POLYOLEFIN COMPOSITION, SEALING COMPOSITION, FILM, MULTILAYER STRUCTURE AND PACKAGING DEVICE

专利摘要:
polyolefin composition, sealant composition, film, multilayer structure and packaging device The present invention provides an olefin composition suitable for sealant applications, sealant compositions, a method of producing them, and films and multilayer structures made therefrom. the polyolefin composition suitable for sealant applications in accordance with the present invention comprises: an ethylene/?-olefin interpolymer composition having a comonomer distribution constant (cdc) in the range of 40 to 110, a vinyl unsaturation of less than 0 .1 vinyls per thousand carbon atoms present in the backbone of the ethylene-based polymer composition; a zero shear viscosity ratio (zsvr) in the range of 1.01 to 2.0; a density in the range of 0.908 to 0.922 g/cm3, a melt index (i2 to 190oc/2.16 kg) in the range of 0.5 to 5.0 g/10 minutes, a molecular weight distribution (defined as the weight average molecular weight divided by the number average molecular weight, (mw/mn)) in the range from 2.0 to 4.0, and tan delta at 0.1 radian/second, determined at 190oc, in the range from 5 to 50.
公开号:BR112015007853B1
申请号:R112015007853-2
申请日:2013-09-30
公开日:2021-06-01
发明作者:Mehmet Demirors；Pradeep Jain；Mridula Kapur；Joshua Gaubert；Douglas S. Ginger；Mustafa Bilgen；Gagan Saini；Michael D. Turner
申请人:Dow Global Technologies Llc；
IPC主号:

专利说明:

technical field
[0001] The present invention relates to a polyolefin composition suitable for sealant applications, sealant compositions, method of producing them, and films and multilayer structures made of the same. Prior Art
[0002] The use of polyolefin compositions in sealant applications is generally known. Any conventional method can be employed to produce such polyolefin compositions.
[0003] Several polymerization techniques using different catalyst systems have been employed to produce such polyolefin compositions suitable for sealing applications.
[0004] Notwithstanding efforts to develop sealant compositions, there is still a need for a sealant composition having good balance of stiffness, toughness, optical properties such as low turbidity, and improved sealing properties such as high hot adhesion strength, high strength sealing, and substantially free of sealing leaks, while facilitating improved film fabrication. Additionally, there is a need for a method to produce such a seal composition having stiffness, toughness, optical properties such as low turbidity, and improved seal properties such as high hot adhesion strength, high seal strength, and substantially free of seal leakage. , while facilitating improved film fabrication. summary
[0005] The present invention provides a polyolefin composition suitable for sealant applications, sealant compositions, method of producing them, and films and multilayer structures made thereof.
[0006] In one embodiment, the present invention provides a polyolefin composition suitable for sealing applications, comprising: an ethylene/α-olefin interpolymer composition having a Comonomer Distribution Constant (CDC) in the range of 40 to 110, unsaturation vinyl of less than 0.1 vinyls per thousand carbon atoms present in the backbone of the ethylene-based polymer composition; a zero shear viscosity ratio (ZSVR) in the range of 1.01 to 2.0; a density in the range of 0.908 to 0.922 g/cm3, a melt index (I2 to 190oC/2.16 kg) in the range of 0.5 to 5.0 g/10 minutes, a molecular weight distribution (defined as the weight average molecular weight divided by the number average molecular weight, (Mw/Mn)) in the range from 2.0 to 4.0, and tan delta at 0.1 rad/second, determined at 190oC, in the range from 5 to 50.
[0007] In another embodiment, the present invention provides a sealant composition comprising: a polyolefin composition suitable for sealant applications comprising an ethylene/α-olefin interpolymer composition having a Comonomer Distribution Constant (CDC) in the range of 40 at 110, vinyl unsaturation of less than 0.1 vinyls per thousand carbon atoms present in the backbone of the ethylene-based polymer composition; a zero shear viscosity ratio (ZSVR) in the range of 1.01 to 2.0; a density in the range of 0.908 to 0.922 g/cm3, a melt index (I2 to 190oC/2.16 kg) in the range of 0.5 to 5.0 g/10 minutes, a molecular weight distribution (defined as the weight average molecular weight divided by the number average molecular weight, (Mw/Mn)) in the range from 2.0 to 4.0, and tan delta at 0.1 rad/second, determined at 190oC, in the range from 5 to 50.
[0008] In another embodiment, the present invention provides a film comprising the inventive sealant composition as described above.
[0009] In another embodiment, the present invention provides a multilayer structure comprising one or more film layers comprising the sealant composition as described above.
[0010] In an alternative embodiment, the present invention provides a multilayer structure in accordance with any of the preceding embodiments, except that the multilayer structure further comprises one or more layers selected from the group consisting of one or more polyamides, one or more polyesters, one or more polyolefins, and combinations thereof.
[0011] In another embodiment, the present invention provides a sealant composition, in accordance with any of the preceding embodiments, except that the sealant composition further comprises one or more ethylene polymers, or more propylene-based polymers, or combinations thereof.
[0012] In an alternative embodiment, the present invention provides a sealant composition, a method for producing it, a sealant composition made thereto, films and multilayer structure made thereto, in accordance with any of the preceding embodiments, except that the polyolefin composition is characterized by at least two of the following: a. having a dart impact B of at least 500 g, measured in accordance with ASTM D1709, when said polyolefin composition is formed into a blown monolayer film having a thickness of 1 mil;b. have a standard machine direction Elmendorf tear of at least 195 g/mil, measured in accordance with ASTM D1922, when the polyolefin composition is formed into a blown monolayer film having a thickness of 1 mil; c. have a 2% secant modulus in the machine direction of at least 110.32 MPa (16,000 psi), measured in accordance with ASTM D882, when said polyolefin composition is formed into a blown monolayer film having a thickness of 1 mil ;d. have a total turbidity of less than or equal to 10%, measured in accordance with ASTM D1003, when said polyolefin composition is formed into a monolayer blown film having a thickness of 1 mil.
[0013] In an alternative embodiment, the present invention provides a polyolefin composition, a method for producing it, a sealant composition made thereto, films and multilayer structure made thereto, in accordance with any of the preceding embodiments, except that the sealant composition has a hot adhesion strength at 130oC of more than 11 N/inch, measured in accordance with ASTM F1921, when said sealant composition is formed into a three-layer co-extruded blown film and subsequently laminated to a PET substrate of 0.5 mil.
[0014] In an alternative embodiment, the present invention provides a polyolefin composition, a method for producing it, a sealant composition made thereto, films and multilayer structure made thereto, in accordance with any of the preceding embodiments, except that the sealant composition has a "moon" resistance in the range equal to greater than 600 g.
[0015] In an alternative embodiment, the present invention provides a polyolefin composition, a method for producing it, a sealant composition made thereto, films and multilayer structure made thereto, in accordance with any of the preceding embodiments, except that films and multilayer structures are used as packaging devices.
[0016] In an alternative embodiment, the present invention provides a packaging device, according to any of the preceding embodiments, except that the packaging device comprises the multilayer structure as described above.
[0017] In an alternative embodiment, the present invention provides a packaging device, according to any of the preceding embodiments, except that the packaging device is used for packaging food.
[0018] In an alternative embodiment, the present invention provides a polyolefin composition, a method for producing it, a sealant composition made thereto, films and multilayer structure made thereto, in accordance with any of the preceding embodiments, except that the polyolefin composition has a ZSVR in the range of 1.12 to 2.0.
[0019] In an alternative embodiment, the present invention provides a polyolefin composition, method for producing it, sealant composition made thereto, films and multilayer structure made thereto, in accordance with any of the preceding embodiments, except that the Polyolefin composition has a melt strength expressed as a steady state force greater than 2.3 cN at a velocity of 8 mm/s measured at 190oC. Description of drawings
[0020] For the purposes of illustrating the invention, an exemplary form is shown in the drawings; it should be understood, however, that this invention is not limited to any of the precise arrangements and instrumentalities shown.
[0021] Figure 1 illustrates an exemplary three-layer co-extruded laminated film structure;
[0022] Figure 2 illustrates an exemplary bag made of the exemplary three-layer co-extruded laminated film structure;
[0023] Figure 3 illustrates a Vertical Sealing and Filling Packaging Process (VFFS) including the following stages: (a) formation of the horizontal bottom seal and vertical side seal; (b) bag filling step; and (c) formation of the upper seal;
[0024] Figure 4 illustrates a "moon" type defect seal formation in a vertical filler shape bag;
[0025] Figure 5 is a graphical illustration of the calculation of the Comonomer Distribution Constant (CDC) obtaining the peak temperature half width and the median temperature from the Elution Fractionation with Crystallization (CEF), showing the distribution profile of an ethylene/α-olefin interpolymer composition;
[0026] Figure 6 shows integration limits in the NMR spectral region of H1 for the determination of unsaturation, where the dashed line means that the position may be slightly different depending on sample/catalyst;
[0027] Figure 7 illustrates the pulse sequences modified for unsaturation with a Bruker AVANCE 400 MHz spectrometer;
[0028] Figure 8 is a graphic illustration of the CEF overlay of inventive and comparative polyolefin compositions; and
[0029] Figure 9 is a graphic illustration of the melt strengths overlap of inventive and comparative polyolefin compositions. Detailed Description
[0030] The present invention provides a polyolefin composition suitable for sealant applications, sealant compositions, a method of producing them, and films and multilayer structures made therefrom.
[0031] In one embodiment, the present invention provides a composition suitable for sealant applications comprising: a polyolefin composition suitable for sealant applications, comprising: an ethylene/α-olefin interpolymer composition having a Comonomer Distribution Constant (CDC) in the range of 40 to 110, a vinyl unsaturation of less than 0.1 vinyls per thousand carbon atoms present in the backbone of the ethylene-based polymer composition; a zero shear viscosity ratio (ZSVR) in the range of 1.01 to 2.0; a density in the range of 0.908 to 0.922 g/cm3, a melt index (I2 to 190oC/2.16 kg) in the range of 0.5 to 5.0 g/10 minutes, a molecular weight distribution (defined as the weight average molecular weight divided by the number average molecular weight, (Mw/Mn)) in the range from 2.0 to 4.0, and tan delta at 0.1 rad/second, determined at 190oC, in the range from 5 to 50.
[0032] In another embodiment, the present invention provides a sealant composition comprising: a polyolefin composition suitable for sealant applications, comprising: an ethylene/α-olefin interpolymer composition having a Comonomer Distribution Constant (CDC) in the range from 40 to 110, a vinyl unsaturation of less than 0.1 vinyls per thousand carbon atoms present in the backbone of the ethylene-based polymer composition; a zero shear viscosity ratio (ZSVR) in the range of 1.01 to 2.0; a density in the range of 0.908 to 0.922 g/cm3, a melt index (I2 to 190oC/2.16 kg) in the range of 0.5 to 5.0 g/10 minutes, a molecular weight distribution (defined as the weight average molecular weight divided by the number average molecular weight, (Mw/Mn)) in the range from 2.0 to 4.0, and tan delta at 0.1 rad/second, determined at 190oC, in the range from 5 to 50.
[0033] The polyolefin composition may additionally comprise additional components such as one or more other polymers. For example, the polyolefin composition may additionally comprise one or more ethylene polymers, or one or more propylene-based polymers, or combinations thereof.
[0034] In one embodiment, the polyolefin composition may further comprise a propylene/α-olefin interpolymer composition.
[0035] In one embodiment, one or more ethylene/α-olefin interpolymer compositions and one or more propylene/α-olefin compositions, as described herein, may be mixed by any method known to one of ordinary skill in the art including, but not limited to, mixing of dry, and mixing of melts by any suitable equipment, in order to produce the inventive sealant composition.
[0036] In one embodiment, the polyolefin composition may comprise from 85 to 100 percent by weight of the ethylene/α-olefin interpolymer composition, for example, from 85 to 97.5 percent by weight of the ethylene interpolymer composition. ethylene/α-olefin, based on the weight of the polyolefin composition. In one embodiment, the polyolefin composition may comprise from 0 to 15 percent by weight of one or more propylene/α-olefin interpolymer compositions, for example, from 2.5 to 15 percent by weight of one or more compositions of propylene/α-olefin interpolymer, based on the weight of the polyolefin composition.
[0037] The polyolefin composition may additionally comprise additional components such as one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, fillers such as TiO2 or CaCO3, opacifiers, nucleants, processing aids, pigments, primary antioxidants, secondary antioxidants, processing aids, stabilizers UV agents, antiblocks, slip agents, driers, flame retardants, antimicrobial agents, odor reducing agents, antifungal agents, and combinations thereof. The ethylene-based polymer composition may contain from about 0.01 to 10 percent by weight combined of such additives, based on the weight of the ethylene-based polymer composition including such additives. Ethylene/α-olefin composition
[0038] The ethylene/α-olefin interpolymer composition comprises (a) less than or equal to 100 percent, for example, at least 70 percent, or at least 80 percent, or at least 90 percent, of ethylene-derived units; and (b) less than 30 percent, for example, less than 25 percent, or less than 20 percent, or less than 10 percent, by weight of units derived from one or more α-olefin comonomers. The term "ethylene/α-olefin interpolymer composition" refers to a polymer that contains more than 50 mole percent polymerized ethylene monomer (based on the total amount of polymerizable monomers) and optionally may contain at least a comonomer.
[0039] α-Olefin comonomers typically have no more than 20 carbon atoms. For example, α-olefin comonomers may 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 may, for example, be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene; or, alternatively, from the group consisting of 1-hexene and 1-octene.
[0040] The ethylene/α-olefin interpolymer composition is characterized by having a Comonomer Distribution Constant in the range of 40 to 200, for example, from 40 to 150, or from 40 to 110.
[0041] The ethylene-based polymer composition is characterized by having a zero shear viscosity ratio (ZSVR) in the range of 1.01 to 2.0, for example, from 1.12 to 2.0.
[0042] The ethylene-based polymer composition is characterized by having a tan of delta at 0.1 radian/second, determined at 190oC, in the range of 5 to 50, for example, from 5 to 45, or from 5 to 40 .
[0043] The ethylene/α-olefin interpolymer composition has a density in the range of 0.908 to 0.920 g/cm3. For example, the density could be from a lower limit of 0.908, 0.909, or 0.910 g/cm3 to an upper limit of 0.918, 0.919, 0.920, or 0.922 g/cm3.
[0044] The ethylene/α-olefin interpolymer composition has a molecular weight distribution (Mw/Mn) in the range of 2.0 to 4.0. For example, the molecular weight distribution (Mw/Mn) could be from a lower limit of 2.0, 2.1, or 2.2 to an upper limit of 3.8, 3.9, or 4.0.
[0045] The ethylene/α-olefin interpolymer composition has a melt index (I2 at 190oC/2.16 kg) in the range of 0.5 to 5.0 g/10 minutes, for example, from 0.5 to 4.5 g/10 minutes, or from 0.5 to 4.0 g/10 minutes, or from 0.5 to 3.5 g/10 minutes, or from 0.5 to 3.0 g/10 minutes , or from 0.5 to 2.5 g/10 minutes, or from 0.5 to 2.0 g/10 minutes, or from 0.5 to 1.8 g/10 minutes, or from 0.6 to 1 .6 g/10 minutes. For example, the melt index (I2 at 190oC/2.16 kg) could be from a lower limit of 0.5, 0.6, or 0.7 to an upper limit of 1.6, 1.7, 1 .8, 1.9, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, or 5.0 g/10 minutes.
[0046] The ethylene/α-olefin interpolymer composition has a vinyl unsaturation of less than 0.15, for example, less than 0.12, or less than 0.1 vinyls per one thousand carbon atoms present in the main chain of the composition of the ethylene-based polymer.
[0047] The polyolefin composition has a melt strength expressed as a steady state force greater than 2.3 cN at a velocity of 8 mm/s measured at 190oC.
[0048] The ethylene/α-olefin interpolymer composition may additionally comprise additional components such as one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, fillers such as TiO2 or CaCO3, opacifiers, nucleants, processing aids, pigments, primary antioxidants, secondary antioxidants, UV stabilizers, anti- blocks, slip agents, driers, flame retardants, antimicrobial agents, odor reducing agents, antifungal agents, and combinations thereof. The ethylene-based polymer composition may contain from about 0.1 to about 10 percent combined by weight of such additives, based on the weight of the ethylene-based polymer composition including such additives.
[0049] In one embodiment, the ethylene/α-olefin interpolymer composition has a comonomer distribution profile comprising a monomodal distribution or a bimodal distribution in the temperature range of 35oC to 120oC, excluding purge.
[0050] Any conventional polymerization processes may be employed to produce the ethylene/α-olefin interpolymer composition. Such conventional polymerization processes include, but are not limited to, a solution polymerization process using one or more conventional reactors, e.g., loop reactors, isothermal reactors, stirred tank reactors, parallel batch reactors, series, and/or any combinations thereof.
[0051] The ethylene/α-olefin interpolymer composition may, for example, be produced by a solution phase polymerization process using one or more loop reactors, isothermal reactors, and combinations thereof.
[0052] In general, the solution phase polymerization process occurs in one or more well stirred reactors such as one or more loop reactors or one or more isothermal reactors at temperatures in the range of 115 to 250oC; for example, from 115 to 200oC, and pressures in the range of 300 to 1000 psi; for example, 2.76 to 5.17 MPa (400 to 750 psi). In one embodiment, in a double reactor, the temperature in the first reactor is in the range of 115 to 190oC, for example, 115 to 150oC, and the temperature of the second reactor is in the range of 150 to 200oC, for example, 170 to 195oC. In another embodiment, in a simple reactor, the temperature in the reactor is in the range from 115 to 190oC, for example from 115 to 150oC. Residence time in the solution phase polymerization process is typically in the range of 2 to 30 minutes; for example, 10 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. Exemplary solvents include, but are not limited to, isoparaffins. For example, such solvents are commercially available under the name ISOPPAR E from ExxonMobil Chemical Co. Houston, Texas. The resulting mixture of ethylene/α-olefin interpolymer and solvent is removed from the reactor and the ethylene/α-olefin interpolymer is isolated. Solvent is typically recovered from a solvent recovery unit, i.e. heat exchangers and liquid vapor separator drum, and is then recycled back to the polymerization system.
[0053] In one embodiment, the ethylene/α-olefin interpolymer composition may be produced by solution polymerization in a dual reactor system, for example, a double loop reactor system, with 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.
[0054] In another embodiment, the ethylene/alpha-olefin interpolymers may be produced by solution polymerization in a single reactor system, for example, a single loop reactor system, where ethylene and optionally one or more α -olefins are polymerized in the presence of one or more catalyst systems.
[0055] An exemplary catalyst system comprises a metal complex of a polyvalent aryloxyether corresponding to the formula:
at each occurrence a substituted C4-20 aryl group, the substituents, independently at each occurrence, being selected from the group consisting of alkyl; cycloalkyl; and aryl groups; and halo, trihydrocarbylsilyl and halohydrocarbyl substituted derivatives thereof, provided that at least one substituent lacks coplanarity with the aryl group to which it is attached; T4 is independently at each occurrence a C2-20 alkylene, cycloalkylene or cycloalkenylene group , or an inertly substituted derivative thereof; R21 is independently at each occurrence hydrogen, halo, a hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or di(hydrocarbyl)amino group of up to 50 atoms not containing hydrogen; R3 is independently at each occurrence hydrogen, halo ,a hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino group of up to 50 atoms not containing hydrogen, or two R3 groups on the same arylene ring together or an R3 group and an R21 group on the same or different arylene rings together form a divalent linking group attached to the arylene group at two positions or linking two different aryl rings and not with each other; and RD is independently at each occurrence halo or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms not containing hydrogen, or two RD groups together are a hydrocarbylene, hydrocarbadiyl, diene, or poly(hydrocarbyl)silylene group. Additionally, one or more cocatalysts may be present.
[0056] Another exemplary catalyst system comprises a metal complex containing polyvalent heteroatom linking group, especially complexes based on pyridylamine or imidazolylamine and Group 4 metal complexes based on biphenylphenol linked by tetradendate oxygen. Metal complexes suitable for use in accordance with the present invention include compounds corresponding to the formulas:

where RD, independently at each occurrence, is chlorine, methyl or benzyl. Specific examples of suitable metal complexes are the following compounds: bis(2-oxoyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl(phenyl)-2-phenoxy)-1,3-propanediylhafnium ( IV) dimethyl and bis(2-oxoyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl(phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium (IV) dimethyl.
Another exemplary catalyst system comprises a catalyst system of 2-[N-(2,6-diisopropylphenylamido)-o-isopropylphenylmethyl]-6-(2—n—l-naphthyl)-pyridyl hafnium(IV)dimethyl, additionally described in US patent no.

[0058] Another catalyst system comprises a constrained geometry catalyst represented by the following formula:

[0059] In one embodiment, the constrained geometry catalyst is (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7ah)-3-(1- pyrrodinyl)-1H-inden-1-yl)silanaminate(2-)-N)(2,3,4,5-h)-2,4-pentadiene)titanium represented by the formula above.
[0060] Another exemplary catalyst system may comprise a Ziegler-Natta catalyst system. Propylene/α-Olefin Interpolymer Compositions
The propylene/α-olefin interpolymer composition comprises a propylene/alpha-olefin copolymer and/or a propylene/ethylene/butene terpolymer, and optionally may additionally comprise one or more polymers, e.g. , a polypropylene random copolymer (PCR, heterogeneously branched).
[0062] The polyolefin composition may comprise from 0 to 15 percent by weight of one or more propylene/α-olefin interpolymer compositions, for example, from 2.5 to 15 percent by weight of one or more compositions of propylene/α-olefin interpolymer, based on the weight of the polyolefin composition.
[0063] In a particular embodiment, the propylene/alpha-olefin copolymer is characterized by having substantially isotactic propylene sequences. "Substantially isotactic propylene sequences" means that the sequences have an isotactic triad (mm) measured by C13 NMR of greater than about 0.85; in the alternative, more than about 0.90; in another alternative, more than about 0.92; and in yet another alternative, greater than about 0.93. Isotactic triads are well known in the art and are described, for example, in US Patent No. 5,504,172 and International Application Publication No. WO 00/01745, which refers to isotactic sequence in terms of a triad unit in the given copolymer molecular chain. by C13 NMR spectra.
[0064] Propylene/α-olefin copolymer may have a melt flow rate in the range of 0.1 to 30 g/10 minutes, measured in accordance with ASTM D1238 (at 230oC/2.16 kg). All values and sub-ranges from 0.1 to 30 g/10 minutes will be included here and disclosed here; for example, the melt flow rate could be from a lower limit of 0.1 g/10 minutes, 0.2 g/10 minutes, 0.5 g/10 minutes, or 1 g/10 minutes to an upper limit of 30 g/10 minutes, or 25 g/10 minutes, or 20 g/10 minutes, or 15 g/10 minutes, or 10 g/10 minutes. For example, the propylene/α-olefin copolymer may have a melt flow rate in the range of 0.1 to 25 g/10 minutes or, alternatively, the propylene/α-olefin copolymer may have a melt flow rate melt in the range of 1 to 20 g/10 minutes or alternatively the propylene/α-olefin copolymer may have a melt flow rate in the range 1 to 10 g/10 minutes or alternatively the copolymer of propylene/α-olefin may have a melt flow rate in the range of 1 to 5 g/10 minutes or alternatively the propylene/α-olefin copolymer may have a melt flow rate in the range of 1 to 3 g/10 minutes.
[0065] The propylene/α-olefin copolymer has a crystallinity in the range of at least 1 percent by weight (a heat of fusion of at least 2 Joules/g) to 45 percent by weight (a heat of fusion of less than 75 Joules/g). All values and sub-ranges from 1 percent by weight (a heat of fusion of at least 2 Joules/g) to 45 percent by weight (a melting heat of less than 75 Joules/g) will be included herein and disclosed herein; for example, the crystallinity could be from a lower limit of 1 percent by weight (a heat of fusion of at least 2 Joules/g), 2.5 percent by weight (a heat of fusion of at least 4 Joules/g ), or 3 percent by weight (a heat of fusion of at least 5 Joules/g), or 10 percent by weight (a heat of fusion of at least 16.5 Joules/g), or 15 percent by weight (a heat of fusion of at least 24.8 Joules/g) to an upper limit of 45 percent by weight (a heat of fusion of less than 75 Joules/g), or 35 percent by weight (a heat of fusion of less than 5 Joules/g), or 30 percent by weight (a heat of fusion of less than 50 Joules/g). For example, the propylene/α-olefin copolymer may have a crystallinity in the range of at least 10 percent by weight (a heat of fusion of at least 16.5 Joules/g) to 45 percent by weight (a heat of fusion of less than 75 Joules/g); or, in the alternative the propylene/α-olefin copolymer may have a crystallinity in the range of at least 15 percent by weight (a heat of fusion of at least 24.8 Joules/g) to 35 percent by weight (a heat of fusion of less than 57.8 Joules/g). Crystallinity is measured by the DSC method, using the 2nd thermal cycle. The propylene/alpha-olefin copolymer comprises units derived from propylene and polymer units derived from one or more alpha-olefin comonomers. Exemplary comonomers used in the manufacture of the propylene/alpha-olefin copolymer are alpha-olefins C2, and C4 to C10; for example, alpha-olefins C2, C4, C6 and C8.
[0066] The propylene/alpha-olefin copolymer comprises from 1 to 40 percent by weight of one or more alpha-olefin comonomers. All values and sub-ranges from 1 to 40 percent by weight will be included here and disclosed here; for example, the comonomer content may be from a lower limit of 1 percent by weight, 3 percent by weight, 4 percent by weight, 5 percent by weight, 7 percent by weight, or 9 percent by weight. to an upper limit of 40 percent by weight, 35 percent by weight, 30 percent by weight, 27 percent by weight, 20 percent by weight, 15 percent by weight, 12 percent by weight, or 9 percent by weight. hundred by weight. For example, the propylene/alpha-olefin copolymer comprises from 1 to 35 percent by weight of one or more alpha-olefin comonomers; or, in the alternative, the propylene/alpha-olefin copolymer comprises from 1 to 30 percent by weight of one or more alpha-olefin comonomers; or, in the alternative, the propylene/alpha-olefin copolymer comprises from 3 to 27 percent by weight of one or more alpha-olefin comonomers; or, in the alternative, the propylene/alpha-olefin copolymer comprises from 3 to 20 percent by weight of one or more alpha-olefin comonomers; or, in the alternative, the propylene/alpha-olefin copolymer comprises from 3 to 15 percent by weight of one or more alpha-olefin comonomers; or, in the alternative, the propylene/alpha-olefin copolymer comprises from 3 to 9 percent by weight of one or more alpha-olefin comonomers.
[0067] The propylene/alpha-olefin copolymer has a molecular weight distribution (MWD), defined as the weight average molecular weight divided by the number average molecular weight (Mw/Mn) of 3.5 or less; in the alternative, 3.0 or less; or in another alternative, from 1.8 to 3.0.
Such propylene/alpha-olefin copolymers are further described in detail in U.S. Patent Nos. 6,960,635 and 6,525,157, incorporated herein by reference. Such propylene/alpha-olefin copolymers are commercially available from The Dow Chemical Company under the tradename VESIFYMR, or from ExxonMobil Chemical Company, under the tradename VISTAMAXXMR.
[0069] In one embodiment, the propylene/alpha-olefin copolymers are further characterized in that they comprise (A) between 60 and less than 100, preferably between 80 and 99 and more preferably between 85 and 99, weight percent of derived units of propylene, and (B) between more than zero and 40, preferably between 1 and 20, more preferably between 4 and 16 and even more preferably between 4 and 15, weight percent of units derived from at least one of ethylene and/ or a C4-10 α-olefin; and containing an average of at least 0.001, preferably an average of at least 0.005 and more preferably an average of at least 0.01, long chain branches/1000 total carbons. The maximum number of long chain branches in the propylene/alpha-olefin copolymer is not critical, but typically does not exceed 3 long chain branches/1000 total carbons. The term long chain branch, as used herein with respect to propylene/alpha-olefin copolymers, refers to a chain length of at least one (1) carbon more than one short chain branch, and one chain branch. short refers to a chain length of two (2) carbons less than the number of carbons in the comonomer. For example, a propylene/1-octene interpolymer has main chains with long chain branches of at least seven (7) carbons in length, but these main chains also have short chain branches of only six (6) carbons in length. Such propylene/alpha-olefin copolymers are further described in U.S. Patent Application Publication No. 2010-0285253 and International Patent Application Publication No. WO 2009/067337, each of which is incorporated herein by reference.
[0070] The propylene/alpha-olefin copolymer composition may additionally comprise one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancing agents, dyes, lubricants, fillers, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. The propylene/alpha-olefin interpolymer composition may contain any amounts of additives. The propylene/alpha-olefin interpolymer composition may contain from about 0 to about 20 weight percent combined of such additives, based on the weight of the propylene/alpha-olefin copolymer composition and one or more additives. of Additional Ethylene-α-Olefin
[0071] In one embodiment, the seal composition may further comprise an additional ethylene/α-olefin interpolymer component. In one embodiment, the one or more ethylene/α-olefin interpolymer compositions is one or more very low density polyethylene (PEMBD) compositions as described herein and may be blended by any method known to one of ordinary skill in the art including, but not limited to, dry mixing, and melt mixing by any suitable equipment, for example an extruder, to produce the inventive sealant composition. PEMBD is characterized as a heterogeneously branched, linear, very low density ethylene-α-olefin interpolymer with a density of less than 0.912 g/cm3 e.g. from 0.890 to 0.904 g/cm3; or, in the alternative, from 0.890 to 0.900 g/cm3; 0.896 to 0.900 g/cm3, and a melt index (I2 at 190°C/2.16 kg) in the range of 0.25 to 10 g/10 minutes, for example, from 0.25 to 8 g/10 minutes; and a molecular weight distribution (Mw/Mn) in the range of 2.5 to 4.0. Such PEMBD can be produced using heterogeneous Ziegler-Natta catalyst systems. PEMBD may be added to the polyolefin composition as a reactor mix or physical mix. Process for Producing Polyolefin Composition
[0072] One or more ethylene/α-olefin interpolymer compositions, optionally one or more propylene/alpha-olefin compositions, optionally one or more additional ethylene-α-olefin interpolymer compositions, as described herein, may be blended by any method known to one of ordinary skill in the art including, but not limited to, dry mixing, and melt mixing by any suitable equipment, for example, an extruder, in order to produce the inventive polyolefin composition. End of Sealing Composition
[0073] The polyolefin compositions according to the present invention may be used in any sealing applications, for example, food packaging applications such as sliced cheese, snacks, and frozen food packaging.
[0074] The sealant compositions according to the present invention may be formed into a film, a sheet, or a multilayer structure. Such multilayer structures typically comprise one or more film layers comprising the inventive sealant compositions. The multilayer structure may further comprise one or more layers comprising one or more polyamides, one or more polyesters, one or more polyolefins, and combinations thereof.
[0075] The inventive polyolefin compositions according to the present invention are characterized by one or more of the following: (a) having a dart B impact of at least 500 g, measured according to ASTM D1709, when said composition of polyolefin is formed into a monolayer blown film having a thickness of 1 mil; (b) have a standard machine direction Elmendorf tear of at least 195 g/mil, measured in accordance with ASTM D1922, when the polyolefin composition is formed into a blown monolayer film having a thickness of 1 mil; (c) have a 2% secant modulus in the machine direction of at least 110.32 MPa (16,000 psi), measured in accordance with ASTM D882, when said polyolefin composition is formed into a blown monolayer film having a thickness of 1 thousand; (d) have a total turbidity of less than or equal to 10%, measured in accordance with ASTM D1003, when said polyolefin composition is formed into a monolayer blown film having a thickness of 1 mil.
[0076] The sealant composition according to the present invention has a hot adhesion strength at 130oC of more than 11 N/inch, for example, in the range of 19 to 30 N/inch, measured according to ASTM F1921, when the sealant composition is formed into a three-layer co-extruded blown film subsequently laminated onto a 0.5 mil PET substrate.
[0077] The sealant composition according to the present invention has a resistance to "moon" fractionation equal to or greater than 600 g, for example, from 900 to 1100 g.
[0078] The following examples illustrate the present invention, but are not intended to limit the scope of the invention. The sealant compositions of the present invention have been shown to have a good balance of stiffness, toughness, optical properties such as low turbidity, and improved seal properties such as hot adhesion strength, high seal strength, and substantially free of seal leakage, while which facilitates the fabrication of films. Inventive Polyolefin Composition 1
[0079] The inventive polyolefin composition 1 (IPC1) comprises an ethylene-octene interpolymer having a density of approximately 0.913 g/cm3, a melt index (I2), measured at 190oC and 2.16 kg, of approximately 0. 81 g/10 minutes, a melt flow rate (I10/I2) of approximately 6.7. Additional properties of IPC1 were measured, and are reported in table 1A.
[0080] IPC1 was prepared by solution polymerization in a double loop reactor system in the presence of a catalyst system based on hafnium in the first reactor and a catalyst system of constrained geometry in the second reactor; a 2-[N-(2,6-diisopropylphenylamido)-o-isopropylphenylmethyl]-6-(2-n-1-naphthyl)-pyridyl hafnium(IV) dimethyl catalyst system, further described in US Patent No. 6,953,764 , incorporated herein by reference, and having a structure in accordance with the following formula:
the constrained geometry catalyst comprising (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-h)-3-(1-pyrrodinyl)- 1H-inden-1-yl)silanaminate(2-)-N)(2,3,4,5-h)-2,4-pentadiene) titanium, represented by the following formula:

[0081] The polymerization conditions for IPC1 are reported in table 2A. Referring to Table 2A, MMAO is modified methyl aluminoxane; and RIBS-2 is bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-) amine, used as cocatalysts. Polyolefin Composition Inventive 2
[0082] The inventive polyolefin composition 2 (IPC2) comprises an ethylene-octene interpolymer having a density of approximately 0.913 g/cm3, a melt index (I2), measured at 190°C and 2.16 kg, of approximately 0 .84 g/10 minutes, a melt flow rate (I10/I2) of approximately 6.6. Additional properties of IPC2 were measured, and are reported in table 1A.
[0083] IPC2 was prepared by solution polymerization in a double loop reactor system in the presence of a zirconium-based catalyst system in both the first and second reactors, and the zirconium-based catalyst system comprises [2,2 "'-(1,3-propanediylbis(oxy-KO)]bis[3",5,5"-tris(1,1-dimethylethyl)-5'-methyl[1,1':3',1"- terphenyl]-2'-olate-KO]]dimethyl-,(OC-6-33)-zirconium,
hydrogenated)methyl, tetrakis(pentafluorophenyl)borate(1-)amine, used as cocatalysts. Inventive Polyolefin Composition 3
[0084] The inventive polyolefin composition 3 (IPC3) comprises an ethylene-octene interpolymer having a density of approximately 0.912 g/cm3, a melt index (I2), measured at 190°C and 2.16 kg, of approximately 0 .81 g/10 minutes, a melt flow rate (I10/I2) of approximately 6.2. Additional properties of IPC3 were measured, and are reported in table 1A.
[0085] IPC3 was prepared by solution polymerization in a double loop reactor system in the presence of a hafnium-based catalyst system in both the first and second reactors, the hafnium-based catalyst system comprising bis(2- oxoyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexane-diylhafnium(IV)dimethyl, represented by the following formula:

[0086] The polymerization conditions for IPC3 are reported in table 2A. Referring to Table 2A, MMAO is modified methyl aluminoxane; and RIBS-2 is bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)amine, used as cocatalysts. Inventive Polyolefin Composition 4
[0087] The inventive polyolefin composition 4 (IPC4) comprises an ethylene-octene interpolymer having a density of approximately 0.913 g/cm3, a melt index (I2), measured at 190°C and 2.16 kg, of approximately 0. 8 g/10 minutes, a melt flow rate (I10/I2) of approximately 6.3. Additional properties of IPC4 were measured, and are reported in table 1B.
[0088] IPC4 was prepared by solution polymerization in a double loop reactor system in the presence of a hafnium-based catalyst system in the first reactor and a zirconium catalyst system in the second reactor; the hafnium-based catalyst comprises a 2-[N-(2,6-diisopropylphenylamido)-o-isopropylphenylmethyl]-6-(2—n—l-naphthyl)-pyridyl hafnium(IV) dimethyl catalyst system, further described in US Patent No. 6,953,764, incorporated herein by reference, and having a structure in accordance with the following formula:
wherein the zirconium catalyst comprises [2,2"'-(1,3-propanediylbis (oxy-KO) ] bis [3", 5, 5"-tris (1,1-dimethylethyl)-5'-methyl[ 1,1':3',1"-terphenyl]-2'-olate-KO]]dimethyl-, (OC-6-33)-zirconium, represented by the following formula:
The polymerization conditions for IPC4 are reported in table 2B. Referring to Table 2B, MMAO is modified methyl aluminoxane; and RIBS-2 is bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)amine, used as cocatalysts. Polyolefin Composition Inventive 5
[0089] The inventive polyolefin composition 5 (IPC5) comprises an ethylene-octene interpolymer having a density of approximately 0.913 g/cm3, a melt index (I2), measured at 190oC and 2.16 kg, of approximately 0. 9 g/10 minutes, a melt flow rate (I10/I2) of approximately 7.2. Additional properties of IPC5 were measured, and are reported in table 1B.
[0090] The IPC5 was prepared by solution polymerization in a double loop reactor system in the presence of a catalyst system based on zirconium in the first reactor and a catalyst system of constrained geometry in the second reactor; the zirconium-based catalyst system comprising [2,2'"- (1,3-propanediylbis (oxy-KO) ] bis [3", 5, 5"-tris(1,1-dimethylethyl)-5'-methyl [1,1':3',1"-terphenyl]-2'-olate-KO]]dimethyl-, (OC-6-33)-zirconium, represented by the following formula:
the constrained geometry catalyst comprising (N-(1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-h)-3-(1-pyrrodinyl)- 1H-inden-1-yl)silanaminate(2-)-N)(2,3,4,5-h)-2,4-pentadiene) titanium, represented by the following formula:

[0091] The polymerization conditions for IPC5 are reported in table 2B. Referring to Table 2B, MMAO is modified methyl aluminoxane; and RIBS-2 is bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)amine, used as cocatalysts. Polyolefin Composition Inventive 6
[0092] The inventive polyolefin composition 6 (IPC6) comprises an ethylene-octene interpolymer having a density of approximately 0.914 g/cm3, a melt index (I2), measured at 190oC and 2.16 kg, of approximately 0. 8 g/10 minutes, a melt flow rate (I10/I2) of approximately 7.1. Additional properties of IPC6 were measured, and are reported in table 1B.
[0093] IPC6 was prepared by solution polymerization in a double loop reactor system in the presence of a hafnium-based catalyst system in the first reactor and a zirconium-based catalyst system in the second reactor; wherein the hafnium-based catalyst comprises a bis(2-oxoyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl(phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium (IV) dimethyl catalyst system , represented by the following formula:
wherein the zirconium catalyst comprises [2,2"'-(1,3-propanediylbis (oxy-KO) ] bis [3", 5, 5"-tris (1,1-dimethylethyl)-5' -

[0094] The polymerization conditions for IPC6 are reported in table 2B. Referring to Table 2B, MMAO is modified methyl aluminoxane; and RIBS-2 is bis(alkyl hydrogenated tallow)methyl, tetrakis(pentafluorophenyl)borate(1-)amine, used as cocatalysts. Inventive Polyolefin Composition 7
[0095] The inventive polyolefin composition 7 (IPC7) comprises an ethylene-octene interpolymer having a density of approximately 0.913 g/cm3, a melt index (I2), measured at 190°C and 2.16 kg, of approximately 0. 8 g/10 minutes, a melt flow rate (I10/I2) of approximately 6.4. Additional properties of IPC7 were measured, and are reported in table 1B.
[0096] The IPC7 was prepared by solution polymerization in a double loop reactor system in the presence of a catalyst system based on hafnium in the first reactor and a catalyst system based on zirconium in the second reactor; a 2-[N-(2,6-diisopropylphenylamido)-o-isopropylphenylmethyl]-6-(2—n—l-naphthyl)-pyridyl hafnium(IV) dimethyl catalyst system, further described in US Patent No. 6,953,764 , incorporated herein by reference, and having a structure in accordance with the following formula:
wherein the zirconium catalyst comprises [2,2"'-(1,3-propanediylbis (oxy-KO) ] bis [3", 5, 5"-tris (1,1-dimethylethyl)-5'-methyl[ 1,1':3',1"-terphenyl]-2'-olate-KO]]dimethyl-, (OC-6-33)-zirconium, represented by the following formula:

[0097] The polymerization conditions for IPC7 are reported in table 2C. Referring to Table 2C, MMAO is modified methyl aluminoxane; and RIBS-2 is bis(alkyl hydrogenated tallow)methyl, tetrakis(pentafluorophenyl)borate(1-)amine, used as cocatalysts.
[0098] The following examples illustrate the comparative compositions. Comparative Polyolefin Composition 1
Comparative Example 1 (CPC1) is EXCEEDMR 1012 commercially available from ExxonMobil Chemical Company. The properties of CPC1 were measured, and reported in table 1A. Comparative Polyolefin Composition 2
[0100] Comparative polyolefin 2 (CPC2) comprises an ethylene-octene interpolymer having a density of approximately 0.907 g/cm3, a melt index (I2), measured at 190oC and 2.16 kg, of approximately 0.9 g /10 minutes, a melt flow rate (I10/I2) of approximately 8.6. Additional properties of CPC2 were measured, and are reported in table 1A.
[0101] CPC2 was prepared by solution polymerization in a double loop reactor system in the presence of a zirconium-based catalyst system in both the first reactor and the second reactor, the zirconium catalyst comprising [2.2" - (1,3-propanediylbis(oxy-KO)]bis[3",5,5"-tris(1,1-dimethylethyl)-5'-methyl[1,1':3',1"-terphenyl] -2'-olate-KO]]dimethyl-, (OC-6-33)-zirconium, represented by the following formula:

[0102] The polymerization conditions for CPC2 are reported in table 2C. Referring to Table 2C, MMAO is modified methyl aluminoxane; and RIBS-2 is bis(alkyl hydrogenated tallow)methyl, tetrakis(pentafluorophenyl)borate(1-)amine, used as cocatalysts.







Layers
[0103] Monolayer and co-ex (three layers) films were manufactured on a Hosokawa Alpine 7 layer blown film line. This line consists of seven 50 mm slotted feed extruders, 30:1 C/D utilizing barrier threads and a 250 mm (9.9 inch) co-ex die. The die is equipped with internal bubble cooling. Monolayer films
[0104] IPC1 to IPC7, CPC1 and CPC2 were formed into inventive monolayer blown films 1-7 and comparative monolayer films 1-2. The inventive single layer blown films (IMBF) 1-7 and the comparative monolayer blown films (CMBF) 1-2 were manufactured in the Hosokawa Alpine 7 layer blown film line. Extrusion setpoints and measured conditions are listed below.Setpoints:BUR = 2.5Die production = 11.3 pph/in Die clearance = 2 mmFreeze line height = 35-37 inDie size = 250 mm Measured extrusion conditions for CBMF1 and IMBF2 are given in tables 3A-G.





Three Layer Co-Extruded Blown Films
[0105] ICP1-7 and CPC1-2 were formed as inventive three-layer co-extruded films ITCBF 1-7 and comparative three-layer co-extruded blown films CTCBF 12. The inventive three-layer co-extruded films 1-7 and comparative three-layer co-extruded blown films 1-2 were manufactured in the Hosokawa-Alpine 7-layer blown film line. Setpoints for extrusion conditions and measured conditions are listed below.Setpoints:BUR = 2.5 Die Production = 14.6 pph/inDie Clearance = 2mmHeight of Freezing Line = 35-37inFlat Layer = 38.6-38.7 inDie Size = 250 mm Measured extrusion conditions for CTCBF1 and ITCBF2 are given in Tables 4A-G.






[0106] Referring to figure 1, an extruder 1 was used to manufacture a layer 1 (skin layer). Extruders 2, 3, 4, 5 and 6 were used to make a layer 2 (the core layer), and an extruder 7 was used to make a layer 3 (the sealing layer) within the blown film bubble. The ratio (quantity) of plies and the thickness per ply number are given in table 5.
Inventive Laminated Structures (ILS) 1-7 and Comparative Laminated Structures (CLS) 1-2
[0107] Inventive laminate structures (ILS) 1-7 and comparative laminate structures (CLS) 1-2 were prepared according to the following process. The 48 g of PET film (primary) was passed through the coating platform where the solvent based bicomponent adhesive (ADCOTEMR 577 A/B from The Dow Chemical Company) was applied at ~28-30% solids with a roller 130 with a volume of 18.2 billion per cubic micron (BCM) at a coating weight of ~1.75 lb per reset. After the adhesive is applied the continuous film travels through a two-zone oven to eliminate all solvent, then moves to a rolling mill consisting of a ~15 inch diameter heated steel roll and a 7 inch EPDM rubber roll inches in diameter. The back side of the PET film makes contact with the hot steel roll. In the meantime, the three-layer co-extruded blown film is corona treated at 38-42 dynes. The corona treated side of the three-layer co-extruded blown film contacts the adhesive side of the PET film and enters between the rubber roller and the heated roller (~140-180oF at a pressure of 40-60 psi where the PET film and three-layer co-extruded blown film are combined. The resulting co-extruded laminated structure is wound into the rewind system thus forming the inventive laminated structures (ILS) 1-7 and the comparative laminated structures (CLS) ) 1-2.
[0108] Referring to Figure 1, the laminated structures comprise (a) a sealing layer (0.4 mil thick) comprising one of IPC1-7 or CPC1-2; (b) a core layer (1.2 mil thick) comprising 80 percent by weight of an ethylene-octene interpolymer having a density of 0.920 g/cm3 and a melt index I2 of 1 g/10 minutes (commercially available under the tradename DOWLEXMR 2045 from The Dow Chemical Company) and 20 weight percent of a low density polyethylene having a density of 0.923 g/cm3 and a melt index I2 of 0.88 g/10 minutes (commercially available under the tradename DOWMR LDPE 611A from The Dow Chemical Company); (c) a skin layer (thickness 4 mil) comprising 80 percent by weight of an ethylene-octene interpolymer having a density of 0.920 g/cm3 and a melt index I2 of 1 g/10 minutes (commercially available under the trade name DOWLEXMR 2045 from The Dow Chemical Company) and 20 percent by weight of a low density polyethylene having a density of 0.923 g/cm3 and a melt index I2 of 0.88 g/10 minutes (commercially available under the trademark DOWMR LDPE 611A from The Dow Chemical Company); (d) an adhesive layer comprising a bicomponent solvent based on an adhesive commercially available under the tradename ADCOTEMR 577 from The Dow Chemical Company; and (e) a layer of polyethylene terephthalate (PET) (0.5 mil thick).
[0109] The inventive laminated structures (ILS) 1-7 and comparative laminated structures (CLS) 1-2 were manufactured as inventive bags (IB) 1-7 and comparative bags (CB) 1-2 in a sealing machine for filling in Hayssen-Sandiarce Model Ultima ST vertical form (VFFS) 12-16 HP. This bag is illustrated in figure 2. The process of bag formation, filling and sealing is illustrated in figure 3.
[0110] The integrity of the sealing layer was tested by conducting airtightness tests on empty inventive bags 1-7 and comparative bags 1-2. The inventive bag seals have been found to provide excellent airtightness and resistance to defect formation.
[0111] Additional properties of inventive monolayer blown films (IMBF) 1-7 and comparative monolayer blown films (CMBF) 1-2 were tested and the results are reported in tables 6A and B.

Test Methods
[0112] Test methods include the following: Density
[0113] Samples that are measured for density are prepared in accordance with ASTM D4703. Measurements are made within one hour of sample pressing using ASTM D792, Method B. fusion index
[0114] The melt index (I2) is measured according to ASTMD1238, Condition 190oC/2.16 kg, and is reported in grams eluted over 10 minutes. Differential Scanning Calorimetry (DSC)
[0115] DSC can be used to measure the melting and crystallization behavior of a polymer over a wide temperature range. For example, a TA Instruments Q 1000 DSC equipped with an RCS (Refrigerated Cooling System) and an autosampler is used to perform this analysis. During the test, a nitrogen purge gas flow of 50 mL/min is used. Each sample is melt pressed into a thin film at about 175oC; the molten sample is then air-cooled to temperature (~25oC). A 3-10 mg sample, 6 mm diameter is extracted from the cooled polymer, weighed, placed in a lightweight aluminum pan (about 50 mg), and resealed. Analysis is then performed to determine thermal properties.
[0116] The thermal behavior of the sample is determined by ramping the sample temperature up and down to create a thermal flow versus temperature profile. First, the sample is quickly heated to 180oC and held isothermally for 3 minutes in order to remove its thermal history. The sample is then cooled to -40oC at a cooling rate of 10oC/minute and held isothermally at -40oC for 3 minutes. The sample is then heated to 150oC (this is the “second heat” ramp) at a heat rate of 10oC/minute. Cooling and second heating curves are recorded. The cooling curve is analyzed by adjusting baseline extreme points from the start of crystallization at -20oC. The heating curve is analyzed by adjusting baseline endpoints from -20oC to the end of melting. The values determined are the peak melting temperature (Tm), peak crystallization temperature (Tc), heat of melting (Hf) (in Joules per gram), and % crystallinity calculated for samples using an appropriate equation, eg for an ethylene/alpha-olefin interpolymer using equation 1. Crystallinity % = ((Hf)/(292 J/g)) X 100 (Equation 1)
[0117] The heat of fusion (Hf) and the peak fusion temperature are reported from the second heating curve. The peak crystallization temperature is determined from the cooling curve. Dynamic Mechanical Spectroscopy (DMS) Scan Frequency
[0118] Samples were compression molded in circular plates 3 mm thick x 25 mm in diameter at 177oC for 5 minutes under a pressure of 10 MPa in air. The sample was then removed from the press and placed on the bench to cool.
[0119] Constant temperature frequency sweep measurements were conducted on an ARES controlled strain rheometer (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 was placed on the plate and allowed to melt for five minutes at 190°C. The plates were then closed to 2 mm, the sample was trimmed, and then the assay was started. The method also has an additional five minute delay built in to allow for temperature equilibrium. The experiments were carried out at 190oC over a frequency range of 0.1-100 rad/s at five points per decade interval. The strain amplitude was constant at 10%. The strain response was analyzed in terms of amplitude and phase, of which the storage modulus (G'), the loss modulus (G”), the complex modulus (G*), the dynamic complex viscosity (n*), and tan(δ) or tan delta were calculated.Gel Permeation Chromatography (GPC)
[0120] The GPC system consists of either a Polymer Laboratories Model PL-210 or Polymer Laboratories Model PL-220 instrument equipped with a refractive index (RI) concentration detector. Column and carousel compartments are operated at 140oC. Three 10 μm Mixed-B columns from Polymer Laboratories are used with 1,2,4-trichlorobenzene solvent. Samples are prepared at a concentration of 0.1 g polymer in 50 milliliters of solvent. The solvent used to prepare the samples contains 200 ppm butylated hydroxytoluene (BHT). Samples are prepared by gently shaking for four hours at 160oC. The injection volume used is 200 microliters and a flow rate of 1.0 mL/min. Calibration of the GPC column is conducted with twenty-one narrow molecular weight distribution polystyrene standards purchased from Polymer Laboratories.
[0121] The peak molecular weights of the polystyrene standards are converted to polyethylene molecular weights (MPE) using equation 1. The equation is described by Williams and Ward, J. Polym. Sci., Polym. Letters, 6, 621 (1968)):MPE = A x (MPS)B (Equation 1) where A has a value of 0.4316 and B is equal to 1.0.
[0122] A third-order polynomial is determined to construct the logarithmic molecular weight calibration as a function of the elution volume.
[0123] Polymer equivalent molecular weight calculations were conducted using PolymerChar's “GPC One” software. The number average molecular weight (Mn), weight average molecular weight (Mw) and z average molecular weight (Mz) were calculated by introducing the GPC results into equations 2 to 4:
where RIi and MPEi are the corrected baseline response from the concentration detector and the molecular weight of conventional calibrated polyethylene for the ith slice of the concentration response, data set paired with the elution volume. The precision of the weight average molecular weight ΔMw is <2.6%.
[0124] The MWD is expressed as the weight average mol (Mw) divided by the film number average molecular weight (Mn).
[0125] The set of GPC columns is calibrated by passing 21 polystyrene standards with narrow molecular weight distribution. The molecular weight (MW) of the standards ranges from 580 to 8,400,000, and the standards are contained in 6 “cocktail” blends. Each mix of standards has a decade of separation between individual molecular weights. Standard blends are purchased from Polymer Laboratories. Polystyrene standards are prepared at 0.025 g in 50 ml solvent for molecular weights equal to or greater than 1,000,000 and at 0.05 g in 50 ml solvent for molecular weights less than 1,000,000. Polystyrene standards were dissolved at 80°C with gentle agitation for 30 minutes. Narrow standard blends are processed in order to reduce the highest molecular weight component so as to minimize degradation. CEF method
[0126] Comonomer distribution analysis is performed with Fractionation by Elution with Crystallization (CEF) (PolymerChar in Spain, (B. Monrabal et al., Macrom. Symp., 257, 71-79, 2007)). Ortho-dichlorobenzene (ODCB) with 600 ppm of butylated hydroxytoluene antioxidant (BHT) is used as a solvent. Sample preparation is done with an autosampler at 160oC for 2 hours under agitation at 4 mg/mL (unless otherwise specified). The injection volume is 300 µL. The temperature profile of CEF is: crystallization at 3oC/min from 110oC to 30oC, thermal equilibrium at 30oC for 5 minutes, elution at 3oC/min from 30oC to 140oC. The flow rate during crystallization is 0.052 ml/min. The flow rate during elution is 0.50 ml/min. Data is collected at one data point/second.
[0127] The CEF column is filled by The Dow Chemical Company with 125 μm+6% glass beads (MO-SCI Specialty Products) with 1/8-inch stainless steel tubing. Glass beads are acid washed by MO-SCI Specialty on request from The Dow Chemical Company. Column volume is 2.06 ml. Column temperature calibration is performed using a mixture of linear polyethylene Reference Material Standard NIST 1475a (1.0 mg/mL), and eicosan (2 mg/mL) in ODCB. The temperature is calibrated by adjusting the elution heat rate such that NIST 1475a linear polyethylene has a peak temperature of 101.0oC, and eicosan has a peak temperature of 30.0oC. The resolution of the CEF column is calculated with a mixture of linear polyethylene NIST 1475a (1.0 mg/ml) and hexacontane (Fluka, purum, >97.0%, 1 mg/ml). A base separation line of hexacontane and NIST 1475a polyethylene is obtained. The hexacontane area (from 35.0 to 67.0oC) for the NIST 1475a area from 67.0 to 110.0oC is 50 to 50, the amount of soluble fraction below 35.0oC is <1.8% w/w. The column resolution of CEF is defined in equation 3, where the column resolution is 6.0.
CDC method
[0128] The comonomer distribution constant (CDC) is calculated from the comonomer distribution profile by CEF. CDC is defined as the Comonomer Distribution Index divided by the Comonomer Distribution Format Factor multiplied by 100 as shown in equation 4.

[0129] The comonomer distribution index corresponds to the total weight fraction of polymeric chains with the comonomer content ranging from 0.5 of median comonomer content (Cmedian) and 1.5 of Cmedian from 35.0 to 119.0oC . Comonomer Distribution Shape Factor is defined as the ratio of the half-width of the comonomer distribution profile divided by the standard deviation of the comonomer distribution profile to peak temperature (Tp).
[0130] CDC is calculated from the comonomer distribution profile by CEF, and CDC is defined as the Comonomer Distribution Index divided by the Comonomer Distribution Shape Factor multiplied by 100 as shown in equation 4, and being that the comonomer distribution index corresponds to the total weight fraction of the polymer chain with the comonomer content ranging from 0.5 of the median comonomer content (Cmedian) and 1.5 of the Cmedian from 35.0 to 119.0oC, and where the Comonomer Distribution Shape Factor is defined as a ratio of the half-width of the comonomer distribution profile divided by the standard deviation of the peak temperature comonomer distribution profile (Tp).
[0131] The CDC is calculated according to the following steps: (A) obtain a fraction by weight at each temperature (T)(wT(T)) from 35.0 to 119.9oC with a step temperature increase of 0 .2oC from CEF according to equation 5.
(B) calculate the median temperature (Tmedian) at the cumulative weight fraction of 0.500, according to equation 6.
(C) calculate the corresponding median comonomer content in moles% (Cmedian) at the median temperature (Tmedian) using the comonomer content calibration curve according to equation 7.
(D) construct a comonomer content calibration curve using a series of reference materials with known amount of comonomer content, ie, eleven reference materials with narrow comonomer distribution (monomodal comonomer distribution in CEF of 35, 0 to 119.0oC) with a weight average molecular weight Mw of 35,000 to 115,000 (measured by conventional GPC) at a comonomer content ranging from 0.0 mol% to 7.0 mol% are analyzed by CEF under the same experimental conditions specified in the experimental sections of CEF;(E) calculate the calibration of comonomer content using the peak temperature (Tp) of each reference material and its comonomer content. Calibration is calculated for each reference material as shown in equation 7 where: R2 is the correlation constant.(F) calculate the Comonomer Distribution Index from the total weight fraction with a comonomer content ranging from 0.5 *Cmedian to 1.5*Cmedian, and if Tmedian is higher than 98.0oC, the Comonomer Distribution Index is set to 0.95.(G) obtain the maximum peak height for the CEF comonomer distribution profile searching each data point for the highest peak from 35.0oC to 119.0oC (if the two peaks are identical then the lowest temperature peak is selected); half-width is defined as the temperature difference between the previous temperature and the posterior temperature in the middle of the maximum peak height, the previous temperature in the middle of the maximum peak being sought forward from 25.0oC, while the temperature back in the middle of the maximum peak is sought behind 119.0oC, in the case of a well-defined bimodal distribution where the difference in peak temperatures is equal to or greater than 1.1 times the sum of the half width of each peak, a half-width of the ethylene-based polymer composition is calculated as the arithmetic mean of the half-width of each peak; e(H) calculate the standard deviation of temperature (Stdev) according to equation 8
Zero Deformation Shear Viscosity Measurement Method
[0132] The zero shear viscosities are obtained by strain tests in an AR-G2 controlled tension rheometer (TA Instruments; New Castle, Del) using parallel plates with a diameter of 25 mm at 190oC. The rheometer oven is adjusted to the test temperature for at least 30 minutes before zeroing the instruments. At the test temperature, a compression molded disc is inserted between the plates and allowed to equilibrate for 5 minutes. The top plate is then lowered to 50 µm above the desired test clearance (1.5 mm). Any superfluous material is trimmed and the top plate is lowered to the desired clearance. Measurements are made under nitrogen purge at a flow rate of 5 L/min. The default deformation time is set to 2 hours.
[0133] A constant low shear stress of 20 Pa is applied to all samples to ensure that the steady state shear rate is low enough to be in the Newtonian region. The resulting steady-state shear rates are in the range of 10-3 to 10-4 s-1 for the samples in this study. Steady state is determined by taking a linear regression for all data in the last 10% time window of the log(J(t)) vs. plot. log(t), where J(t) is the strain recovery and t is the strain time. If the slope of the linear regression is greater than 0.97, it is considered that the steady state has been reached, then the strain test is stopped. In all cases, in this study the slope meets the criteria within 2 hours. The steady-state shear rate is determined from the slope of the linear regression of all data points in the last 10% time window of the ε vs. plot. T, where ε is the deformation. Zero shear viscosity is determined from the ratio of applied stress to steady-state shear rate.
[0134] To determine whether the sample has degraded during the strain test, a small amplitude oscillatory shear test is conducted before and after the strain test on the same test body from 0.1 to 100 rad/s. The complex viscosity values of the two tests are compared. If the difference in viscosity values at 0.1 rad/s is greater than 5%, the sample is considered to have degraded during the strain test, and the result is discarded. Zero Shear Viscosity Ratio (ZSVR)
[0135] It is defined as the ratio of the zero shear viscosity (ZSV) of the branched polyethylene material to the ZSV of the linear polyethylene material at the equivalent weight average molecular weight (Mw-gpc) according to the following equations 9 and 10:

[0136] The ZSV was obtained from the strain test at 190oC by the method described above. The value of Mw-gpc is determined by the conventional GPC method (equation 3). The correlation between ZSV of linear polyethylene and its Mw-gpc was established based on a series of linear polyethylene reference materials. A description of ZSV-Mw can be found in the ANTEC annals: Karjala, Teresa P., Sammler, Robert L., Mangnus, Marc A., Hazlitt, Lonnie G., Johnson, Mark S., Hagen, Charles M., Jr., Huang, Joe WL, Reichek, Kenneth N., “Detection of low levels of long-chain branching in polyolefins”, Annual Technical Conference - Society of Plastics Engineers (2008), 66a 887-891. H1 NMR Method
[0137] 3.26g of stock solution is added to 0.133g of polyolefin sample in a 10mm NMR tube. The stock solution is a mixture of tetrachloroethane-d2 (TCE) and perchlorethylene (50/50, w/w) with Cr3+ 0.001M. The solution in the tube is purged with N2 for 5 minutes to reduce the amount of oxygen. The capped sample tube is left at room temperature overnight to swell the polymer sample. The sample is dissolved at 110oC with stirring. Samples are free of additives that may contribute to unsaturation, eg glidants such as erucamide.
[0138] The NMR of H1 is conducted with a 10 mm cryoprobe at 120oC on a Bruker AVANCE 400 MHz spectrometer.
[0139] Experiments are conducted to obtain unsaturation: the control and double presaturation experiments.
[0140] For the control experiment, the data is processed with exponential window function with LB=1 Hz, the baseline was corrected from 7 to 12 ppm. The residual H1 signal is set to 100, the Itotal integral from -0.5 to 3 ppm is used as the signal for the entire polymer in the control experiment. The number of CH2, NCH2 groups in the polymer is calculated as follows: (Equation 11) NCH2=Itotal/2
[0141] For the double-pressure experiment, the data is processed with exponential window function with LB=1 Hz, the line was corrected to 6.6 to 4.5 ppm. The residual H1 signal is set to 100, the corresponding integrals for unsaturations (Ivinylene, Itrisubstituted, Ivinyl and Ivinylidene) have been integrated based on the region shown in Figure 6. The number of unsaturation units for vinylene, trisubstituted, vinyl and vinylidene is calculated: Nvinylene = Ivinylene/2 (Equation 12) Ntrisubstituted = Itrissubstituted (Equation 13) Nvinyl = Ivinyl/2 (Equation 14)Nvinylidene = Ivinylidene/2 (Equation 15)
[0142] The unsaturation units/1,000 carbons are calculated as follows: Nvinylene /1,000C = (Nvinylene/NCH2)*1,000 (Equation 16)Ntrisubstituted /1,000C = (Ntrisubstituted /NCH2)*1,000 (Equation 17)Nvinyl/1,000C = (Nvinyl/NCH2)*1,000 (Equation 18)Nvinylidene /1,000C = (Nvinylidene /NCH2)*1,000 (Equation 19)
[0143] The chemical shift reference is set at 6.0 ppm for the residual proton H1 signal of TCT-d2. The control is operated with pulse ZG, TD 32768, NS 4, DS 12, SWH 10,000 Hz, AQ 1.64s, D1 14s. The double presaturation experiment is operated with a modified pulse sequence, O1P 1.354 ppm, O2P 0.960 ppm, PL9 57 db, PL21 70 db, TD 32768, NS 200, DS 4, SWH 10,000 Hz, AQ 1.64s, D1 1 s, D13 13s. The pulse sequences modified for unsaturation with the Bruker AVANCE 400 MHz spectrometer are shown in Figure 7. C13 NMR method
[0144] The samples were prepared by adding approximately 2.74 g of tetrachloroethane-d2 containing 0.025 M Cr(AcAc)3 to the sample in a 10 mm Norell 1001-7 NMMR tube. Oxygen was removed manually by purging the tubes with nitrogen using a Pasteur pipette for 1 minute. The samples were dissolved and homogenized by heating the tube and its contents to ~150oC using a heating block with minimal use of a heat gun. Each sample was visually inspected to ensure homogeneity. Samples were judiciously mixed immediately prior to analysis, and were not allowed to cool prior to insertion into the heated NMR probe. This is necessary to ensure that the sample is homogeneous and representative of the whole. Data were collected using a Bruker 400 MHz spectrometer equipped with a Bruker cryoprobe. Data were acquired using 160 scans, a 6 sec pulse repetition delay with a sample temperature of 120oC. All measurements were made on non-rotating samples in locked mode. Samples were allowed to thermally equilibrate for 7 minutes prior to data acquisition. Chemical shifts of C13 NMR were internally referenced to the EEE triad at 30 ppm. Melt Strength Measurement
[0145] The melt strength was measured at 190oC on a Rheotens Model 71.97 melt strength tester. The melt was produced by a Goettfert Rheotens 2000 capillary rheometer with a flat 30/2 die, at a shear rate of 38.2 s-1. The rheometer cylinder (diameter: 12 mm) was filled in less than one minute. A 10 minute delay was allowed for proper fusion. The speed of taking the wheels of the Rheotens was varied, with a constant acceleration of 2.4 mm/sec2. Tension on the extracted web was monitored over time, until the sheet broke. Steady-state force and velocity at break were reported. Monolayer Blown Film Assays
[0146] The following properties have been measured on the monolayer blown films • Total turbidity: Samples measured for internal turbidity and global (total) turbidity are sampled and prepared in accordance with ASTM D1003. Internal turbidity was obtained by combining refractive indices using mineral oil on both sides of the films. A Hazeguard Plus (BYK-Gardner USA; Columbia, MD) is used for the trials. Surface turbidity is determined as the difference between total turbidity and internal turbidity.• Brightness at 45o: ASTM D2457• Elmendorf DM and DT Tear Resistance: ASTM D1922• Tensional Strength DM and DT Secant modulus 1% and 2%: ASTM D882• Dart Impact Resistance: ASTM D1709Laminated Film Assays hot adhesion
[0147] Hot film adhesion measurements are conducted using Enepay commercial testing machines according to ASTM F1921 (Method B). Before testing, samples are conditioned for a minimum of 4 h at 23oC and 50% RH (relative humidity) in accordance with ASTM D618 (Procedure A). Hot adhesion simulates loading of material into a bag or bag before the seal has opportunity to cool completely.
[0148] Sheets with dimensions of 8.5” by 14” are cut from three-layer co-extruded laminated film, with the longest dimension in the machine direction. Strips 1” wide and 14” long are cut from the film [samples need just enough length to be stapled]. Tests are performed on these samples over a range of temperatures and the results reported as the maximum load as a function of temperature. In this case, hot adhesion measurements were conducted in the range of 80oC to 180oC. Typical temperature steps are 5oC or 10oC with 6 replicates performed at each temperature. The parameters used in the test are as follows: Test body width: 15.4 mm (1.0 in) Sealing pressure: 0.275 N/mm2 Sealing application time: 0.5 s Peeling speed: 200 mm/s
[0149] Enepay machines make 0.5 inch seals. The data is reported as a hot adhesion curve where the average hot adhesion strength (N) is plotted as a function of temperature. The Tm of hot adhesion initiation is the temperature required to achieve a predefined minimum hot adhesion strength. This force is typically in the 1-2 N range, but will vary depending on the specific application. The final hot bond strength is the peak on the hot bond curve. The hot adhesion range is the temperature range in which the seal strength exceeds the Minimum Hot Adhesion Strength. Heat sealing
[0150] Thermal seal measurements on the film are conducted on a commercial tension testing machine in accordance with ASTM F88 (Technique A). The heat seal test is a gauge of the strength of seals (Seal Strength) in flexible barrier materials. This is done by measuring the force required to separate a test strip containing the seal and identifying the test specimen's failure mode. Sealing strength is relevant to the opening strength and integrity of the package.
[0151] Before cutting, films are conditioned for a minimum of 40 h at 23oC (+2oC) and 50% (+5%) U.R., in accordance with ASTM D618 (procedure A). Sheets are then cut from the co-extruded laminated film in the machine direction to a length of approximately 11 inches and a width of approximately 8.5 inches. The sheets are heat sealed along the machine direction on a Kopp thermal sealer over a temperature range under the following conditions: Sealing Pressure: 0.275 N/mm2Seal Application Time: 0.5 s
[0152] The temperature range is given approximately by the Hot Adhesion Range (ie, the temperature range over which a minimum thermal adhesion seal is achieved and before the through-burn temperature). In this case, the thermal seal measurement was conducted in the range of 80oC to 140oC.
[0153] The sealed sheets are conditioned for a minimum of 3 hours at 23oC (+2oC) and 50% U.R. (+5%) before testing.
[0154] For testing, the strips are loaded into the grips of a tension testing machine with an initial separation of 2 inches mm and pulled at a grip separation rate of 10 inches/min at 23oC (+2oC) and 50% of RH (+5%). Strips are tested unsupported. Six replicate tests are performed for each sealing temperature.
[0155] Data is reported as peak load; deformation at peak load and failure mode as a function of temperature. The Thermal Seal Initiation Temperature (HSIT) is defined as the temperature at the 1 lb/in seal resistance. The Final Thermal Seal Resistance Temperature (UHSST) is defined as the temperature corresponding to the maximum seal resistance. Hermetic Sealing Resistance
[0156] Bags fabricated from the laminated films were tested for airtightness under 12” vacuum in a Visual Check International Model H seal integrity tester. Bags were fabricated on the Hayssen-Sandiarce Model Ultima ST 12-16 HP VFFS machine. Bag dimension was: length 9.84 inches, width 11 inches. A minimum of ten sealed, empty bags were tested for inventive and comparative samples. An empty bag is defined as not containing solid packaged material. The bags were placed inside the tester's tank filled with water, and pushed down into the water through the tester's lid. A vacuum was applied to create pressure inside the bag. If the seal leaked, air would escape from the bag and create bubbles in the water.
[0157] The percentage of airtightness is calculated as follows: % airtightness = 100*(bags without leakage/total bags) Resistance to Defect Formation (“moon”).
[0158] The opening of seals, while the seal is still hot, due to the weight of the packed contents, was tested by conducting the defect test (moon formation) on the filled bags. An example of moon formation is given in figure 4. The bags are manufactured on the Hayssen-Sandiarce Model Ultima ST 12-16 HP VFFS machine. The grip temperature was maintained at 180oC and the seal application time was 250 milliseconds. Weights, ranging from 100 g to 1500 g, were added to the bag. The weight was dropped into the bag as the VFFS sealing jaws opened after formation of the bottom seal. A minimum of ten filled bags were tested per inventive and comparative sample. The bags were visually inspected for moon formation or seal opening at the bottom seal. The number of bags with and without moon formation was recorded. The minimum weight required to cause bottom seal failure in 20% of the bags was reported as the minimum weight required for defect formation.
[0159] The present invention may be carried out in other ways without departing from its essential spirits and attributes, and, consequently, reference should be made to the appended claims, rather than the description above, as indicative of the scope of the invention.

权利要求:
Claims (11)
[0001]
1. Polyolefin composition, suitable for sealing applications, characterized in that it comprises:- an ethylene/α-olefin interpolymer composition having a Comonomer Distribution Constant (CDC) in the range of 40 to 110, a vinyl unsaturation of less that 0.1 vinyls per thousand carbon atoms present in the backbone of the ethylene-based polymer composition; a zero shear viscosity ratio (ZSVR) in the range of 1.01 to 2.0; a density in the range of 0.908 to 0.922 g/cm3, a melt index (I2 to 190oC/2.16 kg) in the range of 0.5 to 5.0 g/10 minutes, a molecular weight distribution (defined as the weight average molecular weight divided by the number average molecular weight, (Mw/Mn)) in the range of 2.0 to 4.0, and tan delta at 0.1 radian/second and 190oC, in the range of 5 to 50; the polyolefin composition comprises from 85 to 100 percent by weight of the ethylene/α-olefin interpolymer composition.
[0002]
2. Sealing composition, characterized in that it comprises:- a polyolefin composition suitable for sealing compositions comprising:- an ethylene/α-olefin interpolymer composition having a Comonomer Distribution Constant (CDC) in the range of 40 to 110, a vinyl unsaturation of less than 0.1 vinyls per thousand carbon atoms present in the backbone of the ethylene-based polymer composition; a zero shear viscosity ratio (ZSVR) in the range of 1.01 to 2.0; a density in the range of 0.908 to 0.922 g/cm3, a melt index (I2 to 190oC/2.16 kg) in the range of 0.5 to 5.0 g/10 minutes, a molecular weight distribution (Mw/Mn ) in the range of 2.0 to 4.0, and tan delta at 0.1 radian/second and 190°C, in the range of 5 to 50; wherein the polyolefin composition comprises from 85 to 100 percent by weight of the composition of ethylene/α-olefin interpolymer;- density is measured using ASTM D792, Method B; e- the melt index (I2) is measured according to ASTM D1238, Condition 190°C/2.16 Kg.
[0003]
3. Sealing composition according to claim 2, characterized in that it additionally comprises one or more ethylene polymers, or one or more polymers based on propylene, or combinations thereof.
[0004]
4. Film, characterized in that it comprises the sealant composition, as defined in claim 2.
[0005]
5. Multilayer structure, characterized in that it comprises: - one or more layers of film comprising the sealant composition, as defined in claim 2.
[0006]
6. A multilayer structure according to claim 5, characterized in that the multilayer structure further comprises one or more layers selected from the group consisting of one or more polyamides, one or more polyesters, one or more polyolefins, and combinations thereof .
[0007]
7. Polyolefin composition according to claim 1, characterized in that said polyolefin composition is identified by at least two of the following: a. have a dart impact B of at least 500 g, measured in accordance with ASTM D1709, when said polyolefin composition is formed into a monolayer blown film having a thickness of 1 mil;b. have a standard machine direction Elmendorf tear of at least 195 g/mil, measured in accordance with ASTM D1922, when the polyolefin composition is formed into a blown monolayer film having a thickness of 1 mil; c. have a 2% secant modulus in the machine direction of at least 110.32 MPa (16,000 psi), measured in accordance with ASTM D882, when said polyolefin composition is formed into a blown monolayer film having a thickness of 1 mil ;d. have a total turbidity of less than or equal to 10%, measured in accordance with ASTM D1003, when said polyolefin composition is formed into a monolayer blown film having a thickness of 1 mil.
[0008]
8. Sealing composition according to claim 2, characterized in that said sealing composition has a hot adhesion strength at 130oC of more than 4.33 N/cm (11 N/inch), measured in accordance with ASTM F1921 , when said sealant composition is formed as a three-layer co-extruded blown film and subsequently laminated to a 0.5 mil PET substrate.
[0009]
9. Sealing composition according to claim 2, characterized in that said sealing composition has a resistance to moon formation in the range of more than 600 g.
[0010]
10. Packaging device, characterized in that it comprises the multilayer structure, as defined in claim 5.
[0011]
11. Packaging device according to claim 10, characterized in that it is used for food packaging.

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法律状态:
2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |

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2019-11-26| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-02-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-06-01| 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 30/09/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201261711513P| true| 2012-10-09|2012-10-09|

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US61/711,513|2012-10-09|

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US201261715105P| true| 2012-10-17|2012-10-17|

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US61/715,105|2012-10-17|

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PCT/US2013/062597|WO2014058639A1|2012-10-09|2013-09-30|Sealant composition|

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