catalyst system comprises the Ziegler-Natta premix (CAT 2) as discussed above.
[0184] The polymerization conditions for comparative compositions A and B are shown in Table 1. As can be seen in Table 1, Cocat. 1 (modified methylaluminoxane (MMAO)) and Cocat. 2 (bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)amine) were each used as a cocatalyst for CAT 3. Additional properties of comparative compositions A and B were measured and are shown in Table 2. The MWD GPC profiles and corresponding comonomer distribution overlaps are shown in Figures 5 and 6. Each polymer composition was stabilized with small (ppm) amounts of stabilizers. Comparative C (first composition)
[0185] Comparative C is an ethylene-hexene copolymer composition, commercially available under the tradename EXCEED 1018CA from ExxonMobil Chemical Company and having a density of approximately 0.918 g/cm3, a melt index of (I2 or I2), measured at 190°C and 2.16 kg, approximately 1.0 g/10 minutes. The additional properties of comparative example C have been measured and are shown in Table 2. The MWD GPC profile and the corresponding comonomer distribution overlap is shown in Figure 5. Comparative Db (first composition)
[0186] Comparative D is an ethylene-octene copolymer composition, supplied by The Dow Chemical Company, under the tradename ELITE 5230G and having a density of approximately 0.916 g/cm3, a melt index (I2 or I2) , measured at 190°C and 2.16 kg, of approximately 4.0 g/10 minutes. The additional properties of comparative example D have been measured and are shown in Table 2. The GPC profile of MWD and the corresponding comonomer distribution overlap is shown in Figure 7. Table 1: Polymerization Conditions (Rx1 = reactor 1; Rx2 = reactor 2)


* solvent = ISOPAR E Table 2: Properties of inventive and comparative compositions

EXAMPLE 2: Inventive Compositions 4 and 5
[0187] The inventive compositions 4 and 5 each contain an ethylene-octene copolymer. Inventive compositions 4 and 5 were prepared in the same way and using the same catalyst system in the form of inventive compositions 1-3, with the exception that the polymerization conditions are indicated in Table 3. Table 3: Polymerization Conditions (Rx1 = reactor 1; Rx2 = reactor 2)


[0188] A breathable film was formed from Inventive Composition 4. Inventive Composition 4 was compounded using a Farrel continuous mixer with underwater pelletizing. The amounts of the components that were composed into pellets are shown in Table 4: Table 4

[0189] The calcium carbonate was Imerys FilmLink® 500, which is commercially available from Imerys Carbonates. The LDPE was DOW™ LDPE 640I, which is commercially available from The Dow Chemical Company.
[0190] The films were manufactured on a 5-layer Egan Davis Standard co-extrusion cast film line. The cast line consisted of three 2-1/2" extruders and two 2" 30:1 L/D Egan Davis Standard MAC extruders that are air cooled. All extruders had moderate duty DSB (Davis Standard Barrier) screws. Equipment specifications included a 5-layer Cloeren dual flat feed block and a Cloeren 36" Epich II 5.1 automatic mold. The primary coolant roller had a matte finish and was 40" OD x 40" in length with a surface finish of 30-40 RMS for best release characteristics. The secondary coolant roller was 20" OD x 40" long, with a surface of 2-4 RMS for better web tracking. Both the primary and secondary cooling rollers had chilled water circulating through them to provide quenching.A Scantech X-ray gauge sensor for gauge thickness and automatic gauge control was available if needed.The films were fabricated under the following conditions: melting temperature = 204.4°C (400°F); temperature profile (B1 148.9°C (300°F), B2 204.4°C (400°F), B3-5 204 .4°C (400°F), 204.4°C 400°F screen, 204.4°C (400°F) adapter, mol de in all zones 204.4°C (400°F)), yield rate = 90.7-122.5 kg/h (200-270 lb/h), cooled roll temperature = 70°F, temperature cast roll = 21.1°C (70°F), air knife = 7.4" H2O, vacuum box = OFF, mold gap = 20-25 mil, and air gap = 4".
[0191] Each film was oriented using a machine direction orientation (MDO) system such as those available from Marshall and Williams Plastics and Parkinson Technologies, Inc. The film was oriented in the machine direction through a series of rollers with the same or different speeds to provide guidance. The width of the film roll over the feed roll was 24 inches, with a thickness of 2.0 mil. The rollers were maintained at the following temperatures: preheat roller 1 (73.9°C) (165°F), preheat roller 2, (73.9°C) (165°F), slow drag (85°C) (185°F), fast drag roller (79.4°C) (175°F), annealing roller (73.9°C) (165°F) and cooled roller (60 °C) (140°F). The slow drag roller speed was 1.55 m (5.1 ft) per minute, and the fast drag roller speed was 5.82 m (19.1 ft) per minute to provide a drag rate of 3.75. The exit width of the film roll was 548.5 mm (21.6 inches), with a thickness of 0.7-0.8 mil. The temperature profile used in the MDO System is shown in Table 5:


[0192] Various film properties of the oriented film were measured. The number of samples, mean values and standard deviations are shown in Table 6: Table 6
EXAMPLE 3:
[0193] The stretch windows of Inventive Composition 4 and DOWLEX™ 2047G polyethylene resin (commercially available from The Dow Chemical Company) were determined using MDO conditions as described above with modification of roll temperatures as shown in Table 7: Table 7
The stretch windows are shown in Table 8: Table 8

[0194] The minimum drag ratio was the stretch ratio where the haze variations (tiger stripes) were visually absent from the film, and the maximum drag ratio was the stretch ratio, where holes or breaks in the weft were observed. film. EXAMPLE 4: Inventive Compositions 6 and 7
[0195] The inventive compositions 6 and 7 each contain an ethylene-octene copolymer. Inventive compositions 6 and 7 were prepared in the same way and using the same catalyst system in the form of inventive compositions 13, with the exception that the polymerization conditions are indicated in Table 9. Table 9: Polymerization Conditions (Rx1 = reactor 1; Rx2 = reactor 2)


[0196] The properties of Inventive Compositions were measured and are presented in Table 10. Table 10: Properties of Inventive Compositions

[0197] Breathable films can be formed from Inventive Compositions 6 and 7.

权利要求:
Claims (14)
[0001]
1. Breathable film, characterized in that it comprises a first composition, the first composition comprising at least one ethylene-based polymer and the first composition comprising a MWCDI value greater than 1.2 and a melt index ratio (I10/I2) that meets the following equation: I10/I2 > 7.0 - 1.2 x log (I2), the film further comprising 40 to 65 percent by weight of a mineral filler material.
[0002]
2. Breathable film according to claim 1, characterized by the fact that the first composition has a MWCDI value less than or equal to 10.0.
[0003]
3. Breathable film according to any one of claims 1 or 2, characterized in that the first composition has a density of 0.910-0.940 g/cm3 and a melt index (I2) of 0.5 to 30 g/10 minutes .
[0004]
4. Breathable film according to any one of claims 1 to 3, characterized in that the film has a basis weight of 10 to 20 g/m2.
[0005]
5. Breathable film according to any one of claims 1 to 4, characterized in that it further comprises a second polymer, and the second polymer is selected from the following: an LLDPE, a VLDPE, an LDPE, an MDPE , an HDPE, an HMWHDPE, a propylene-based polymer, a polyolefin plastomer, a polyolefin elastomer, an olefin block copolymer, an ethylene vinyl acetate, an ethylene acrylic acid, an ethylene methacrylic acid, a methyl ethylene acrylate, an ethyl ethylene acrylate, a butyl ethylene acrylate, a polyisobutylene, a maleic anhydride grafted polyolefin, an ionomer of any of the above, or a combination thereof.
[0006]
6. Breathable film according to any one of claims 1 to 5, characterized in that it further comprises a first layer comprising the first composition, and a second layer, the second layer comprising a polymer selected from the following: a first composition, one LLDPE, one VLDPE, one LDPE, one MDPE, one HDPE, one HMWHDPE, one propylene based polymer, one polyolefin plastomer, one polyolefin elastomer, one block olefin copolymer, one vinyl acetate ethylene, an ethylene acrylic acid, an ethylene methacrylic acid, an ethylene methyl acrylate, an ethylene ethyl acrylate, a butyl ethylene acrylate, a polyisobutylene, a polyolefin grafted with maleic anhydride, an ionomer of any of the above, or a combination thereof.
[0007]
7. A breathable film according to any one of claims 1 to 6, characterized in that the breathable film comprises at least 30 percent by weight of the first composition.
[0008]
8. Breathable film according to any one of claims 1 to 7, characterized in that the breathable film has a water vapor transmission rate of at least 500 g/m2-day-atm and up to 10,000 g/m2 -day-atm.
[0009]
9. Breathable film according to any one of claims 1 to 8, characterized in that the breathable film is oriented in at least one of the machine direction and the transverse direction.
[0010]
10. Breathable film according to any one of claims 1 to 9, characterized in that the breathable film is oriented in the machine direction and in the transverse direction.
[0011]
11. Laminate, characterized in that it comprises a breathable film as defined in any one of claims 1 to 10.
[0012]
12. Laminate, according to claim 11, characterized in that it comprises a non-woven material.
[0013]
13. Article, characterized in that it comprises the laminate as defined in claim 11 or claim 12.
[0014]
14. Article, characterized in that it comprises the breathable film as defined in any one of claims 1 to 10.

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112016029614B1|2021-08-17|BREATHABLE FILM, LAMINATED AND ARTICLE

---

US20170129229A1|2017-05-11|Blown films with improved toughness

---

EP3160742A1|2017-05-03|Cast films with improved toughness

---

CN111406090A|2020-07-10|Uniaxially oriented polymeric films and articles made therefrom

---

ES2881182T3|2021-11-29|Polyethylene laminates for use in flexible packaging materials

---

JP2020526412A|2020-08-31|Multilayer polyethylene laminates and films for use in flexible packaging materials

---

TW202000707A|2020-01-01|Blown films comprising bimodal ethylene-based polymers having high molecular weight high density fractions

---

TW201800427A|2018-01-01|Microporous films, and articles made therefrom

---

BR112021009458A2|2021-08-10|curly fiber

---

BR112020003952A2|2020-09-08|thermoformed film compositions with enhanced toughness after thermoforming processes

---

CN113613899A|2021-11-05|Multilayer films, laminates, and articles comprising multilayer films

同族专利:

---

公开号 | 公开日

---

AR101003A1|2016-11-16|

---

US20170226332A1|2017-08-10|

---

EP3160741A1|2017-05-03|

---

BR112016029269A2|2017-08-22|

---

KR20170026475A|2017-03-08|

---

EP3162560A1|2017-05-03|

---

US20170152377A1|2017-06-01|

---

MX2016017268A|2017-05-08|

---

AR101002A1|2016-11-16|

---

KR20170023955A|2017-03-06|

---

CN106471020B|2021-03-19|

---

AR101004A1|2016-11-16|

---

WO2015200740A2|2015-12-30|

---

KR20170023078A|2017-03-02|

---

CN106459533A|2017-02-22|

---

CN106459533B|2020-10-02|

---

WO2015198138A1|2015-12-30|

---

WO2015200740A3|2016-02-18|

---

CN106471020A|2017-03-01|

---

AR101001A1|2016-11-16|

---

JP6846200B2|2021-03-24|

---

BR112016029614A2|2017-08-22|

---

JP2017519080A|2017-07-13|

---

US20170081444A1|2017-03-23|

---

US11174600B2|2021-11-16|

---

WO2015200741A1|2015-12-30|

---

JP6716473B2|2020-07-01|

---

CN106460238B|2021-03-30|

---

JP6716473B6|2020-07-29|

---

KR102324444B1|2021-11-12|

---

BR112016029364A2|2017-08-22|

---

EP3160739A2|2017-05-03|

---

CN106460238A|2017-02-22|

---

SG11201610598SA|2017-01-27|

---

TWI679236B|2019-12-11|

---

US10138362B2|2018-11-27|

---

JP2017522411A|2017-08-10|

---

TW201609915A|2016-03-16|

---

CN112457561A|2021-03-09|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

CA849081A|1967-03-02|1970-08-11|Du Pont Of Canada Limited|PRODUCTION OF ETHYLENE/.alpha.-OLEFIN COPOLYMERS OF IMPROVED PHYSICAL PROPERTIES|

---

US4116892A|1975-03-31|1978-09-26|Biax-Fiberfilm Corporation|Process for stretching incremental portions of an orientable thermoplastic substrate and product thereof|

---

US4153751A|1975-03-31|1979-05-08|Biax-Fiberfilm Corporation|Process for stretching an impregnated film of material and the microporous product produced thereby|

---

US4314912A|1977-02-03|1982-02-09|The Dow Chemical Company|High efficiency, high temperature catalyst for polymerizing olefins|

---

US4547475A|1984-09-07|1985-10-15|The Dow Chemical Company|Magnesium halide catalyst support and transition metal catalyst prepared thereon|

---

US4612300A|1985-06-06|1986-09-16|The Dow Chemical Company|Novel catalyst for producing relatively narrow molecular weight distribution olefin polymers|

---

US5153157A|1987-01-30|1992-10-06|Exxon Chemical Patents Inc.|Catalyst system of enhanced productivity|

---

US7163907B1|1987-01-30|2007-01-16|Exxonmobil Chemical Patents Inc.|Aluminum-free monocyclopentadienyl metallocene catalysts for olefin polymerization|

---

US5064802A|1989-09-14|1991-11-12|The Dow Chemical Company|Metal complex compounds|

---

JP2545006B2|1990-07-03|1996-10-16|ザダウケミカルカンパニー|Addition polymerization catalyst|

---

US5721185A|1991-06-24|1998-02-24|The Dow Chemical Company|Homogeneous olefin polymerization catalyst by abstraction with lewis acids|

---

KR100478377B1|1996-11-13|2005-03-23|다우 글로벌 테크놀로지스 인크.|Shrink Film Having Balanced Properties or Improved Toughness and Methods of Making the Same|

---

US5677383A|1991-10-15|1997-10-14|The Dow Chemical Company|Fabricated articles made from ethylene polymer blends|

---

US5847053A|1991-10-15|1998-12-08|The Dow Chemical Company|Ethylene polymer film made from ethylene polymer blends|

---

US6545088B1|1991-12-30|2003-04-08|Dow Global Technologies Inc.|Metallocene-catalyzed process for the manufacture of EP and EPDM polymers|

---

DE69211569T2|1991-12-30|1997-01-23|Dow Chemical Co|ETHYLENE INTERPOLYMER POLYMERIZATION|

---

US5296433A|1992-04-14|1994-03-22|Minnesota Mining And Manufacturing Company|Trisborane complexes and catalysts derived therefrom|

---

US5350723A|1992-05-15|1994-09-27|The Dow Chemical Company|Process for preparation of monocyclopentadienyl metal complex compounds and method of use|

---

US6691455B1|1992-06-22|2004-02-17|Turf Stabilization Technologies, Inc.|Sports playing surfaces with biodegradable backings|

---

US6448341B1|1993-01-29|2002-09-10|The Dow Chemical Company|Ethylene interpolymer blend compositions|

---

BR9405715A|1993-01-29|1995-11-28|Dow Chemical Co|Process for preparing an ethylene / a-olefin interpolymer composition and ethylene / a-olefin interpolymer composition|

---

US5372682A|1993-06-24|1994-12-13|The Dow Chemical Company|Electrochemical preparation of addition polymerization catalysts|

---

JP3292897B2|1993-10-07|2002-06-17|大塚化学株式会社|Artificial grass|

---

US5625087A|1994-09-12|1997-04-29|The Dow Chemical Company|Silylium cationic polymerization activators for metallocene complexes|

---

CA2271482A1|1996-11-13|1998-05-22|The Dow Chemical Company|Polyolefin compositions with balanced sealant properties and improved modulus and method for same|

---

US5869575A|1995-08-02|1999-02-09|The Dow Chemical Company|Ethylene interpolymerizations|

---

KR20000005027A|1996-03-27|2000-01-25|그레이스 스티븐 에스.|Solution polymerization process with dispersed catalyst activator|

---

EP0889912B1|1996-03-27|2000-07-12|The Dow Chemical Company|Highly soluble olefin polymerization catalyst activator|

---

US5977251A|1996-04-01|1999-11-02|The Dow Chemical Company|Non-adiabatic olefin solution polymerization|

---

WO1998026000A1|1996-12-12|1998-06-18|The Dow Chemical Company|Interpolymer compositions and cast stretch film therefrom|

---

US5783512A|1996-12-18|1998-07-21|The Dow Chemical Company|Catalyst component dispersion comprising an ionic compound and solid addition polymerization catalysts containing the same|

---

US6103657A|1997-07-02|2000-08-15|Union Carbide Chemicals & Plastics Technology Corporation|Catalyst for the production of olefin polymers|

---

US6696379B1|1997-09-19|2004-02-24|The Dow Chemical Company|Supported modified alumoxane catalyst activator|

---

JP2003517487A|1997-09-19|2003-05-27|ザダウケミカルカンパニー|Ethylene interpolymer compositions exhibiting narrow MWD with optimized composition, methods of making the same, and articles made therefrom|

---

US20050014431A1|1999-07-21|2005-01-20|Carmody Debra J.|Polymer coated web with good water vapor permeability|

---

AU1773901A|1999-12-10|2001-06-18|Dow Chemical Company, The|Substituted group 4 metal complexes, catalysts and olefin polymerization process|

---

EP1724379B1|2001-11-06|2008-01-02|Dow Gloval Technologies Inc.|Isotactic propylene homopolymer fibers and use|

---

US6906160B2|2001-11-06|2005-06-14|Dow Global Technologies Inc.|Isotactic propylene copolymer fibers, their preparation and use|

---

EP1375584B1|2002-06-20|2010-08-18|Borealis Technology Oy|Breathable Films|

---

US7596433B2|2005-12-30|2009-09-29|Canadian National Railway Company|System and method for computing rail car switching solutions in a switchyard with partially occupied classification track selection logic|

---

EP1845117A1|2006-04-11|2007-10-17|Solvay Solexis S.p.A.|Polymerisation process|

---

WO2007146875A2|2006-06-15|2007-12-21|Dow Global Technologies Inc.|Functionalized olefin interpolymers, compositions and articles prepared therefrom, and methods for making the same|

---

WO2008077530A2|2006-12-22|2008-07-03|Basell Polyolefine Gmbh|Multimodal polyethylene composition, mixed catalyst and process for preparing the composition|

---

US20080193890A1|2007-02-08|2008-08-14|Rogers James H|Textile Curing Oven With Active Cooling|

---

WO2009005375A1|2007-07-03|2009-01-08|Tigerturf Nz Limited|A yarn for synthetic turf and a synthetic turf|

---

GB0802550D0|2008-02-12|2008-03-19|Ineos Mfg Belguim Nv|Polymers and articles thereof|

---

CN102449003B|2009-03-31|2013-12-11|陶氏环球技术有限责任公司|Film made from heterogeneous ethylene/alpha-olefin interpolymer|

---

CN101659769B|2009-09-17|2011-09-21|宁波山泉建材有限公司|Waterproof air and moisture permeable microporous film, three-layer composite material and preparation method and application thereof|

---

CN103038281B|2010-03-02|2015-11-25|陶氏环球技术有限责任公司|Based on the polymer composition of ethene|

---

EP2374917B1|2010-04-07|2013-02-13|Dow Global Technologies LLC|Artificial turf yarn|

---

WO2012004422A1|2010-07-06|2012-01-12|Dow Global Technologies Llc|Ethylene polymer blends and oriented articles with improved shrink resistance|

---

WO2012061168A1|2010-11-02|2012-05-10|Dow Global Technologies Llc|A sealant composition, method of producing the same|

---

US9428636B2|2011-03-28|2016-08-30|Dow Global Technologies Llc|Process to produce enhanced melt strength ethylene/α-olefin copolymers and articles thereof|

---

US20130080208A1|2011-09-23|2013-03-28|Fujitsu Limited|User-Centric Opinion Analysis for Customer Relationship Management|

---

EP2751313B1|2011-10-05|2018-01-10|Dow Global Technologies LLC|Spunbond nonwoven fabrics and staple or binder fibres|

---

ES2625475T3|2011-10-24|2017-07-19|Dow Global Technologies Llc| Strand of artificial grass|

---

NO2931763T3|2012-12-14|2018-06-30|

---

ES2661993T3|2012-07-20|2018-04-05|Dow Global Technologies Llc|A linear low density polyethylene composition suitable for a cast molded film|

---

SG10201703271QA|2012-10-09|2017-07-28|Dow Global Technologies Llc|Sealant Composition|

---

CA2800056A1|2012-12-24|2014-06-24|Nova Chemicals Corporation|Polyethylene blend compositions|

---

JP6393693B2|2012-12-27|2018-09-19|ダウ グローバル テクノロジーズ エルエルシー|Catalytic system for olefin polymerization.|

---

ES2626786T3|2013-03-11|2017-07-26|Dow Global Technologies Llc|Fiber comprising a mixture of polyethylene|

---

CN103174081B|2013-03-19|2015-11-04|广州鹿山新材料股份有限公司|A kind of novel artificial grassplot structure and building method thereof|

---

US9181370B2|2013-11-06|2015-11-10|Chevron Phillips Chemical Company Lp|Low density polyolefin resins with low molecular weight and high molecular weight components, and films made therefrom|

---

US20150204027A1|2014-01-22|2015-07-23|Dow Global Technologies Llc|Artificial turf filaments, and articles made therefrom|

---

US20170152377A1|2014-06-26|2017-06-01|Dow Global Technologies Llc|Breathable films and articles incorporating same|

---

US20170129230A1|2014-06-26|2017-05-11|Dow Global Technologies Llc|Cast films with improved toughness|

---

EP3160740A1|2014-06-26|2017-05-03|Dow Global Technologies LLC|Blown films with improved toughness|

---

EP3054038A1|2015-02-06|2016-08-10|Dow Global Technologies LLC|Artificial turf filaments, and articles made therefrom|US20170152377A1|2014-06-26|2017-06-01|Dow Global Technologies Llc|Breathable films and articles incorporating same|

---

US20170129230A1|2014-06-26|2017-05-11|Dow Global Technologies Llc|Cast films with improved toughness|

---

EP3160740A1|2014-06-26|2017-05-03|Dow Global Technologies LLC|Blown films with improved toughness|

---

EP3161022A1|2014-06-30|2017-05-03|Dow Global Technologies LLC|Ethylene-based polymers|

---

EP3245318B1|2015-01-16|2020-05-27|BFS Europe NV|Fire-retardant artificial grass|

---

EP3054038A1|2015-02-06|2016-08-10|Dow Global Technologies LLC|Artificial turf filaments, and articles made therefrom|

---

KR101924198B1|2015-12-23|2018-11-30|주식회사 엘지화학|Low density polyethylene copolymer having superior film processibility and transmittance|

---

EP3214116B1|2016-03-03|2021-06-23|Dow Global Technologies LLC|Breathable films and method of making the same|

---

ES2849149T3|2016-03-03|2021-08-16|Dow Global Technologies Llc|Artificial grasses and method of making them|

---

RU2664263C1|2016-05-04|2018-08-15|Авент, Инк.|One-use surgical coat|

---

US20200325313A1|2016-07-28|2020-10-15|Dow Global Technologies Llc|Compositions suitable for manufacturing polyethylene foam, and articles thereof|

---

US20210276303A1|2016-09-30|2021-09-09|Dow Global Technologies Llc|Resins for use as tie layers in multilayer films and multilayer films comprising the same|

---

AR111555A1|2017-04-07|2019-07-24|Dow Global Technologies Llc|POLYETHYLENE LAMINATES FOR USE IN FLEXIBLE PACKING MATERIALS|

---

CN110730798A|2017-05-10|2020-01-24|埃克森美孚化学专利公司|Polymer compositions comprising broad molecular weight distribution polypropylene and articles made therefrom|

---

WO2019098283A1|2017-11-16|2019-05-23|三菱ケミカル株式会社|Oriented porous film|

---

DE102018207728A1|2018-05-17|2019-11-21|Heidelberger Druckmaschinen Ag|Compensation of density fluctuations|

---

WO2020163079A1|2019-02-06|2020-08-13|Exxonmobil Chemical Patents Inc.|Films and backsheets for hygiene articles|

---

KR102055555B1|2019-03-29|2019-12-13|김세학|Eco-friendly antifungal artificial turf structure|

---

KR102096244B1|2019-10-25|2020-04-06|코오롱글로텍주식회사|Artificial Turf for Photovoltaic Power Generation|

---

WO2021242801A1|2020-05-29|2021-12-02|Dow Global Technologies Llc|Attenuated hybrid catalysts|

---

WO2021242800A1|2020-05-29|2021-12-02|Dow Global Technologies Llc|Attenuated post-metallocene catalysts|

法律状态:
2020-02-04| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

---

2021-06-01| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2021-08-17| 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 26/06/2015, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

---

申请号 | 申请日 | 专利标题

---

US201462017525P| true| 2014-06-26|2014-06-26|

---

US62/017,525|2014-06-26|

---

PCT/US2015/037870|WO2015200741A1|2014-06-26|2015-06-26|Breathable films and articles incorporating same|

---