WO2008155404A1 - Process for the production of polypropylene articles with increased response to surface energy increasing treatment. - Google Patents
Process for the production of polypropylene articles with increased response to surface energy increasing treatment. Download PDFInfo
- Publication number
- WO2008155404A1 WO2008155404A1 PCT/EP2008/057847 EP2008057847W WO2008155404A1 WO 2008155404 A1 WO2008155404 A1 WO 2008155404A1 EP 2008057847 W EP2008057847 W EP 2008057847W WO 2008155404 A1 WO2008155404 A1 WO 2008155404A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metallocene
- polypropylene
- catalyzed polyethylene
- treatment
- surface energy
- Prior art date
Links
- -1 polypropylene Polymers 0.000 title claims abstract description 118
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 63
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 62
- 238000011282 treatment Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000001965 increasing effect Effects 0.000 title claims abstract description 21
- 230000008569 process Effects 0.000 title claims abstract description 16
- 230000004044 response Effects 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 229920000573 polyethylene Polymers 0.000 claims abstract description 46
- 239000004698 Polyethylene Substances 0.000 claims abstract description 45
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- 238000003851 corona treatment Methods 0.000 claims description 18
- 238000001125 extrusion Methods 0.000 claims description 13
- 238000010103 injection stretch blow moulding Methods 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000001746 injection moulding Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 8
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 8
- 229920005604 random copolymer Polymers 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 239000012792 core layer Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 238000000071 blow moulding Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 229920005606 polypropylene copolymer Polymers 0.000 description 3
- 238000013329 compounding Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229920001384 propylene homopolymer Polymers 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- RSPAIISXQHXRKX-UHFFFAOYSA-L 5-butylcyclopenta-1,3-diene;zirconium(4+);dichloride Chemical compound Cl[Zr+2]Cl.CCCCC1=CC=C[CH-]1.CCCCC1=CC=C[CH-]1 RSPAIISXQHXRKX-UHFFFAOYSA-L 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000006653 Ziegler-Natta catalysis Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- RYPKRALMXUUNKS-UHFFFAOYSA-N hex-2-ene Chemical compound CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000011426 transformation method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/08—Heat treatment
-
- 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
- C08L23/10—Homopolymers or copolymers of propene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0094—Condition, form or state of moulded material or of the material to be shaped having particular viscosity
-
- 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
- C08J2323/10—Homopolymers or copolymers of propene
-
- 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
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/06—Metallocene or single site catalysts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2555/00—Characteristics of bituminous mixtures
- C08L2555/40—Mixtures based upon bitumen or asphalt containing functional additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31—Surface property or characteristic of web, sheet or block
Definitions
- a major disadvantage of flame- and Corona-treatment is that the effect of the treatment quickly wears off. Within one week from treating the polypropylene a decay of 3 mN/m may occur. Thus, in many cases the treated polypropylene requires a "refresher" treatment before further transformation.
- the present invention relates to the use of a metallocene-catalyzed polyethylene as surface energy increasing additive. Detailed description of the invention
- Blends of polypropylene and metallocene-catalyzed polyethylene are for example known from WO 2005/005143 for improving the impact performance of containers.
- WO 2005/005143 is silent on the use of such compositions for improving the response to surface energy increasing treatments.
- the metallocene-based catalytic system used to produce the metallocene- catalyzed polyethylene comprises a metallocene, a support and an activating agent.
- metallocene-based catalytic systems are known to the person skilled in the art and need not be explained in detail.
Abstract
The present invention relates to a process for the production of polypropylene articles with improved response to a surface energy increasing treatment, wherein the polypropylene comprises a metallocene-catalyzed polyethylene. The present invention further relates to the use of metallocene-catalyzed polyethylene as an additive for improving the response of polypropylene to surface energy increasing treatments.
Description
PROCESS FOR THE PRODUCTION OF POLYPROPYLENE ARTICLES WITH INCREASED RESPONSE TO SURFACE ENERGY INCREASING
TREATMENT
Field of the invention
The present invention relates to a process for the production of polypropylene articles with improved response to a surface energy increasing treatment, wherein the polypropylene comprises a metallocene-catalyzed polyethylene. The present invention further relates to the use of metallocene-catalyzed polyethylene as an additive for improving the response of polypropylene to surface energy increasing treatments.
The technical problem and the prior art
Polypropylene has become one of the most widely used commercial polymers. While its mechanical, chemical and processing properties make it the material of choice in a wide range of applications, its chemical inertness and low surface energy pose problems in applications that require printing, coating, bonding or adhesion with other substrates. For these applications it is therefore necessary to subject the polypropylene to a surface-modifying treatment that increases the surface energy. In printing applications the surface energy needs to be increased from around 30 mN/m to around 38 mN/m for solvent-based inks and to around 45 mN/m for water-based inks. Increasing the surface energy of polypropylene is especially difficult as the energy that is required to increase the surface energy is much higher than for other polymers.
Methods to increase the surface energy of polypropylene include chemical treatment, flame-treatment, and Corona-treatment. For safety and environmental reasons chemical treatment using strong oxidizing agents such
as chromic acid is less and less used. In flame-treatment the polypropylene surface is treated with an oxidizing gas flame. In Corona-treatment the polypropylene surface is treated with air that has been electrically ionized. All methods have in common that oxidized centers are generated, which facilitate the adhesion of inks etc.
A major disadvantage of flame- and Corona-treatment is that the effect of the treatment quickly wears off. Within one week from treating the polypropylene a decay of 3 mN/m may occur. Thus, in many cases the treated polypropylene requires a "refresher" treatment before further transformation.
WO 00/54968 discloses oriented multilayer films comprising a core layer, which comprises syndiotactic polypropylene, and at least one additional layer adjacent to the core layer comprising an ethylene or propylene homopolymer, an ethylene copolymer, a terpolymers containing propylene, ethylene and butene-1 as comonomers, or a blend thereof. The polymer of the additional layer can be produced by Ziegler-Natta catalysis or metallocene catalysis. The oriented multilayer films may be subjected to a treatment that increases the surface energy, such as for example a Corona-treatment. However, WO 00/54968 does not disclose how the response of polypropylene to Corona-treatment could be improved.
WO 2004/098868 discloses a multilayer film which may have a skin layer comprising polypropylene, a filler and a metal locene-catalyzed polyethylene with the metallocene-catalyzed polyethylene having a density in the range from 0.850 g/cm3 to 0.925 g/cm3, thus being a low-density polyethylene. The multilayer film may be subjected to a surface-energy enhancing treatment, e.g. a Corona-treatment, to enhance its printability. However, WO 2004/098868 does not disclose how the susceptibility of polypropylene to Corona-treatment could be increased.
WO 00/58090 discloses multilayer films comprising (a) a core layer, which in turn comprises a propylene polymer, (b) an embossed outer ayer on one side of the core layer, and (c) an additional outer layer on a side of said core layer opposite to said embossed outer layer. The polymer of the embossed outer layer (b) is selected from the group consisting of ethylene-propylene-butylene (EPB) terpolymers, ethylene-propylene (EP) copolymers, metallocene-catalyzed polyethylenes, syndiotactic polypropylenes, propylene-butylene random copolymers, and blends of any of the above components, with or without isotactic polypropylene homopolymer. The embossed outer layer (b) may be flame-treated or Corona-treated. However, WO 00/58090 does not disclose how the performance of polypropylene towards Corona-treatment may be improved.
There is therefore a strong interest in the industry to facilitate the surface modification of polypropylene.
Brief description of the invention
We have now discovered a process that allows the production of polypropylene articles with improved response to surface energy increasing treatments.
Thus, the present invention provides a process for the production of polypropylene articles with improved response to surface energy increasing treatment, said process comprising the steps of (a) providing a polypropylene comprising metallocene-catalyzed polyethylene,
(b) subsequently forming an article, and
(c) subjecting said article to a treatment that increases the surface energy.
Further, the present invention relates to the use of a metallocene-catalyzed polyethylene as surface energy increasing additive.
Detailed description of the invention
The polypropylene used in the present invention can be a homopolymer, random copolymer or heterophasic copolymer. Homopolymer and random copolymer are the preferred polypropylenes. Random copolymer is the most preferred polypropylene. The random copolymer and heterophasic copolymer are copolymers of propylene and at least one comonomer, said comonomer selected from the group consisting of ethylene and C4-CiO alpha-olefins, such as 1 -butene, 1-pentene, 1-hexene, 1-octene.
The random copolymer comprises up to 6 wt%, preferably up to 5 wt% and most preferably up to 4 wt% of at least one comonomer. It comprises at least 0.1 wt%, more preferably at least 0.5 wt%, even more preferably at least 1 wt% and most preferably at least 2 wt% of at least one comonomer. Preferably, the random copolymer is a copolymer of propylene and ethylene.
The heterophasic copolymer comprises a matrix, which in turn is made of propylene homopolymer or random copolymer as defined above, and a rubber phase. The heterophasic copolymer may comprise from 5 wt% to 35 wt% of a rubber phase. Preferably, the heterophasic copolymer is a copolymer of propylene and ethylene. It has an ethylene content in the range from 4 wt% to 15 wt%. Preferably, the rubber phase is an ethylene propylene rubber.
The polypropylene used in the present invention can be produced by polymerizing propylene and one or more optional comonomers according to methods well known to the skilled person.
The polypropylene used in the present invention has a melt flow index in the range from 0.1 dg/min to 100 dg/min (measured according to ISO 1133, condition L, at a temperature of 2300C under a load of 2.16 kg). The person skilled in the art is aware that the suitable melt flow range of the polypropylene depends upon the respective method of forming an article. Thus, for injection
stretch blow molding (ISBM) the preferred melt flow index range is from 1.5 dg/min to 30 dg/min. For cast film extrusion the preferred melt flow index range is from 3.0 dg/min to 15 dg/min. For blown film extrusion the preferred melt flow index range is from 0.3 dg/min to 3.0 dg/min. For blow molding the preferred melt flow index range is from 0.3 dg/min to 3.0 dg/min. For sheet extrusion the preferred range is from 2.0 dg/min to 10 dg/min. For injection molding the preferred range is from 10 dg/min to 100 dg/min..
The polypropylene of the present invention comprises at least 1 wt%, preferably at least 2 wt% of metallocene-catalyzed polyethylene, i.e. a polyethylene that has been produced using a metallocene-based catalytic system. The polypropylene comprises at most 20 wt%, preferably at most 15 wt% and most preferably at most 10 wt% of metallocene polyethylene
The polypropylene comprising metallocene-catalyzed polyethylene can be prepared by dry-blending or compounding. It is also possible to conduct the compounding during the peptization step in a polypropylene production facility.
Blends of polypropylene and metallocene-catalyzed polyethylene are for example known from WO 2005/005143 for improving the impact performance of containers. However, WO 2005/005143 is silent on the use of such compositions for improving the response to surface energy increasing treatments.
The already cited WO 00/54968 does not directly disclose blends of polypropylene and metallocene-catalyst polyethylene for use in Corona- treatment. Neither WO 00/54968 nor WO 2004/098868 discloses that the response of polypropylene to Corona-treatment can be improved by the addition of metallocene-catalyzed polyethylene. The already cited WO 00/58090 does not disclose the improvement in Corona-treatment of polypropylene when a certain amount of metallocene-catalyzed polyethylene is added to the polypropylene.
The metallocene-catalyzed polyethylene can be a homopolymer or copolymer of ethylene and at least one comonomer, said comonomer being a C3 to C10 alpha-olefin, such as 1 -butene, 1 -pentene, 1 -hexene, 1 -octene, 1- methylpentene, with 1 -butene and 1 -hexene being the preferred comonomers and 1 -hexene being the most preferred comonomer.
The metallocene-based catalytic system used to produce the metallocene- catalyzed polyethylene comprises a metallocene, a support and an activating agent. Such metallocene-based catalytic systems are known to the person skilled in the art and need not be explained in detail.
For the purposes of the present invention any known metallocene can be used, such as for example bis(n-butylcyclopentadienyl)zirconium dichloride. It is, however, preferred to use a metallocene of the following general formula
R"(lnd)2 MQq
wherein lnd is an indenyl or a tetrahydroindenyl, substituted or unsubstituted, R" is a structural bridge imparting rigidity between the two indenyls and is a CrC4 alkylene radical, a dialkyl germanium or silicon or siloxane, or a alkyl phosphine or amine radical, preferably Me2C, ethylene, Ph2C or Me2Si; M is a group 4, 5 or
6 transition metal; Q is a hydrocarbyl radical such as aryl, alkyl, alkenyl, alkylaryl, or aryl alkyl radical having from 1 to 20 carbon atoms, hydrocarboxy radical having from 1 to 20 carbon atoms or halogen and can be the same or different from each other; and q is the valence of M minus 2.
Preferably, the indenyls or tetrahydroindenyls, if substituted are symmetrically substituted in positions 2 and/or 4, and more preferably they are unsubstituted.
Such metallocene components are disclosed in WO 96/35729. The most preferred metallocene is ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride.
The molecular weight distribution of the metallocene-catalyzed polyethylene can be defined by a parameter known as the dispersion index D, which is the ratio between the average molecular weight by weight (Mw) and the average molecular weight by number (Mn). The dispersion index D constitutes a measure of the width of the molecular weight distribution. For the metallocene- catalyzed polyethylene of the present invention the dispersion index D is from 2 to 7, preferably from 2 to 5.
The metallocene-catalyzed polyethylene used in the present invention has a melt flow index in the range from 0.1 dg/min to 100 dg/min (measured according to ISO 1133, condition D, at a temperature of 1900C and a load of 2.16 kg). The person skilled in the art is aware that the suitable melt flow range of the polyethylene depends upon the respective method of forming an article. Thus, for injection stretch blow molding (ISBM) the preferred melt flow index range is from 1.5 dg/min to 30 dg/min. For cast film extrusion the preferred melt flow index range is from 3.0 dg/min to 15 dg/min. For blown film extrusion the preferred melt flow index range is from 0.3 dg/min to 3.0 dg/min. For blow molding the preferred melt flow index range is from 0.3 dg/min to 3.0 dg/min. For sheet extrusion the preferred range is from 2.0 dg/min to 10 dg/min. For injection molding the preferred range is from 10 dg/min to 100 dg/min.
The metallocene-catalyzed polyethylene used in the present invention has a density of at least 0.920 g/cm3, preferably of at least 0.925 g/cm3, more preferably of at least 0.927 g/cm3, even more preferably of at least 0.930 g/cm3 and most preferably of at least 0.932 g/cm3. It has a density of at most 0.965 g/cm3, preferably of at most 0.955 g/cm3, more preferably of at most 0.950 g/cm3, even more preferably of at most 0.945 g/cm3, and most preferably of at
most 0.940 g/cm3. The density is measured at 23°C following the method described in ASTM D 1505.
Without wishing to be bound by theory, it is believed that the amount of crystallization plays a role in the compatibility between polypropylene and metallocene-catalyzed polyethylene, when measured at high temperature or at low equivalent Short Chain Branches (SCB) content. The amount of crystallization as a function of short chain branches is determined by the Stepwise Isothermal Segregation Technique (SIST). In this technique, the sample is heated from room temperature (25 0C) to 220 0C at a rate of 200 °C/min. It is kept at 220 0C for 5 minutes. It is then dropped to the temperature of 140 0C at a rate of 20 °C/min and kept at that temperature for 40 minutes. The temperature is then dropped by steps of 5 0C at a rate of 20 °C/min and kept at each step for 40 minutes until the temperature of 90 0C is reached. It is then allowed to cool down to 25 0C at the fastest cooling rate and maintained at 25 0C for 3 minutes. It is next reheated from 25 0C to 180 0C at a rate of 5 °C/min. The percentage of crystallization is deduced from the curve representing the SCB as a function of melting temperature following the method described by Satoru Hosada in Polymer Journal, vol. 20, p. 383, 1988. In the metallocene-catalyzed polyethylene used in the present invention, the percentage of crystallization corresponding to chains having less than 10 SCB for 1000 carbon atoms is at least 4 %, preferably it is at least 7 %.
Both, the polypropylene as well as the metallocene-catalyzed polyethylene may contain additives such as, by way of example, antioxidants, light stabilizers, acid scavengers, lubricants, antistatic additives, nucleating/clarifying agents, colorants, slip agents. An overview of such additives may be found in Plastics Additives Handbook, ed. H. Zweifel, 5th edition, 2001 , Hanser Publishers.
Using the polypropylene comprising metallocene-catalyzed polyethylene according to the present invention articles may be formed by any known transformation method, such as for example injection molding, blow molding,
injection stretch blow molding (ISBM), cast or blown film extrusion, fiber or nonwoven extrusion, sheet extrusion.
Following their production the polypropylene articles are subjected to a surface energy increasing treatment, such as for example chemical treatment, flame- treatment and Corona-treatment. The preferred methods are flame- and Corona-treatment. The most preferred method is Corona-treatment.
For Corona-treating the polypropylene articles are passed between two electrodes with a voltage usually in the range from about 10 kV to about 20 kV. At such voltages spray or corona discharge can occur, which then causes the air above the article to ionize and react with the surface molecules of the polypropylene article, thus forming polar centers.
For flame treatment with a polarized flame an electrical voltage is applied between a burner, serving as the negative pole, and another element, for example a chill roll in film or sheet extrusion. The applied voltage is in the range from about 0.5 kV to about 3 kV. It causes an acceleration of ionized atoms, which hit the polypropylene surface at great speed and then break bonds on the surface of the polypropylene article. In consequence, polar centers are created.
The polypropylene comprising metallocene-catalyzed polyethylene has been found to be more responsive to surface energy increasing treatments. Very surprisingly, the polypropylene of the present invention has also been found to have a slower decay of the effects of the surface-modifying treatment. Compared to surface energy enhanced articles made from pure polypropylene, the polypropylene articles comprising metallocene-catalyzed polyethylene can be stored for a longer period of time before further transformation, e.g. printing, without having to undergo a "refresher" treatment.
Thus, the metallocene-catalyzed polyethylene serves as an additive in polypropylene for improving the response to surface energy increasing
treatments, such as for example chemical treatment, flame-treatment and Corona-treatment. The preferred methods are flame- and Corona-treatment. The most preferred method is Corona-treatment.
Claims
1. Process for the production of polypropylene articles with improved response to surface energy increasing treatment, said process comprising the steps of
(a) providing a polypropylene comprising metallocene-catalyzed polyethylene,
(b) subsequently forming an article, and
(c) subjecting said article to a treatment that increases the surface energy, wherein the polypropylene in step provided in step (a) comprises from 1 wt% to 20 wt% of metallocene-catalyzed polyethylene..
2. The process according to claim 1 , wherein the polypropylene comprises from 2 wt% to 15 wt%, of metallocene-catalyzed polyethylene.
3. The process according to any of the preceding claims, wherein the density of the metallocene-catalyzed polyethylene is at least 0.920 g/cm3, preferably at least 0.925 g/cm3, 0.927 g/cm3, 0.930 g/cm3 or 0.932 g/cm3 as measured at 23°C according to ASTM D 1505.
4. The process according to any of the preceding claims, wherein the density of the metallocene-catalyzed polyethylene is at most 0.965 g/cm3, preferably at most 0.955 g/cm3, 0.950 g/cm3, 0.945 g/cm3, or 0.940 g/cm3 as measured at 23°C according to ASTM D 1505.
5. The process according to any of the preceding claims, wherein the metallocene-catalyzed polyethylene has a percentage of crystallization corresponding to chains having less than 10 short chain branches per 1000 carbon atom of at least 4 %, preferably at least 7 %.
6. The process according to claim 1 , wherein the surface energy increasing treatment of step (c) is a Corona-treatment or a flame-treatment.
7. The process according to any of the preceding claims, wherein in step (b) the polypropylene articles is formed by a method selected from the group consisting of injection stretch blow molding, cast film extrusion, blown film extrusion, sheet extrusion and injection molding.
8. Use of a metallocene-catalyzed polyethylene as an additive for improving the response of polypropylene to surface energy increasing treatments.
9. Use of a metallocene-catalyzed polyethylene according to claim 8, wherein the metallocene-catalyzed polyethylene is added to the polypropylene in an amount of from 1 wt% to 20 wt%.
10. Use of a metallocene-catalyzed polyethylene according to claim 8 or claim 9, wherein the density of the metallocene-catalyzed polyethylene is at least 0.920 g/cm3, preferably at least 0.925 g/cm3, 0.927 g/cm3, 0.930 g/cm3 or 0.932 g/cm3 as measured at 23°C according to ASTM D 1505.
11. Use of a metallocene-catalyzed polyethylene according to any of claims 8 to 10, wherein the density of the metallocene-catalyzed polyethylene is at most 0.965 g/cm3, preferably at most 0.955 g/cm3, 0.950 g/cm3, 0.945 g/cm3 or 0.940 g/cm3 as measured at 23°C according to ASTM D 1505.
12. Use of a metallocene-catalyzed polyethylene according to any of claims 8 to 11 , wherein the metallocene-catalyzed polyethylene has a percentage of crystallization corresponding to chains having less than 10 short chain branches per 1000 carbon atom of at least 4 %, preferably at least 7 %.
13. Polypropylene articles made according to the process of any of claims 1 to 7.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010512699A JP2010530460A (en) | 2007-06-21 | 2008-06-20 | Method for producing polypropylene article having increased responsiveness to surface energy increase treatment |
| US12/664,456 US20100261016A1 (en) | 2007-06-21 | 2008-06-20 | Process for the Production of Polypropylene Articles with Increased Response to surface Energy Increasing Treatment |
| CN200880020717A CN101678579A (en) | 2007-06-21 | 2008-06-20 | Process for the production of polypropylene articles with increased response to surface energy increasing treatment |
| KR1020097025878A KR101168191B1 (en) | 2007-06-21 | 2008-06-20 | Process for the production of polypropylene articles with increased response to surface energy increasing treatment |
| EP08761261A EP2158072A1 (en) | 2007-06-21 | 2008-06-20 | Process for the production of polypropylene articles with increased response to surface energy increasing treatment |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP07110775A EP2014438A1 (en) | 2007-06-21 | 2007-06-21 | Process for the production of polypropylene articles with increased response to surface energy increasing treatment |
| EP07110775.9 | 2007-06-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2008155404A1 true WO2008155404A1 (en) | 2008-12-24 |
Family
ID=38611096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2008/057847 WO2008155404A1 (en) | 2007-06-21 | 2008-06-20 | Process for the production of polypropylene articles with increased response to surface energy increasing treatment. |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20100261016A1 (en) |
| EP (2) | EP2014438A1 (en) |
| JP (1) | JP2010530460A (en) |
| KR (1) | KR101168191B1 (en) |
| CN (1) | CN101678579A (en) |
| WO (1) | WO2008155404A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3031853A1 (en) | 2014-12-12 | 2016-06-15 | Borealis AG | Polypropylene films with improved printability |
| US10385197B2 (en) | 2014-12-12 | 2019-08-20 | Borealis Ag | Polypropylene films with improved sealing behaviour, especially in view of improved sealing properties |
| EP3967716A1 (en) | 2020-09-11 | 2022-03-16 | Borealis AG | Polypropylene-based article having an increased surface tension retention |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2532600B1 (en) * | 2011-06-06 | 2020-01-22 | Kuraray Europe GmbH | Plastic containers with gas barrier coating and optionally hydrophilic inside coating |
| US20150252066A1 (en) * | 2012-09-28 | 2015-09-10 | Clairant Finance (Bvi) Limited | Process For Preparing A Polypropylene-Based Object Having An Increased Surface Energy |
| CN104070663B (en) * | 2014-06-27 | 2017-04-05 | 广州金发绿可木塑科技有限公司 | The technique that continuous fiber strengthens wood plastic product |
| US9827705B2 (en) * | 2015-04-16 | 2017-11-28 | The Procter & Gamble Company | High gloss high density polyethylene containers |
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| WO2000054968A1 (en) * | 1999-03-17 | 2000-09-21 | Mobil Oil Corporation | Multi-layer film with core layer of syndiotactic polypropylene |
| WO2000058090A1 (en) | 1999-03-30 | 2000-10-05 | Mobil Oil Corporation | Polyolefin film with embossed surface |
| WO2004098868A2 (en) * | 2003-05-01 | 2004-11-18 | Avery Dennison Corporation | Multilayered film |
| EP1495861A1 (en) * | 2003-07-10 | 2005-01-12 | Total Petrochemicals Research Feluy | High transparency, high impact resistance containers |
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| DE69024040T2 (en) * | 1990-03-23 | 1996-07-18 | Agfa Gevaert Nv | Laminated product. |
| JP3733667B2 (en) * | 1996-11-27 | 2006-01-11 | 三菱化学株式会社 | Propylene resin thermoformed product manufacturing method and thermoformed product |
| JP3702628B2 (en) * | 1997-12-15 | 2005-10-05 | 三菱化学エムケーブイ株式会社 | Film for decorative sheet |
| US7371465B2 (en) * | 1999-03-30 | 2008-05-13 | Exxonmobil Oil Corporation | Polyolefin film with embossed surface |
| US6432527B1 (en) * | 1999-12-14 | 2002-08-13 | 3M Innovative Properties Company | Embossed film having controlled tear |
| US7537829B2 (en) * | 2001-02-22 | 2009-05-26 | Exxonmobil Oil Corporation | Multi-layer films having improved sealing properties |
-
2007
- 2007-06-21 EP EP07110775A patent/EP2014438A1/en not_active Withdrawn
-
2008
- 2008-06-20 WO PCT/EP2008/057847 patent/WO2008155404A1/en active Application Filing
- 2008-06-20 JP JP2010512699A patent/JP2010530460A/en active Pending
- 2008-06-20 KR KR1020097025878A patent/KR101168191B1/en not_active IP Right Cessation
- 2008-06-20 US US12/664,456 patent/US20100261016A1/en not_active Abandoned
- 2008-06-20 EP EP08761261A patent/EP2158072A1/en not_active Withdrawn
- 2008-06-20 CN CN200880020717A patent/CN101678579A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000054968A1 (en) * | 1999-03-17 | 2000-09-21 | Mobil Oil Corporation | Multi-layer film with core layer of syndiotactic polypropylene |
| WO2000058090A1 (en) | 1999-03-30 | 2000-10-05 | Mobil Oil Corporation | Polyolefin film with embossed surface |
| WO2004098868A2 (en) * | 2003-05-01 | 2004-11-18 | Avery Dennison Corporation | Multilayered film |
| EP1495861A1 (en) * | 2003-07-10 | 2005-01-12 | Total Petrochemicals Research Feluy | High transparency, high impact resistance containers |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3031853A1 (en) | 2014-12-12 | 2016-06-15 | Borealis AG | Polypropylene films with improved printability |
| US10385197B2 (en) | 2014-12-12 | 2019-08-20 | Borealis Ag | Polypropylene films with improved sealing behaviour, especially in view of improved sealing properties |
| US10385196B2 (en) | 2014-12-12 | 2019-08-20 | Borealis Ag | Polypropylene films with improved printability |
| EP3967716A1 (en) | 2020-09-11 | 2022-03-16 | Borealis AG | Polypropylene-based article having an increased surface tension retention |
| WO2022053475A1 (en) | 2020-09-11 | 2022-03-17 | Borealis Ag | Polypropylene-based article having an increased surface tension retention |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101168191B1 (en) | 2012-07-25 |
| EP2014438A1 (en) | 2009-01-14 |
| US20100261016A1 (en) | 2010-10-14 |
| KR20100005246A (en) | 2010-01-14 |
| CN101678579A (en) | 2010-03-24 |
| JP2010530460A (en) | 2010-09-09 |
| EP2158072A1 (en) | 2010-03-03 |
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