• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    COMPOSITION OF MATTER AND FILM. A composition of matter suitable for use in extrusion coating applications is disclosed. The composition comprises a mixture of a particular LDPE with a particular LDPE. LLDPE has the following characteristics: a density in the range of 0.89 g / cm3 to 0.97 g / cm3; an MWD of less than 2.8; a melt index (12) in the range of 4.0 to 25 g / 10 min; a Comonomer Distribution Constant in the range of 45 to 400; and a vinyl unsaturation of less than 0.12 vinyls per thousand carbon atoms present in the main chain of the ethylene-based polymer composition. LDPE has a melt index (12) in the range of 0.1 to 15 g / 10 min, and a melt resistance that meets the inequality Log melt resistance (cN)> 1.14 - 0.6 x Log 12 (g / 10 min, 190 ° C).
    公开号:BR112014012382B1
    申请号:R112014012382-9
    申请日:2012-12-27
    公开日:2020-11-03
    发明作者:Jian Wang
    申请人:Dow Global Technologies Llc.；
    IPC主号:
    专利说明:

    Technical field
    [001] This invention relates to polyethylene extrusion compositions. In particular, the invention relates to extrusion compositions having high stretch and substantially reduced lateral shrinkage of the extrudate. The invention also relates to a method for making the extrusion composition from ethylene polymer and to a method for making an extrusion-coated article, an article in the form of an extrusion profile and an article in the form of an extruded cast film . Prior Art and Summary
    [002] Low density polyethylene (LDPE) made by high pressure polymerization of ethylene with free radical initiators as well as heterogeneous or homogeneous linear low density polyethylene (LDPE) and ultra low density polyethylene (LDPE) made by copolymerizing ethylene and α-olefins with metallocene or Ziegler coordination catalysts (transition metals) at low to medium pressures can be used, for example, for extrusion coating substrates such as cardboard, paper, and / or polymeric substrates; to prepare extruded cast films. For applications such as disposable diapers and food packaging; and to prepare extrusion profiles such as wire and cable covers. However, although LDPE generally exhibits excellent extrusion processability and high stretchability rates, LDPE extrusion compositions lack sufficient resistance to misuse and toughness for many applications. For the purposes of extrusion coating and extrusion casting, efforts to improve resistance to misuse by providing compositions having high molecular weights (i.e., having a melting index, I2, less than about 2 g / 10 min) are not effective since such compositions inevitably have a melt strength too weak to be successfully stretched on high speed lines.
    [003] While extrusion compositions of LLDPE and PEUBD offer properties of resistance to misuse and toughness and extrusion compositions of PEMD (medium density polyethylene) offer improved barrier resistance (with respect to, for example, permeation of moisture and greases ), these linear ethylene polymers exhibit unacceptably high lateral contraction of extrudates and stretching instability; they also exhibit relatively poor extrusion processability compared to pure LDPE. A proposal commonly used by the industry is to mix LDPE with LLDPE. With LDPE currently used, large amounts (eg, more than 60%) of LDPE should be used in order to achieve the required stretch. In some cases, the availability of LDPE may be limited, or there may be other reasons for wanting a lower level of LDPE, such as improving physical characteristics, without unduly increasing the lateral contraction of the extrudate. It has been found that the use of appropriate linear PEs allows for an improved combination of physical properties with good processability as evidenced by low lateral contraction of the extrudate, while using less LDPE (eg less than 50%, 45% or even 40% of LDPE) ).
    [004] It is generally believed that the lateral contraction of the extrudate and the melt strength are inversely related. Thus, in references such as U.S. patents Nos. 5,582,923 and 5,777,155 to Kale et al. (each of which is incorporated herein by reference), adding LLDPE to improve physical toughness came at the expense of extrudability factors such as the lateral contraction of the extrudate. Hence, in the extrusion coating industry, the current practice is to use LDPE with a low melting index in equipment with narrower width dies and relatively low take-off rates. Such low melt index autoclave LDPE resins provide low lateral shrinkage of the extrudate (less than about 2.5 inches (1.25 inches on each side)) and sufficient stretching speed. This is typically with older equipment. Faster equipment, typically with wider die widths and improved internal deckling, are supplied with autoclave LDPE with a higher melting index which, unfortunately, tends to generate greater lateral contraction of the extruded.
    [005] In the preferred practice of the present invention, the lateral contraction of the extrudate is less than approximately two and a half inches (1.25 "on each side) at a drag rate of approximately 880 feet / minute. The lateral contraction of the extrudate generally decreases with increased drag rates, making lateral contraction of extrudate particularly problematic when using older equipment that is limited in the drag rate obtainable. The practical melt index range is about 3 to about 30 g / 10 min in most coating applications, and the compositions of the present invention will be able to cover all this range It would be desirable that the maximum operating speed of the extrusion coating equipment should not be limited by the properties of the resin being used. a resin that exhibits neither extraction instability nor rupture before the maximum line speed is reached. It is even more desirable for such resin to exhibit a very low lateral contraction of extrudate, less than about 2.5 inches. The resins in this invention exhibit low lateral shrinkage of the extrudate and excellent stability in the extraction while the required stretching capacity is obtained by selecting the correct melting index. Typically, the melt index of the mixture as a whole is in the range of 4-20 g / 10 min. In both situations, the lateral contraction of the extrudate may be less than 2.5 inches.
    [006] LLDPE in the preferred mixtures for making the compositions of the present invention has the following characteristics: a density in the range of 0.89 g / cm3 to 0.97 g / cm3; an MWD of less than 2.8; a melt index (I2) in the range of 4.0 to 25 g / 10 min; a Monomer Distribution Constant in the range of more than 45 to 400; and a vinyl unsaturation of less than 0.12 vinyls per thousand carbon atoms present in the main chain of the ethylene-based polymer composition.
    [007] The low pressure high pressure polymer type has a melting index (I2) in the range of 0.1 to 15 g / 10 min, and has a melt resistance that satisfies the following inequality: Log melt resistance ( cN)> 1.14-0.6 x Log I2 (g / 10 min, 190 ° C)
    [008] Another aspect of the present invention is a process for improving the performance of extrusion coating to use the resins of the present invention. Detailed Description
    [009] The following terms will have the meaning given for the purposes of this invention:
    [0010] "Drag" is defined here as the speed at which the substrate is moving, thus stretching or stretching a molten polymer extrudate.
    [0011] "Stretchability" is defined as the drag speed at which the molten polymer breaks from the die or the speed at which edge instability has been noted.
    [0012] "Melt strength" measures the elongational flow behavior of the polymer melt, and is determined by the force required to drag a melted polymer filament through a pair of counter-rotating wheels at a constant rate of acceleration. The polymer filament can be fed by a capillary rheometer at a constant rate of production at a temperature above the melting temperature of the polymer. The melt strength, measured by the strength at the threshold before the filament rupture, is reported here in centi-Newtons (cN), and is typically determined using a Gottfert Rheotens 71.97 at 190 ° C.
    [0013] "Lateral shrinkage of the extrudate" is defined here as the difference between the width of the die and the width of the extrudate in the manufactured article. The lateral shrinkage values of extrudate reported here are determined at a drag rate of 440 feet / minute which produces a coating thickness of 1,000 as well as a drag rate of 880 feet / minute which produces a coating thickness of 0 , 5,000 at an extrusion rate of approximately 250 lb / h, using a 3.5-inch diameter Black-Clawson extrusion coater, 30: 1 L / D equipped with a 30-inch wide die and constriction for 24 inches and having a die clearance of 25 mils.
    [0014] The term "polymer", as used here, refers to a polymeric compound prepared by polymerizing monomers, whether of the same or different types. The generic term polymer thus encompasses the term "homopolymer", generally used to refer to polymers prepared from only one type of monomer, as well as "copolymer" which refers to polymers prepared from two or more different monomers.
    [0015] The term "LDPE" may also be referred to here as "high pressure ethylene polymer" or "highly branched polyethylene" and is defined as meaning that the polymer is partially or integrally homopolymerized or copolymerized in autoclaves or pressure reactors in pressures above 100 MPa (14,500 psi) with the use of free radical initiators, such as peroxides (see, for example, US patent No. 4,599,392, incorporated herein by reference).
    [0016] The term "LLDPE" is defined to mean any linear or substantially linear polyethylene copolymer. LLDPE can be made by any process such as gas phase, solution phase, or paste or combinations thereof. Fusion Index Assay Methods
    [0017] The melting index, or I2, is measured according to ASTM D 1238, Condition 190 ° C / 2.16 kg, and is reported in grams eluted for 10 minutes. Density
    [0018] Compression molded samples for density measurement are prepared according to ASTM D 4703. Density measurements are performed according to ASTM 792, Method B within 1 hour of molding. Dynamic Mechanical Spectroscopy
    [0019] The resins were molded by compression as a circular plate 3 mm thick x 25 mm in diameter at 1776 ° C for 5 minutes under an air pressure of 10 MPa. The sample is then taken from the press and placed on the bench to cool. The sample is then removed from the press and placed on the bench to cool.
    [0020] A frequency scan at constant temperature is performed using an "Advanced Rheometric Expansion System (ARES)", equipped with 25 mm parallel plates, under a nitrogen purge. The sample is placed on a plate and allowed to melt for five minutes at 190 ° C. The plates are then closed to 2 mm, the samples are trimmed, and then the test is started. The method has a built-in delay of an additional five minutes, in order to allow temperature equilibrium. The experiments are carried out at 190 ° C over a frequency of 0.1-100 rad / s at five points per decade of interval. The strain range is constant at 10%. The voltage response is analyzed in terms of amplitude and phase, from which the storage module, (G '), the loss module (G "), the complex module (G *), the dynamic viscosity (η * ) and tan (δ) are calculated. Cast Resistance
    [0021] The melt strength measurements were conducted on a Gottfert Rheotens 71.97 (Gõettfert Inc .; Rock Hill, SC) connected to a Gottfert Rheotester 2000 capillary rheometer. The molten sample (approximately 25 to 30 grams) was fed to the cylinder (L = 300 mm, Diameter = 12 mm) of the capillary rheometer Gottfert Rheotester 2000, equipped with a shallow-angle (180 degree) inlet with a length of 30 mm, diameter of 2.0 mm and an aspect ratio (length / diameter ) of 15. After equilibrating the samples at 190 ° C for 10 minutes, the piston was operated at a piston speed of 0.265 mm / second, which corresponds to a shear rate of 38.2 s-1 at a given diameter die. The standard test temperature was 190 ° C. The sample was extracted uniaxially for a set of accelerator nipples located 100 mm below the die, with an acceleration of 2.4 mm / s2. The tension force was recorded as a function of the winding speed of the nip rollers. The melt strength was reported as the threshold strength (cN) before the filament broke. The following conditions were used in melt strength measurements: piston speed = 0.265 mm / second; wheel acceleration = 2.4 mm / s2; capillary diameter = 2.0 mm; capillary length = 30 mm; and diameter = 12 mm.
    [0022] High Temperature Gel Permeation Chromatography
    [0023] The Gel Permeation Chromatography (GPC) system consists of a Waters (Milford, Mass) 150C high temperature chromatograph (other high temperature GPC instruments include Polymer Laboratories (Shropshire, UK) Model 210 and Model 220) equipped with an embedded differential refractometer (RI) (other suitable concentration detectors may include an IR-4 infrared detector from Polymer ChAR (Valencia, Spain)). Data collection is performed using Viscotek TriSEC, Version 3 software, and a 4-channel Viscotek Data Manager DM400. The system is also equipped with an online solvent degassing device from Polymer Laboratories (Shropshire, UK).
    [0024] Suitable GPC columns may be used such as four 113 cm Shodex HT803 13 columns 30 cm long or four 30 cm Polymer Labs columns with mixed 20 micron pore size filling (MixA LS, Polymer Labs) . The sample carousel compartment is operated at 140 ° C and the column compartment is operated at 150 ° C. The samples are prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent. The chromatographic solvent and the sample preparation solvent contain 200 ppm of trichlorobenzene (TCB). Both solvents are sparged with nitrogen. The polyethylene samples are gently stirred at 160 ° C for four hours. The injection volume is 200 microliters. The flow rate through the GPC set is adjusted to 1 mL / minute. The GPC column 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 are contained in 6 mixtures of "cocktails". Each standard has at least a decade of separation between individual molecular weights. The standards are purchased from Polymer Laboratories. Polystyrene standards were prepared at 0.025 g in 50 ml of solvent for molecular weights equal to or greater than 1,000,000 and at 0,055 g in 50 ml of solvent for molecular weights less than 1,000,000. The polystyrene standards were dissolved at 80 ° C with gentle stirring for 30 minutes. Mixtures of narrow patterns are processed initially and in decreasing order of the highest molecular weight in order to minimize degradation. The peak molecular weights of polystyrene standards were converted to molecular weights of polyethylene using equation 2 (as described by Williams and Ward, J. Poly. Sci. Let., 6, 621 (1968)): M (polyethylene) —AXM (polystyrene) (Eq. 2) where M is the molecular weight of polyethylene or polystyrene (as marked), and B is equal to 1.0. It is known to the moderately skilled in the subject that A may be in the range of 0.38 to 0.44 and is determined at the time of calibration using a wide polyethylene standard. The use of this polyethylene calibration method to obtain molecular weight values, such as molecular weight distribution (MWD or Mw / Mn), and related statistics (generally referring to conventional GPC or cc-GPC results), is defined here as the modified Williams and Ward method.
    [0025] The frequency of Long Chain Branching (LCBf); Zero Shear Viscosity Ratio (ZSVR) (including fluency zero shear viscosity and weight average molecular weight); the Comonomer Distribution Constant (CDC); and the levels of vinyl unsaturation are determined as described in WO / 2011/002868, and especially in PCT / US11 / 057780, which are incorporated herein by reference. Composition Description
    [0026] The compositions of the present invention comprise at least two components. The first component, which is a low density polyethylene, comprises from 50 to 97% by weight of the composition, preferably more than or equal to 55, more preferably more than or equal to 60 percent by weight of the composition as a whole.
    [0027] LLDPE in the preferred mixtures for use in the preparation of the compositions of the present invention have the following characteristics: First, a density in the range of 0.89 to 0.90 g / cm3, preferably 0.90 g / cm3, more preferably 0.905 g / cm to 0.97 g / cm 3, preferably 0.96 g / cm 3, more preferably 0.93 g / cm 3. Second, the LLDPE should have an MWD of less than 2.8, preferably in the range of 1.9 to 2.5, more preferably in the range of 2.0 to 2.3. Third, the LLDPE should have a melting index (I2) in the range of 4.0 g / 10 min, preferably 6 g / 10 min, more preferably 8 g / 10 min, up to 25 g / 10 min, preferably 20 g / 10 min, more preferably 15 g / 10 min. Fourth, the LLDPE should have a Comonomer Distribution Constant in the range of more than 45, preferably 50, more procedure 55 to 400, preferably 200, more preferably 150. Fifth, the LLDPE should have a vinyl unsaturation of less than 0, 12 vinyls per thousand carbon atoms present in the main chain of the ethylene-based polymer composition. Preferably, the level of vinyl unsaturation should be in the range of 0.01 to 0.1 or even 0.08 vinyl groups per thousand carbon atoms present in the main chain of the ethylene-based polymer composition. Preferably the LLDPE in the preferred mixtures of the present invention will also have a Long Chain Branch (LCBf) frequency of 0.02 to 3 long chain branches per 1000 carbon atoms, preferably from 0.02 to 1, or more preferably from 0 , 02 to 3 long chain branches per 1000 carbon atoms. Preferably the LLDPE in the preferred mixtures of the present invention will also have a Zero Shear Viscosity Ratio (ZSVR) of at least 1.4, preferably at least 1.5. Although there is no upper limit for the ZSVR, in general the PWBDL will have a ZSVR of less than 20 or even less than 10.
    [0028] A LLDPE meeting these parameters can be obtained according to the processes described in WO / 2011/002868.
    [0029] The compositions of the present invention also comprise a second polyethylene resin comprising a high pressure low density polyethylene. The second polyethylene comprises from 3 to 50 percent by weight of the total composition, alternatively from 10 to 40 percent, more preferably from 15 to 35 percent. In general, the more of this resin can be included, the less of the LLDPE component will be needed to achieve to achieve good lateral contraction properties. Such LDPE materials are well known in the art and include resins made in autoclave or tubular reactors. The preferred LDPE for use in the second polyethylene has a density in the range of 0.915 to 0.930 g / cm, preferably 0.916 to 0.925 g / cm, more preferably 0.917 to 0.920 g / cm3. The preferred LDPE for use in the second polyethylene has a melt strength that satisfies the inequality Log melt strength (cN)> 1.14 - 0.6 x Log I2 (g / 10 min, 190 ° C), preferably Log strength melt (cN)> 1.16 - 0.6 x Log i2, more preferably Log melt resistance (cN)> 1.18 - 0.6 x Log I2.
    [0030] The composition as a whole preferably has a melt index of 4 to 20 g / 10 min, preferably 6 to 15 g / 10 min, and an overall density of 0.90 to 0.96 g / cm3.
    [0031] Additives such as antioxidants (eg, hindered phenolics such as Irganox * 1010 or Irganox * 1076 supplied by Ciba-Geigy), phosphites (eg, Irgafos 168 also supplied, handle additives (eg ., PIB), StandostabMR (supplied by Sandoz), pigments, colorants, fillers and the like may also be included in the ethylene polymer extrusion composition of the present invention, as far as they do not interfere with the high stretch and lateral contraction of the extrudate. substantially reduced discovered by applicants.These compositions preferably do not contain any or only limited amounts of antioxidants since these compounds may interfere with adhesion to the substrate.The article made from or using the inventive composition may also contain additives to improve the characteristics anti-blocking and friction coefficient including, but not limited to, untreated and treated silicon dioxide, talc, calcium carbonate, and clay, as well as such as primary, secondary and substituted fatty acid amides, thermal transfer roller release agents, silicone coatings, etc. Other additives may also be added to improve the anti-fogging characteristics of, for example, clear fused films, as described, for example, by Niemann in U.S. Patent No. 4,486,552, the disclosure of which is hereby incorporated by reference. Still other additives, such as quaternary ammonium compounds alone or in combination with ethylene-acrylic acid (EAA) copolymers or other functional polymers, can also be added to improve the antistatic characteristics of coatings, profiles and films of this invention and allow, for example, example, packaging or making electronically sensitive products. Other functional polymers such as polyethylene grafted with maleic anhydride may also be added to improve adhesion, especially to polar substrates.
    [0032] Preferred mixtures for making the extrusion compositions of this invention may be prepared by any suitable means known in the art including dry mixing by drumming, weighing by weight ("weigh feeding"), mixing by solvent, mixing by melting via extrusion of compound or side tube, and the like, as well as combinations thereof.
    [0033] The inventive extrusion composition may also be mixed with other polymeric materials, such as polypropylene, high pressure ethylene copolymers, such as ethylene vinyl acetate (EVA), ethylene ethyl acrylate (EAA), and ethylene acrylic acid (EAA) and similar, ethylene-styrene interpolymers, as long as the necessary rheology and molecular architecture as evidenced by the multiple GPC detector are maintained. The composition can be used to prepare articles and structures in monolayer and multilayer, for example, as a sealant, adhesive or mooring layer. The other polymeric materials may be mixed with the inventive composition to modify processing characteristics, film strength, heat seal or adhesion as is generally known in the art.
    [0034] The ethylene polymer extrusion compositions of this invention, whether in monolayer or multilayer, may be used to make extrusion coatings, extrusion profiles, and extrusion cast films as is generally known in the art. When the inventive composition is used for coating purposes or in multilayer constructions, adjacent substrates or layers of material may be polar or support included, for example, but not limited to, paper products, metals, ceramics, glass and various polymers, particularly other polyolefins, and combinations thereof. For the production of extrusion profiles, several articles can potentially be manufactured including, but not limited to, gaskets for refrigerators, wire and cable sheaths, wire coating, medical pipes and water pipes, where the physical properties of the composition are adequate for the purpose. An extruded cast film made from the inventive composition could also potentially be used in food packaging and industrial stretch packaging applications. Experimental
    [0035] To demonstrate the effectiveness of the compositions of the present invention, the following experiments are run.
    [0036] Four different low density polyethylene resins were used. Resins A, B, and D are produced in a double reactor solution process with constrained geometry catalysts in one reactor and a Ziegler-Natta catalyst in a second reactor. A-D resins are more fully described in table 1.
    [0037] The LDPE used in each example is a high pressure low density polyethylene made in an autoclave reactor having a density of 0.918 g / cm3 and a melting index (I2) of 8 g / 10 min, which is commercially available The Dow Chemical Company under the name LDPE 722. Mixing
    [0038] The resins were mixed as follows for characterization. The LLDPE component and the LEBD component are formulated in an 18 mm (micro-18) twin screw extruder. The twin screw extruder used is a software controlled Lestriz machine from Haake. The extruder has five heated zones, a feed zone, and a 3 mm filament die. The feed zone is cooled by flowing river water, while the remaining zones 1-5 and the die are electrically heated and cooled in air at 120, 135, 150, 190, 190, and 190 ° C, respectively. The pellet mixing components are combined in a plastic bag and mixed manually by tapping. After preheating the extruder, the die cell load and pressure transducers are calibrated. The extruder drive unit is operated at 200 rpm resulting in a gear ratio for a thread speed of 250 rpm. The dry mixture is then fed (6-8 lb / h) to the extruder through a K-Tron model # K2VT20 twin screw feeder using pellet threads. The hopper of the feeder is lined with nitrogen and the feed cone to the extruder is sealed with laminate to minimize air intrusion in order to minimize possible oxygen degradation of the polymer. The resulting filament is quenched with water, dried with an air knife, and pelleted in a Conair mincer. These mixtures were then characterized and the results are shown in table 2. Extrusion Coating
    [0039] The same resins, in the same proportions, were then mixed dry for use in the extrusion coating. All coating experiments are carried out on a Black-Clawson extrusion coating / lamination line. The amount of lateral contraction of the extrudate (the difference in effective coating against the narrowing width with a 15 cm (6 ") air gap) is measured at 440 fpm at 880 fpm resulting in coatings with 1 mil and 0.5 mil respectively Stretchability is the speed at which edge imperfections were noticed or the speed at which the melt curtain breaks completely from the die. Although the equipment is capable of drag speeds of 3000 fpm, in these experiments the maximum speed used was 1500 fpm This is a normal operation and is done to conserve paper and maximize the number of experiments that can be done on the machine for each cardboard roll purchased.The motor current is also registered in the extruder of 3U inches in diameter and power 150 horses resulting in a production of 250 lb./h. Mixtures of several components are produced by weighing the pellets according to the proportions listed in table 3 and mixing samples by drum until a homogeneous mixture is obtained (approximately 30 minutes for each sample). The lateral contraction of extrudate and stretch for each mixture are shown in table 3. As seen in the table, the inventive example showed lateral contraction of the upper extrudate without a decrease in maximum stretch. Table 1: Properties of LLDPE components
    Table 2: Characteristics of Mixtures
    Table 3: Lateral contraction of extrudate, stretch in the extrusion coating line for mixtures

    [0040] Although the invention has been described in considerable detail by means of the description and examples above, this detail is for the purpose of illustration and should not be understood as a limitation on the scope of the invention as described in the appended claims. It should be understood that it is expressly contemplated that the following claims may be combined in any order, unless such combination would result in a structure containing improper presentations. All patents, patent applications and other references identified above are hereby incorporated by reference, to the extent permitted by law.
    [0041] The following embodiments are considered to be within the scope of the invention, and claimants reserve the right to amend the claims or to file additional patent applications to specifically claim any of these embodiments that are not already expressly presented in the present claim listing .
    [0042] 1. A composition of matter comprising: a. from about 97 to about 50 weight percent of the composition, of a Linear PE having i. a density in the range of 0.89 g / cm3 to 0.97 g / cm3 ii. a Mw / Mn of less than 2.8, iii. a melting index (I2) in the range of 4.0 to 25 g / 10 min, iv. a Comonomer Distribution Constant in the range of 45 to 400, see a vinyl unsaturation of less than 0.12 vinyls per thousand carbon atoms present in the main chain of the ethylene-based polymer composition; and
    [0043] b. from about 3 to about 50 weight percent of the composition of a high pressure low density polyethylene resin having a melting index (I2) in the range of 0.1 to 15 g / 10 min, and having a resistance of melt that meets the inequality Log melt resistance (cN)> 1.14 - 0.6 x Log I2 (g / 10 min, 190 ° C) with the MI of the composition of matter being in the range of 4 g / io minutes at 20 g / 10 min.
    [0044] 2. The material composition of embodiment 1 with the Linear PE having an MWD of at least 1.8.
    [0045] 3. The material composition of embodiment 1 with the Linear PE having a density in the range of 0.90 to 0.96 g / cm3.
    [0046] 4. The composition of matter of embodiment 1 with the Linear PE having a density in the range of 0.905 to 0.93 g / cm3.
    [0047] 5. The material composition of embodiment 1 with the Linear PE having a MWD in the range of 1.9 to 2.5.
    [0048] 6. The material composition of embodiment 1 with the Linear PE having a MWD in the range of 2.0 to 2.3.
    [0049] 7. The composition of matter of embodiment 1 with the Linear PE having a melting index of 6 to 20 g / 10 min.
    [0050] 8. The composition of matter of embodiment 1 with the Linear PE having a melting index of 8 to 15 g / 10 min.
    [0051] 9. The material composition of embodiment 1 with the Linear PE having a Comonomer Distribution Constant of 50 to 200.
    [0052] 10. The matter composition of embodiment 1 with the Linear PE having a Comonomer Distribution Constant of 55 to 150.
    [0053] 11. The material composition of embodiment 1 with Linear PE having a vinyl unsaturation in the range of 0.01 to 0.1 vinyl per thousand carbon atoms in the main chain of the ethylene-based polymer composition.
    [0054] 12. The material composition of embodiment 1 with the Linear PE having a vinyl unsaturation in the range of 0.01 to 0.08 vinyl per thousand carbon atoms in the main chain of the ethylene-based polymer composition.
    [0055] 13. The composition of matter of embodiment 1 being that Linear PE is additionally characterized by having a Long Chain Branches (LCBf) frequency of 0.02 to 3 long chain branches per 1000 carbon atoms.
    [0056] 14. The composition of matter of embodiment 13 wherein the Linear PE has a frequency of Long Chain Branches (LCBf) from 0.02 to 1 long chain branch per 1000 carbon atoms.
    [0057] 15. The matter composition of embodiment 13 with Linear PE having a Long Chain Branching frequency (LCBf) of 0.02 to 0.5 long chain branching per 1000 carbon atoms.
    [0058] 16. The composition of matter of embodiment 1 wherein the Linear PE is additionally characterized by having a Shear Viscosity Ratio of Zero (ZSVR) of at least 1.4.
    [0059] 17. The material composition of embodiment 16, with the Zero Shear Viscosity Ratio (ZSVR) being at least 1.5.
    [0060] 18. The composition of matter of embodiment 1 wherein the Linear PE comprises from 97 to 55% by weight of the composition.
    [0061] 19. The composition of matter of embodiment 1 wherein the Linear PE comprises from 97 to 60% by weight of the composition.
    [0062] 20. The material composition of embodiment 1 with the low-pressure high-density polyethylene resin having a melt strength that satisfies the inequality Log melt strength (cN)> 1.16 - 0.6 x Log I2.
    [0063] 21. The composition of matter of embodiment 1 being that the low density high pressure polyethylene type resin has a melt strength that satisfies the unevenness Log melt strength (cN)> 1.18 - 0.6 x Log I2.
    [0064] 22. The material composition of embodiment 1 with the low pressure high density polyethylene resin having a melting index in the range of 0.4 to 12 g / 10 min.
    [0065] 23. The matter composition of embodiment 1 with the MI of the matter composition being 4 g / 10 minutes to 15 g / 10 minutes.
    [0066] 24. The matter composition of embodiment 1 with the MI of the matter composition being 7 g / 10 minutes to 12 g / 10 minutes.
    [0067] 25. A film made of the composition of matter as defined in any of embodiments 1 to 24.
    [0068] 26. The film of embodiment 25 additionally comprising one or more additional layers.
    [0069] 27. The matter composition of embodiment 1 additionally comprising one or more additional resin components.
    [0070] 28. The matter composition of embodiment 1 additionally comprising one or more additives.
    [0071] 29. The material composition of embodiment 28 being that the additive is selected from the group consisting of antioxidants, phosphites, tack additives, pigments, colorants, fillers, or combinations thereof.
    权利要求:
    Claims (15)
    [0001]
    1. Composition of the material, cβ-characteristic by the photo of the understanding: a. from 97 to 50 weight percent of the composition, of a Linear PE having i. a density in the range of 0.89 g / cm3 to 0.97 g / cm3 ii. an Mw / Mn of less than 2.8, iii. a melting index (I2) in the range of 4.0 to 25 g / 10 min, iv. a Comonomer Distribution Constant in the range of 45 to 400, see a vinyl unsaturation of less than 0.12 vinyls per thousand carbon atoms present in the main chain of the ethylene-based polymer composition; and b. 3 to 50 weight percent of the composition of a high pressure low density polyethylene resin having a melting index (I2) in the range of 0.1 to 15 g / 10 min, and having a melt strength that meets to inequality: Log melt strength (cN)> 1.14 - 0.6 x Log I2 (g / 10 min, 190 ° C); the MI (I2) of the composition of matter is in the range of 4 g / 10 minutes at 20 g / 10 min.
    [0002]
    2. Material composition, according to claim 1, characterized by the fact that the Linear PE has a MWD of at least 1.8, or that the linear PE has a MWD in the range of 2.0 to 2.3.
    [0003]
    3. Material composition, according to claim 1, characterized by the fact that Linear PE has a density in the range of 0.905 to 0.93 g / cm3.
    [0004]
    4. Material composition, according to claim 1, characterized by the fact that the Linear PE has a melting index of 8 to 15 g / 10 min.
    [0005]
    5. Material composition, according to claim 1, characterized by the fact that Linear PE has a Comonomer Distribution Constant of 55 to 150.
    [0006]
    6. Material composition, according to claim 1, characterized by the fact that Linear PE has a vinyl unsaturation in the range of 0.01 to 0.08 vinyl per thousand carbon atoms present main chain of the ethylene-based polymer composition .
    [0007]
    7. Material composition, according to claim 1, characterized in that the Linear PE additionally has a frequency of Long Chain Branches (LCBf) of 0.02 to 3 long chain branches per 1000 carbon atoms, preferably Linear PE has a Long Chain Branch (LCBf) frequency of 0.02 to 0.5 long chain branches per 1000 carbon atoms.
    [0008]
    8. Material composition, according to claim 1, characterized by the fact that the Linear PE additionally has a Viscosity Ratio to Zero Shear (ZSVR) of at least 1.4.
    [0009]
    9. Material composition, according to claim 1, characterized by the fact that the Linear PE comprises from 97 to 60% by weight of the composition.
    [0010]
    10. Material composition, according to claim 1, characterized by the fact that the high pressure low density polyethylene resin has a melt resistance that satisfies the inequality Log Melt Resistance (cN)> 1.18 - 0, 6 x Log I2, or the low pressure high density polyethylene resin having a melting index in the range of 0.4 to 12 g / 10 min.
    [0011]
    11. Material composition according to claim 1, characterized by the fact that the MI (I2) of the material composition is in the range of 4 g / 10 minutes to 15 g / 10 min, or that the MI (I2) the composition of matter is in the range of 7 g / 10 minutes to 12 g / 10 min.
    [0012]
    12. Film, characterized by the fact that it is made from the composition of matter, as defined in any of claims 1 to 12.
    [0013]
    13. Film according to claim 12, characterized by the fact that it comprises one or more additional layers.
    [0014]
    14. Composition of matter according to claim 1, characterized in that it additionally comprises one or more additional resin components.
    [0015]
    15. Composition of matter according to claim 1, characterized in that it additionally comprises one or more additives, preferably, the additive being selected from the group consisting of antioxidants, phosphites, tack additives, pigments, colorants, fillers, or combinations of these.
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    同族专利:
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    JP6243852B2|2017-12-06|
    JP2015503664A|2015-02-02|
    CN104136521A|2014-11-05|
    US20130164552A1|2013-06-27|
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    MX336639B|2016-01-26|
    MX2014007930A|2014-07-30|
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    US8889794B2|2014-11-18|
    KR101965469B1|2019-08-07|
    WO2013101930A1|2013-07-04|
    EP2798003A1|2014-11-05|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-08| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-06-23| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-11-03| 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 27/12/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/337,626|2011-12-27|
    US13/337,626|US8889794B2|2011-12-27|2011-12-27|Resin compositions for extrusion coating|
    PCT/US2012/071821|WO2013101930A1|2011-12-27|2012-12-27|Improved resin compositions for extrusion coating|
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