[go: up one dir, main page]

WO2011071843A1 - Films photodégradables avec bonnes propriétés à la traction et à l'essai de résistance au choc au mouton - Google Patents

Films photodégradables avec bonnes propriétés à la traction et à l'essai de résistance au choc au mouton Download PDF

Info

Publication number
WO2011071843A1
WO2011071843A1 PCT/US2010/059167 US2010059167W WO2011071843A1 WO 2011071843 A1 WO2011071843 A1 WO 2011071843A1 US 2010059167 W US2010059167 W US 2010059167W WO 2011071843 A1 WO2011071843 A1 WO 2011071843A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
copolymer
eco
films
ethylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2010/059167
Other languages
English (en)
Inventor
Colleen M. Tice
Teresa P. Karjala
Lori L. Kardos
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
Original Assignee
Dow Global Technologies LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Priority to US13/515,014 priority Critical patent/US8859671B2/en
Priority to MX2012006658A priority patent/MX2012006658A/es
Priority to BR112012014024A priority patent/BR112012014024B1/pt
Priority to RU2012129179/04A priority patent/RU2012129179A/ru
Priority to EP10795513.0A priority patent/EP2510049B1/fr
Priority to JP2012543188A priority patent/JP5723385B2/ja
Priority to CN201080063740.XA priority patent/CN102753615B/zh
Publication of WO2011071843A1 publication Critical patent/WO2011071843A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

  • This invention relates to photodegradable films.
  • the invention relates to photodegradable films comprising a copolymer with units derived from ethylene and carbon monoxide (ECO copolymer) while in another aspect, the invention relates to industrial, consumer and food packaging films comprising an ECO copolymer.
  • ECO copolymer units derived from ethylene and carbon monoxide
  • Ethylene/carbon monoxide copolymers have been known since at least as early as the 1940s, and their susceptibility to photodegradation has been know since at least as early the 1960s.
  • the use of ECO copolymers in the manufacture of industrial and consumer packaging films has been reported since at least as early as the 1970s, e.g., USP 3,676,401, 3,929,727 and 4,714,741 and GB 1 448 062.
  • these copolymers have not achieved the expected acceptance in industrial and consumer packaging applications because of their less than desirable mechanical properties, particularly tensile and puncture resistance.
  • the invention is a film structure comprising an ethylene/carbon monoxide (ECO) copolymer and an olefinic, particularly an ethylenic, polymer other than an ECO copolymer.
  • ECO copolymer comprises at least 40, preferably at least 60 to 85, weight percent (wt%) of the film structure with the remainder of the structure comprising at least one olefinic, preferably ethylenic, polymer other than the ECO copolymer.
  • Preferred olefinic polymers include, but are not limited to, low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and high density polyethylene (HDPE).
  • the film structure can either be a monolayer film in which the monolayer comprises both the ECO copolymer and other olefinic polymer, or a multilayer film in which (A) at least one of the layers comprises the ECO copolymer, and (B) at least one of the other layers comprises (1) an olefinic polymer other than an ECO copolymer, and (2) is free of ECO copolymer.
  • the film structure of this invention is one of a shrink film, lamination film, liner film, consumer bag, agriculture film, food packaging film like form-fill-seal and bag-in-box structures, and heavy-duty shipping sacks (HDSS).
  • Figure 1 is a line graph reporting the percent elongation of various inventive and comparative films after 300 hours of exposure to UV light on an accelerated QUV tester.
  • Figure 2 is a graph reporting the same information reported in Figure 1 except in bar format.
  • Numerical ranges are provided within this disclosure for, among other things, the amount of units derived from carbon monoxide in the ECO copolymer, the amount of ECO copolymer in the film structure, and the various tensile and puncture properties of the film structures of this invention.
  • composition and like terms mean a mixture or blend of two or more components.
  • Polymer blend and like terms mean a blend of two or more polymers. Such a blend may or may not be miscible. Such a blend may or may not be phase separated. Such a blend may or may not contain one or more domain configurations, as determined from transmission electron spectroscopy, light scattering, x-ray scattering, and any other method known in the art.
  • Polymer and like terms mean a macromolecular compound prepared by reacting (i.e., polymerizing) monomers of the same or different type. “Polymer” includes homopolymers and interpolymers.
  • Interpolymer means a polymer prepared by the polymerization of at least two different monomers. This generic term includes copolymers, usually employed to refer to polymers prepared from two different monomers, and polymers prepared from more than two different monomers, e.g., terpolymers, tetrapolymers, etc.
  • Olefmic polymer means a polymer that comprises 50 weight percent or more of polymerized olefin monomer (based on the total weight of polymer).
  • the olefin monomer can comprise two or more different olefin monomers.
  • Ethylene polymer means a polymer that comprises 50 weight percent or more of polymerized ethylene monomer (based on the total weight of polymer).
  • the ECO copolymer used in the practice of this invention has a melt index (I 2 , ASTM D1238 (190 °C/2.16 kg)) typically of 0.1 to 12, more typically of 0.25 to 6 and even more typically of 0.25 to 1.5 grams per 10 minutes (g/10 min); a density (ASTM D792) typically of 0.91 to 0.95, more typically of 0.92 to 0.94 and even more typically of 0.922 to 0.935, grams per cubic centimeter (g/cc); and a carbon monoxide content typically of 0.1 to 18, more typically of 0.5 to 10 and even more typically of 1 to 3, weight percent of the copolymer as measured by infrared spectroscopy.
  • One ECO copolymer useful in the practice of this invention is available from The Dow Chemical Company. It is an LDPE copolymer with a carbon monoxide content of 1 wt%, a melt index (MI or I 2 ) of 0.52 g/10 min, and a density of 0.93 g/cc.
  • the carbon monoxide content of the ECO copolymer can be measured by any conventional technique, e.g., Fourier Transform Infrared Spectroscopy.
  • the olefmic polymers that can be used in the practice of this invention include polymers based on a wide range of olefins, e.g., ethylene, propylene, butene and the like
  • the olefinic polymers of preference for use in this invention are the ethylenic polymers.
  • These ethylenic polymers include both homopolymers and interpolymers, random and blocky copolymers, and functionalized (e.g., ethylene vinyl acetate, ethylene ethyl acrylate, etc.) and non-functionalized polymers.
  • the ethylenic interpolymers include elastomers, flexomers and plastomers.
  • the ethylene polymer comprises at least 50, preferably at least 60 and more preferably at least 80, wt% of units derived from ethylene.
  • the other units of the ethylenic interpolymer are typically derived from one or more a-olefins.
  • ECO copolymers are not included in the definition of olefinic polymers.
  • the a-olefin is preferably a C 3-2 o linear, branched or cyclic -olefin.
  • Examples of C 3-20 oc-olefins include propene, 1 -butene, 4-methyl-l-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene.
  • the a-olefins also can contain a cyclic structure such as cyclohexane or cyclopentane, resulting in an a-olefin such as 3-cyclohexyl-l-propene (allyl cyclohexane) and vinyl cyclohexane.
  • a-olefin such as 3-cyclohexyl-l-propene (allyl cyclohexane) and vinyl cyclohexane.
  • certain cyclic olefins such as norbornene and related olefins, particularly 5-ethylidene-2-norbornene, are ⁇ -olefins and can be used in place of some or all of the a-olefins described above.
  • styrene and its related olefins are ⁇ -olefins for purposes of this invention.
  • Illustrative ethyleneic interpolymers include copolymers of ethylene/propylene, ethylene/butene, ethylene/1 -hexene, ethylene/1 -octene, ethylene/styrene, and the like.
  • Illustrative ethylenic terpolymers include ethylene/propylene/ 1-octene, ethylene/propylene- /butene, ethylene/butene/ 1 -octene, ethylene/propylene/diene monomer (EPDM) and ethylene/butene/styrene.
  • Examples of ethylenic polymers useful in the practice of this invention include high density polyethylene (HDPE); medium density polyethylene (MDPE); low density polyethylene (LDPE); very low density polyethylene (VLDPE); homogeneously branched, linear ethylene/a-olefin copolymers (e.g.
  • TAFMER® by Mitsui Petrochemicals Company Limited and EXACT® by DEX-Plastomers
  • homogeneously branched, substantially linear ethylene/a-olefin polymers e.g. , AFFINITY® polyolefin plastomers and ENGAGE® polyolefin elastomers available from The Dow Chemical Company
  • ethylene block copolymers INFUSE® also available from The Dow Chemical Company
  • substantially linear ethylene copolymers are more fully described in USP 5,272,236, 5,278,272 and 5,986,028, and the ethylene block copolymers are more fully described in USP7,579,408, 7,355,089 7,524,91 1, 7,514,517, 7,582,716 and 7,504,347.
  • Olefinic interpolymers of particular interest for use in the practice of this invention are LDPE, linear low density polyethylene (LLDPE) and HDPE. These ethylenic copolymers are commercially available from a number of difference sources including The Dow Chemical Company under such trademarks as DOWLEXTM, ATTANETM and FLEXOMEPvTM; Equistar/LyondellBasell under such trademarks as PETROTHENE; Nova Chemical Company under such trademarks as NOVAPOL and SCLAIR; and ExxonMobil Chemical Company under such trademarks as EXCEED, EXACT and ENABLE.
  • Useful film structures or articles of this invention include cast, blown, calendered and extrusion coated (including, but not limited to, multi-layer films, greenhouse films, shrink films including clarity shrink film, lamination film, biaxially-oriented film, extrusion coating, liners, clarity liners, overwrap film and agricultural film).
  • Monolayer and multilayer films may be made according to the film structures and fabrication methods described in USP 5,685,128.
  • the film structure is monolayer
  • the ECO copolymer and olefinic interpolymer e.g., LDPE
  • optional additives including one or more other polymers
  • the ECO copolymer comprises at least 40, 50, 60, 70, 80 or 90 wt% of the ECO/olefinic polymer blend, with the olefinic copolymer comprising at least 1, 10, 20, 30 or 40 wt% of the blend.
  • the olefinic copolymer comprising at least 1, 10, 20, 30 or 40 wt% of the blend.
  • the film structure is made from a polymeric blend comprising 40 to 90, preferably 60 to 85, wt% ECO copolymer and the 60 to 10, preferably 40 to 15, wt% LDPE, LLDPE or HDPE, preferably LLDPE.
  • the ECO copolymer can comprise all (100wt%) of one or more layers, but typically not of all layers, of the structure, or it can be present in one or more layers, including in each of the layers, of the structure as part of an ECO copolymer/olefinic polymer blend.
  • those layers are typically positioned within the structure to have interfacial contact with at least one layer that does comprise ECO copolymer.
  • the films of this invention have many utilities, including over-wrapping films such as tissue over-wraps, bundled bottled water over-wraps; clarity films such as candy bags, bread bags, envelope window films; food and specialty packaging films, such as produce bags, meat wraps, cheese wraps, etc.; pouches such as milk pouch, bags-in-box such as wine and other vertical form fill and seal techniques such as those taught by Dow, DuPont and Exxon.
  • Shrinkage films are particularly within the purview of the invention, and these can be made using a variety of techniques, such as double bubble films, tenter frame techniques, biaxial orientation techniques.
  • the films of the invention can also be elastic.
  • Useful film structures are also suitably prepared from polymeric blends comprising an ECO copolymer, an ethylenic copolymer of at least one of LDPE, LLDPE and HDPE, and at least one other natural or synthetic polymer other than the ECO copolymer and ethylenic copolymer.
  • Preferred other polymers include, but are not limited to, thermoplastics, such as styrene-butadiene block copolymers, polystyrene (including high impact polystyrene), ethylene vinyl alcohol copolymers, ethylene acrylic acid copolymers, polyamides, polyethers, polyurethanes, polyesters, cellulose, etc. If present, these other polymers typically comprise less than 50, more typically less than 40 and even more typically less than 20, wt% of the polymeric blend.
  • the ECO copolymer and olefinic polymer blend may be blended, if desired or necessary, with various additives such as antioxidants, ultraviolet absorbing agents, anti-fogging agents, antistatic agents, nucleating agents, lubricants, flame retardants, anti-blocking agents, colorants, inorganic or organic fillers or the like. If used, these additives are used in known manners and in known amounts including, but not limited to, addition as part of a masterbatch and in amounts typically of 0.01 to 10 or more wt% based on the total weight of the film structure (although fillers may be used in much larger amounts).
  • additives such as antioxidants, ultraviolet absorbing agents, anti-fogging agents, antistatic agents, nucleating agents, lubricants, flame retardants, anti-blocking agents, colorants, inorganic or organic fillers or the like. If used, these additives are used in known manners and in known amounts including, but not limited to, addition as part of a masterbatch and in amounts typically of 0.01
  • the film structures of this invention may be made by conventional fabrication techniques, e.g. simple bubble extrusion, biaxial orientation processes (such as tenter frames or double bubble processes), simple cast/sheet extrusion, co- extrusion, lamination, etc.
  • conventional simple bubble extrusion processes also known as hot blown film processes are described, for example, in The Encyclopedia of Chemical Technology, Kirk-Othmer, Third Edition, John Wiley & Sons, New York, 1981, Vol 16, pp. 416-417 and Vol. 18, pp. 191-192.
  • Biaxial orientation film manufacturing processes such as those described in the "double bubble” process of USP 3,456,044, and the processes described in USP 4,352,849, 4,820,557, 4,837,084, 4,865,902, 4,927,708, 4.952,451 , 4,963,419 and 5,059,481 can also be used to make the film structures of this invention.
  • Biaxially oriented film structures can also be made by a tenter-frame technique, such as that used for oriented polypropylene.
  • the thickness of the multilayer structures is typically from 1 to 4 mils (total thickness).
  • Multilayer film structures typically comprise from 2 to 7 layers, but the only limits on the total number of layers are those imposed by economics and practicality.
  • the thickness is typically 0.4 to 4 mils, preferably 0.8 to 2.5 mils.
  • the film structures of the invention can be made into packaging structures such as form-fill-seal structures and bag-in-box structures.
  • packaging structures such as form-fill-seal structures and bag-in-box structures.
  • form-fill-seal and bag-in-box structures one such operation is described in Packaging Foods With Plastics by Wilmer A. Jenkins and James P. Harrington (1991), pp. 78-83.
  • Packages can also be formed from multilayer packaging roll stock by vertical or horizontal form-fill (see packaging and thermoform-fill-seal packaging, as described in "Packaging Machinery Operations: No. 8, Form-Fill-Sealing, A Self-Instructional Course” by C. G. Davis, Packaging Machinery Manufacturers Institute (April 1982); The Wiley Encyclopedia of Packaging Technology by M.
  • Bakker Editor
  • Packaging An Introduction by S. Sacharow and A. L. Brody, Harcourt Brace Javanovich Publications, Inc. (1987), pp.322-326).
  • a process for making a pouch with a vertical form-fill-seal machine is described generally in USP 4,503,102 and 4,521,437.
  • Film structures containing one or more layers comprising an ECO copolymer are well suited for the packaging of potable water, wine, condiments, and similar food products.
  • Extrusion coating is yet another technique for producing multilayer packaging materials. Similar to cast film, extrusion coating is a flat die technique. A film can be extrusion coated or laminated onto a substrate either in the form of a monolayer or a coextruded film. The film structure may also be formed into a lid stock for an injection molded, blow molded or thermoformed tray.
  • the film structure is a shrink film.
  • a shrink film Upon exposure to heat, a shrink film will either shrink or, if restrained, create shrink tension within the film.
  • This heat reaction is generally activated when the wrapped product is passed through a hot air or hot water shrink tunnel. Generally, this process causes the film to shrink around the product to produce a tight, transparent wrapping which conforms to the contour of the product, while protecting the product from dirt and contamination.
  • Hot-blown shrink film is made by a hot-blown simple bubble film process and, conversely, oriented shrink film is made by elaborate biaxial orientation processes known as double bubble, tape bubble, trapped bubble or tenter framing.
  • oriented shrink film is made by elaborate biaxial orientation processes known as double bubble, tape bubble, trapped bubble or tenter framing.
  • Both amorphous and semi-crystalline polymers can be made into oriented shrink films using elaborate biaxial orientation processes.
  • the orientation is performed at a temperature immediately above the glass transition temperature of the polymer.
  • semi-crystalline polymers the orientation is performed at a temperature below the peak melting point of the polymer.
  • Samples for density measurement are prepared according to ASTM D1928. Measurements are made within one hour of sample pressing using ASTM D792, Method B.
  • Total (Overall), Surface and Internal Haze Samples measured for internal haze and overall haze are sampled and prepared according to ASTM D1003. Internal haze is obtained via refractive index matching using mineral oil on both sides of the films. A Hazegard Plus (BYK-Gardner USA; Columbia, MD) is used for testing. Surface haze is determined as the difference between overall haze and internal haze as shown in the Equation below. Surface haze tends to be related to the surface roughness of the film, where surface haze increases with increasing surface roughness.
  • Puncture is measured on an Instron Model 4201 with Sintech Testworks Software Version 3.10. Specimen size is 6" x 6" and 4 measurements are made to determine an average puncture value.
  • the film is conditioned for 40 hours after film production and at least 24 hours in an ASTM controlled laboratory.
  • a 100 lb load cell is used with a round specimen holder 12.56" square.
  • the puncture probe is a 1 ⁇ 2" diameter polished stainless steel ball with a 7.5" maximum travel length. There is no gauge length; the probe is as close as possible to, but not touching, the specimen.
  • the crosshead speed used is lO'Yminute.
  • the thickness is measured in the middle of the specimen. The thickness of the film, the distance the crosshead traveled, and the peak load are used to determine the puncture by the software.
  • the puncture probe is cleaned using a "Kim-wipe" after each specimen.
  • Shrink tension for MD and CD is measured according to the method described in Y. Jin, T. Hermel-Davidock, T. Karjala, M. Demirors, J. Wang, E. Leyva, and D. Allen, “Shrink Force Measurement of Low Shrink Force Films", SPE ANTEC Proceedings, p. 1264 (2008).
  • the film of Example 1 comprises 85 wt% of an ethyl enic copolymer (an LDPE) of ethylene and carbon monoxide (MI or I 2 of 0.52 g/ 10 min, density of 0.930 g/cc and a CO content of 1 wt%) and 15 wt% ELITE 51 11G (I 2 of 0.85 g/10 min, density of 0.9255 g/cc and without any CO content), both available from The Dow Chemical Company.
  • an LDPE ethyl enic copolymer
  • MI or I 2 ethylene and carbon monoxide
  • MI or I 2 ethylene and carbon monoxide
  • ELITE 51 11G I 2 of 0.85 g/10 min, density of 0.9255 g/cc and without any CO content
  • the film of Comparative Example 1 (CE-1) comprises 85 wt% LDPE 535E (MI of 0.60 g/10 min, density of 0.928 g/cc and without any CO content, also available from The Dow Chemical Company) and 15 wt% ELITE 5111G.
  • the film of Example 2 comprises 60 wt% of the CO- containing LDPE of Example 1 and 40 wt% ELITE 51 1 1 G.
  • the film of Comparative Example 2 (CE-2) comprises 60 wt% LDPE 535E and 40 wt% ELITE 51 1 1G. Melt index is measured according to ASTM Dl 238 (190 °C/2.16 kg), and density is measured according to ASTM D792.
  • Blown films of Examples 1 and 2 and CE-1 and 2 are made on a 6" die with a LLDPE type screw. No internal bubble cooling is used. Pellets of each polymer are physically blended with one another in their proper proportion, and the physical blend of pellets is then fed to the extruder through the pellet hopper.
  • the general blown film parameters used to produce the blown films are reported in Table 1. The reported temperatures begin near the pellet hopper and follow the polymer as it moves to and through the die (melt temperature).
  • the blow-up ratio (BUR) for each film is shown in Table 1, and each film is fabricated to a thickness of 2.5 mil.
  • Table 2 Table 1
  • the films of this invention exhibit lower modulus for higher density (2% secant modulus CD of Ex. 1 vs. CE-1), enhanced CD and MD Elmendorf tear, and higher ultimate CD and MD tensile and elongation.
  • Each sample is measured for percent elongation according to ASTM D3826. Samples that have less than 5% elongation after 300 hours in the QUV tester are considered degraded.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Wrappers (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des structures en film faites d'un mélange polymère comportant un copolymère d'éthylène/monoxyde de carbone (ECO) et un polymère oléfinique, en particulier éthylénique, par exemple le LDPE. Ces structures présentent non seulement une photodégradation, mais encore des propriétés souhaitables à la traction et à l'essai de résistance au choc au mouton. Dans un mode de réalisation, la structure en film est une monocouche dans laquelle le copolymère ECO représente au moins 40 pour cent en poids, le reste de la structure comportant au moins l'un parmi le LDPE, le LLDPE et le HDPE.
PCT/US2010/059167 2009-12-11 2010-12-07 Films photodégradables avec bonnes propriétés à la traction et à l'essai de résistance au choc au mouton Ceased WO2011071843A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US13/515,014 US8859671B2 (en) 2009-12-11 2010-12-07 Photodegradable films with good tensile and dart properties
MX2012006658A MX2012006658A (es) 2009-12-11 2010-12-07 Peliculas fotodegradables con buenas propiedades de tension y dardo.
BR112012014024A BR112012014024B1 (pt) 2009-12-11 2010-12-07 estrutura de filme encolhível
RU2012129179/04A RU2012129179A (ru) 2009-12-11 2010-12-07 Фоторазлагаемые пленки с хорошими показателями прочностных свойств при растяжении и ударе
EP10795513.0A EP2510049B1 (fr) 2009-12-11 2010-12-07 Shrink-films photodégradables avec bonnes propriétés à la traction et à l'essai de résistance au choc au mouton
JP2012543188A JP5723385B2 (ja) 2009-12-11 2010-12-07 優れた引張特性およびダーツ特性を備える光分解性フィルム
CN201080063740.XA CN102753615B (zh) 2009-12-11 2010-12-07 具有良好的拉伸和落镖性质的光可降解的膜

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US28574109P 2009-12-11 2009-12-11
US61/285,741 2009-12-11

Publications (1)

Publication Number Publication Date
WO2011071843A1 true WO2011071843A1 (fr) 2011-06-16

Family

ID=43426149

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2010/059167 Ceased WO2011071843A1 (fr) 2009-12-11 2010-12-07 Films photodégradables avec bonnes propriétés à la traction et à l'essai de résistance au choc au mouton

Country Status (10)

Country Link
US (1) US8859671B2 (fr)
EP (1) EP2510049B1 (fr)
JP (1) JP5723385B2 (fr)
KR (1) KR20120103697A (fr)
CN (1) CN102753615B (fr)
BR (1) BR112012014024B1 (fr)
MX (1) MX2012006658A (fr)
MY (1) MY161385A (fr)
RU (1) RU2012129179A (fr)
WO (1) WO2011071843A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014105608A1 (fr) 2012-12-28 2014-07-03 Dow Global Technologies Llc Polymères à base d'éthylène et leurs procédés de production
WO2015200430A1 (fr) 2014-06-27 2015-12-30 Dow Global Technologies Llc Procédé pour préparer des polymères à base d'éthylène à l'aide d'une distribution de monoxyde de carbone
WO2015200426A1 (fr) 2014-06-27 2015-12-30 Dow Global Technologies Llc Polymères à base d'éthylène comprenant des motifs dérivés du monoxyde de carbone et d'un agent modifiant la rhéologie
WO2017189299A1 (fr) 2016-04-29 2017-11-02 Dow Global Technologies Llc Compositions comprenant des copolymères d'éthylène-monoxyde de carbone
WO2019089750A1 (fr) 2017-10-31 2019-05-09 Dow Global Technologies Llc Interpolymères d'éthylène/co et procédés de fabrication associés
CN111393738A (zh) * 2020-05-06 2020-07-10 常州祎唯诺塑业有限公司 一种光降解型pe缠绕膜及其制备方法

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080003332A1 (en) * 2006-05-12 2008-01-03 Dimitrios Ginossatis Multilayer heat shrinkable cook-in film
ATE552304T1 (de) 2008-01-02 2012-04-15 Flexopack Sa Pvdc-formulierung und wärmeschrumpfbare folie
GB2475961B (en) * 2009-12-02 2015-07-08 Flexopack Sa Thin film for waste packing cassettes
EP2520518B1 (fr) 2011-05-03 2020-09-23 Flexopack S.A. Dispositif de conditionnement de déchets
DE202011110797U1 (de) 2011-06-16 2016-08-10 Flexopack S.A. Abfallverpackungssystem und Folie
US9604430B2 (en) 2012-02-08 2017-03-28 Flexopack S.A. Thin film for waste packing cassettes
CN103009761B (zh) * 2012-12-25 2015-07-15 海南赛诺实业有限公司 一种高收缩率聚烯烃热收缩薄膜及其制造方法
EP2813362B1 (fr) 2013-06-14 2019-05-22 Flexopack S.A. Film thermorétractable
AU2015258191B2 (en) 2014-11-19 2020-02-27 Flexopack S.A. Oven skin packaging process
EP3262402B1 (fr) 2015-02-27 2019-08-07 Dow Global Technologies LLC Procédés et systèmes de mesure des forces d'un film rétractable
EP3501822A1 (fr) 2017-12-22 2019-06-26 Flexopack S.A. Film de revêtement pour fibc
US12215232B2 (en) 2019-01-31 2025-02-04 Dow Global Technologies Llc Asphalt compositions including recycled polymer and epoxy-functionalized ethylene copolymer
KR20230002569A (ko) * 2020-04-10 2023-01-05 다우 글로벌 테크놀로지스 엘엘씨 포스트 컨슈머 수지를 포함하는 필름
CN116987339B (zh) * 2023-09-26 2024-01-16 东莞市贵来新材料科技有限公司 一种可降解的竹纤维基高分子材料及其制备方法

Citations (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3456044A (en) 1965-03-12 1969-07-15 Heinz Erich Pahlke Biaxial orientation
US3676401A (en) 1964-11-16 1972-07-11 Eastman Kodak Co Environmentally disintegratable plastic compositions comprising copolymers of ethylene and carbon monoxide and a degradation accelerator
DE2316697A1 (de) * 1972-04-07 1973-10-11 Leer Koninklijke Emballage Durch einwirken von ultravioletter bestrahlung photozersetzbare polymersubstanz
US3929727A (en) 1975-06-18 1975-12-30 Atlantic Richfield Co Stabilized ethylene-carbon monoxide copolymers
GB1448062A (en) 1973-01-16 1976-09-02 Ruhrchemie Ag Degradable ofelin polymers
US4352849A (en) 1981-03-26 1982-10-05 W. R. Grace & Co. Coextruded, heat-shrinkable, multi-layer, polyolefin packaging film
US4503102A (en) 1982-01-20 1985-03-05 Du Pont Of Canada, Inc. Pouches of ethylene-α-olefin copolymer/ethylene-vinyl acetate copolymer blends
US4521437A (en) 1982-06-02 1985-06-04 Du Pont Canada Inc. Pouches of ethylene/octene-1 copolymer film containing a flowable material
US4714741A (en) 1986-04-25 1987-12-22 Owens-Illinois Plastic Products Inc. Degradable polymer composition
US4820557A (en) 1987-09-17 1989-04-11 W. R. Grace & Co.-Conn. Thermoplastic packaging film of low I10 /I2
US4837084A (en) 1987-07-02 1989-06-06 W. R. Grace & Co.-Conn. Thermoplastic multi-layer packaging film and bags made therefrom
US4865902A (en) 1986-01-17 1989-09-12 E. I. Du Pont De Nemours And Company Multilayered polyolefin high shrinkage, low-shrink force shrink film
US4927708A (en) 1987-04-10 1990-05-22 W. R. Grace & Co.-Conn. Flexible stretch/shrink film
US4952451A (en) 1988-11-17 1990-08-28 W. R. Grace & Co.-Conn. Stretch/shrink film with improved oxygen transmission
US4963419A (en) 1987-05-13 1990-10-16 Viskase Corporation Multilayer film having improved heat sealing characteristics
US5059481A (en) 1985-06-17 1991-10-22 Viskase Corporation Biaxially stretched, heat shrinkable VLDPE film
WO1991018944A1 (fr) * 1990-05-18 1991-12-12 The Dow Chemical Company Agents de photodegradation et de thermosoudage pour materiaux matriciels polymeres
US5272236A (en) 1991-10-15 1993-12-21 The Dow Chemical Company Elastic substantially linear olefin polymers
US5278272A (en) 1991-10-15 1994-01-11 The Dow Chemical Company Elastic substantialy linear olefin polymers
US5685128A (en) 1991-10-15 1997-11-11 The Dow Chemical Company Method of packaging food products
US5707751A (en) 1992-10-02 1998-01-13 E. I. Du Pont De Nemours And Company Shrink film and methods relating thereto
US5852152A (en) 1991-10-15 1998-12-22 The Dow Chemical Company Packaging and wrapping film
US5972444A (en) 1991-10-15 1999-10-26 The Dow Chemical Company Polyolefin compositions with balanced shrink properties
US5986028A (en) 1991-10-15 1999-11-16 The Dow Chemical Company Elastic substantially linear ethlene polymers
US6306969B1 (en) 1996-11-13 2001-10-23 The Dow Chemical Company Shrink film having balanced properties or improved toughness and methods of making the same
US6558809B1 (en) * 1999-05-18 2003-05-06 The Dow Chemical Company Flexible, halogen-free, radio-frequency sealable films
EP1529633A1 (fr) 2003-09-24 2005-05-11 ExxonMobil Chemical Patents Inc. Regroupement en feuille rétractable.
EP1532203A1 (fr) 2002-07-29 2005-05-25 Borealis Technology Oy Film retrecissable
US7355089B2 (en) 2004-03-17 2008-04-08 Dow Global Technologies Inc. Compositions of ethylene/α-olefin multi-block interpolymer for elastic films and laminates
US7504347B2 (en) 2004-03-17 2009-03-17 Dow Global Technologies Inc. Fibers made from copolymers of propylene/α-olefins
US7514517B2 (en) 2004-03-17 2009-04-07 Dow Global Technologies Inc. Anti-blocking compositions comprising interpolymers of ethylene/α-olefins
US7524911B2 (en) 2004-03-17 2009-04-28 Dow Global Technologies Inc. Adhesive and marking compositions made from interpolymers of ethylene/α-olefins
US7579408B2 (en) 2004-03-17 2009-08-25 Dow Global Technologies Inc. Thermoplastic vulcanizate comprising interpolymers of ethylene/α-olefins
US7582716B2 (en) 2004-03-17 2009-09-01 Dow Global Technologies Inc. Compositions of ethylene/α-olefin multi-block interpolymer for blown films with high hot tack

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR8607069A (pt) 1985-12-31 1988-04-05 Dow Chemical Co Agente fotodegradante,composicoes polimericas de etileno fotodegradaveis e artigos produzidos com as mesmas
US4962164A (en) 1988-06-27 1990-10-09 Owens-Illinois Plastic Products Inc. Degradable polymers and articles made therefrom
GB8908342D0 (en) * 1989-04-13 1989-06-01 Bp Chem Int Ltd Photodegradable polymer composition
DE3921144A1 (de) * 1989-06-28 1991-01-10 Hoechst Ag Abbaufaehige polymerisatmischungen
WO1996006889A1 (fr) 1994-08-26 1996-03-07 Bp Chemicals Limited Melanges de polycetone et de polyethylene basse densite a structure lineaire
GB9622716D0 (en) 1996-10-31 1997-01-08 Bp Chem Int Ltd Multi-layer structures
JP2000290403A (ja) * 1999-04-08 2000-10-17 Asahi Chem Ind Co Ltd 密着性耐熱ラップフィルム

Patent Citations (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3676401A (en) 1964-11-16 1972-07-11 Eastman Kodak Co Environmentally disintegratable plastic compositions comprising copolymers of ethylene and carbon monoxide and a degradation accelerator
US3456044A (en) 1965-03-12 1969-07-15 Heinz Erich Pahlke Biaxial orientation
DE2316697A1 (de) * 1972-04-07 1973-10-11 Leer Koninklijke Emballage Durch einwirken von ultravioletter bestrahlung photozersetzbare polymersubstanz
GB1448062A (en) 1973-01-16 1976-09-02 Ruhrchemie Ag Degradable ofelin polymers
US3929727A (en) 1975-06-18 1975-12-30 Atlantic Richfield Co Stabilized ethylene-carbon monoxide copolymers
US4352849A (en) 1981-03-26 1982-10-05 W. R. Grace & Co. Coextruded, heat-shrinkable, multi-layer, polyolefin packaging film
US4503102A (en) 1982-01-20 1985-03-05 Du Pont Of Canada, Inc. Pouches of ethylene-α-olefin copolymer/ethylene-vinyl acetate copolymer blends
US4521437A (en) 1982-06-02 1985-06-04 Du Pont Canada Inc. Pouches of ethylene/octene-1 copolymer film containing a flowable material
US5059481A (en) 1985-06-17 1991-10-22 Viskase Corporation Biaxially stretched, heat shrinkable VLDPE film
US4865902A (en) 1986-01-17 1989-09-12 E. I. Du Pont De Nemours And Company Multilayered polyolefin high shrinkage, low-shrink force shrink film
US4714741A (en) 1986-04-25 1987-12-22 Owens-Illinois Plastic Products Inc. Degradable polymer composition
US4927708A (en) 1987-04-10 1990-05-22 W. R. Grace & Co.-Conn. Flexible stretch/shrink film
US4963419A (en) 1987-05-13 1990-10-16 Viskase Corporation Multilayer film having improved heat sealing characteristics
US4837084A (en) 1987-07-02 1989-06-06 W. R. Grace & Co.-Conn. Thermoplastic multi-layer packaging film and bags made therefrom
US4820557A (en) 1987-09-17 1989-04-11 W. R. Grace & Co.-Conn. Thermoplastic packaging film of low I10 /I2
US4952451A (en) 1988-11-17 1990-08-28 W. R. Grace & Co.-Conn. Stretch/shrink film with improved oxygen transmission
WO1991018944A1 (fr) * 1990-05-18 1991-12-12 The Dow Chemical Company Agents de photodegradation et de thermosoudage pour materiaux matriciels polymeres
US5272236A (en) 1991-10-15 1993-12-21 The Dow Chemical Company Elastic substantially linear olefin polymers
US5278272A (en) 1991-10-15 1994-01-11 The Dow Chemical Company Elastic substantialy linear olefin polymers
US5685128A (en) 1991-10-15 1997-11-11 The Dow Chemical Company Method of packaging food products
US5852152A (en) 1991-10-15 1998-12-22 The Dow Chemical Company Packaging and wrapping film
US5972444A (en) 1991-10-15 1999-10-26 The Dow Chemical Company Polyolefin compositions with balanced shrink properties
US5986028A (en) 1991-10-15 1999-11-16 The Dow Chemical Company Elastic substantially linear ethlene polymers
US5707751A (en) 1992-10-02 1998-01-13 E. I. Du Pont De Nemours And Company Shrink film and methods relating thereto
US6306969B1 (en) 1996-11-13 2001-10-23 The Dow Chemical Company Shrink film having balanced properties or improved toughness and methods of making the same
US6558809B1 (en) * 1999-05-18 2003-05-06 The Dow Chemical Company Flexible, halogen-free, radio-frequency sealable films
EP1532203A1 (fr) 2002-07-29 2005-05-25 Borealis Technology Oy Film retrecissable
EP1529633A1 (fr) 2003-09-24 2005-05-11 ExxonMobil Chemical Patents Inc. Regroupement en feuille rétractable.
US7355089B2 (en) 2004-03-17 2008-04-08 Dow Global Technologies Inc. Compositions of ethylene/α-olefin multi-block interpolymer for elastic films and laminates
US7504347B2 (en) 2004-03-17 2009-03-17 Dow Global Technologies Inc. Fibers made from copolymers of propylene/α-olefins
US7514517B2 (en) 2004-03-17 2009-04-07 Dow Global Technologies Inc. Anti-blocking compositions comprising interpolymers of ethylene/α-olefins
US7524911B2 (en) 2004-03-17 2009-04-28 Dow Global Technologies Inc. Adhesive and marking compositions made from interpolymers of ethylene/α-olefins
US7579408B2 (en) 2004-03-17 2009-08-25 Dow Global Technologies Inc. Thermoplastic vulcanizate comprising interpolymers of ethylene/α-olefins
US7582716B2 (en) 2004-03-17 2009-09-01 Dow Global Technologies Inc. Compositions of ethylene/α-olefin multi-block interpolymer for blown films with high hot tack

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
"The Wiley Encyclopedia of Packaging Technology", vol. 334, 1986, JOHN WILEY & SONS, pages: 364 - 369
C. G. DAVIS: "Packaging Machinery Operations: No. 8, Form-Fill-Sealing, A Self-Instructional Course", April 1982, PACKAGING MACHINERY MANUFACTURERS INSTITUTE
KIRK-OTHMER: "The Encyclopedia of Chemical Technology", vol. 16, 18, 1981, JOHN WILEY & SONS, pages: 416 - 417,191-
S. SACHAROW; A. L. BRODY: "Packaging: An Introduction", 1987, HARCOURT BRACE JAVANOVICH PUBLICATIONS, INC., pages: 322 - 326
WILMER A. JENKINS; JAMES P. HARRINGTON, PACKAGING FOODS WITH PLASTICS, 1991, pages 78 - 83
Y. JIN; T. HERMEL-DAVIDOCK; T. KAIJALA; M. DEMIRORS; J. WANG; E. LEYVA; D. ALLEN: "Shrink Force Measurement of Low Shrink Force Films", SPE ANTEC PROCEEDINGS, 2008, pages 1264

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9523015B2 (en) 2012-12-28 2016-12-20 Dow Global Technologies Llc Ethylene-based polymers and processes to make the same
EP3470483A1 (fr) 2012-12-28 2019-04-17 Dow Global Technologies Llc Polymères à base d'éthylène et leurs procédés de production
WO2014105608A1 (fr) 2012-12-28 2014-07-03 Dow Global Technologies Llc Polymères à base d'éthylène et leurs procédés de production
JP2016508175A (ja) * 2012-12-28 2016-03-17 ダウ グローバル テクノロジーズ エルエルシー エチレン系ポリマーおよびその製造プロセス
US9856338B2 (en) 2014-06-27 2018-01-02 Dow Global Technologies Llc Processes to prepare ethylene-based polymers using a distribution of carbon monoxide
WO2015200426A1 (fr) 2014-06-27 2015-12-30 Dow Global Technologies Llc Polymères à base d'éthylène comprenant des motifs dérivés du monoxyde de carbone et d'un agent modifiant la rhéologie
WO2015200430A1 (fr) 2014-06-27 2015-12-30 Dow Global Technologies Llc Procédé pour préparer des polymères à base d'éthylène à l'aide d'une distribution de monoxyde de carbone
US10654955B2 (en) 2014-06-27 2020-05-19 Dow Global Technologies Llc Ethylene-based polymers comprising units derived from carbon monoxide and a rheology modifying agent
WO2017189299A1 (fr) 2016-04-29 2017-11-02 Dow Global Technologies Llc Compositions comprenant des copolymères d'éthylène-monoxyde de carbone
WO2019089750A1 (fr) 2017-10-31 2019-05-09 Dow Global Technologies Llc Interpolymères d'éthylène/co et procédés de fabrication associés
US11542368B2 (en) 2017-10-31 2023-01-03 Dow Global Technologies Llc Ethylene/CO interpolymers and processes to make the same
CN111393738A (zh) * 2020-05-06 2020-07-10 常州祎唯诺塑业有限公司 一种光降解型pe缠绕膜及其制备方法
CN111393738B (zh) * 2020-05-06 2022-12-02 江苏祎唯诺新材料科技有限公司 一种光降解型pe缠绕膜及其制备方法

Also Published As

Publication number Publication date
RU2012129179A (ru) 2014-01-20
KR20120103697A (ko) 2012-09-19
CN102753615B (zh) 2014-05-28
JP5723385B2 (ja) 2015-05-27
BR112012014024B1 (pt) 2019-09-03
CN102753615A (zh) 2012-10-24
US8859671B2 (en) 2014-10-14
MY161385A (en) 2017-04-14
BR112012014024A2 (pt) 2017-03-28
EP2510049B1 (fr) 2017-01-25
MX2012006658A (es) 2012-09-12
US20120289645A1 (en) 2012-11-15
JP2013513695A (ja) 2013-04-22
EP2510049A1 (fr) 2012-10-17

Similar Documents

Publication Publication Date Title
US8859671B2 (en) Photodegradable films with good tensile and dart properties
CA2658945C (fr) Compositions destinees a fabriquer des films disposes en couches, conditionnements prepares a partir de ces compositions et leurs procedes d'utilisation
US9388306B2 (en) Polyethylene stretch film
US20060188678A1 (en) Multi-layer polyethylene films
US6482532B1 (en) Easy tear non-halogenic food wrap
JP5857046B2 (ja) Ｕｌｄｐｅリッチ配合物から作製されたストレッチフード
JP7744919B2 (ja) ポストコンシューマレジンを含むフィルム
JP6005580B2 (ja) ポリエチレン系多層フィルム
US10717833B2 (en) Methods of preparing a peelable seal layer
TW202009140A (zh) 具有改善的抗穿刺效能的多層熱塑性薄膜
MX2010014546A (es) Peliculas, articulos preparados a partir de las mismas y metodos para hacer las mismas.
JP2006305886A (ja) シーラントフィルム、包装材料、蓋材及び容器
JP5453411B2 (ja) フィルム、フィルムから調製される物品及びその作製方法
JP7549648B2 (ja) エチレン系樹脂組成物及びフィルム
JP2004358683A (ja) 加熱殺菌処理食品包装用フィルム
EP4241985A1 (fr) Film multicouches
JP2838120B2 (ja) ポリエチレン樹脂組成物およびその積層フィルム
JP4802687B2 (ja) ポリプロピレン系複合無延伸フィルム
JP2008162163A (ja) ポリプロピレン系樹脂積層フィルム
KR20140007784A (ko) 초저밀도 폴리에틸렌이 농후한 제제로부터 제조된 스트레치 후드
WO2025028357A1 (fr) Film étiré biaxialement et son procédé de production
JP2006299063A (ja) 加熱殺菌処理包装フィルム用樹脂組成物及びそれを用いた加熱殺菌処理包装フィルム

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201080063740.X

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10795513

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
WWE Wipo information: entry into national phase

Ref document number: MX/A/2012/006658

Country of ref document: MX

NENP Non-entry into the national phase

Ref country code: DE

REEP Request for entry into the european phase

Ref document number: 2010795513

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 13515014

Country of ref document: US

Ref document number: 2012543188

Country of ref document: JP

Ref document number: 5090/CHENP/2012

Country of ref document: IN

Ref document number: 2010795513

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 20127017863

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2012129179

Country of ref document: RU

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112012014024

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 112012014024

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20120611