Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
  • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
  • C09J123/10—Homopolymers or copolymers of propene
• • E—FIXED CONSTRUCTIONS
  • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
  • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
  • E06B1/00—Border constructions of openings in walls, floors, or ceilings; Frames to be rigidly mounted in such openings
  • E06B1/04—Frames for doors, windows, or the like to be fixed in openings
  • E06B1/36—Frames uniquely adapted for windows
  • E06B1/363—Bay windows
• • 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
• • 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
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
  • C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • 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
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
  • Y10T428/24917—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including metal layer
• • 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
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31678—Of metal

Definitions

• the present invention relates to the field of packaging using in particular multilayer films, bi-oriented or not, metallized and laminated with a film of polypropylene bi-oriented (abbreviated BOPP) or polyethylene terephthalate bi-oriented (abbreviated BOPET) or not, having very good adhesion of the layers to each other even when the films are weakened by welding.
• BOPP polypropylene bi-oriented
• BOPET polyethylene terephthalate bi-oriented
• the invention applies, inter alia, to packaging of the sachets, bags, pockets or packages type made from these welded films, the composition of which generates good manual opening of the packaging. Mention may be made, without limitation, for example, of packets of crisps, cookies, candies, meat.
• the films constituting the packaging must have oxygen and water vapor barrier properties in order to preserve the foodstuffs, solid or liquid, food or the like, which are inside the packaging. .
• the Applicant has now found a film having a strong adhesion between a metallic layer and a layer having a composition based (i) mainly on polypropylene, (ii) on the minority of a mixture of either co-grafted polyethylenes (abbreviated PEg), or polyethylene and cografted polypropylene and (iii) optionally polyethylene or ungrafted elastomer.
• This film allows inter alia the manufacture of packages closed by a sealing strip of said film, the opening taking place at the same strip.
• the packaging according to the invention opens cleanly at the weld strip without damage to the multilayer structure otherwise.
• the subject of the invention is a binder comprising: - 5 to 50% by weight of a mixture (A), said mixture (A) comprising:
• a mixture of polymers (C1) and (C2) consisting of 90 to 20% by weight of a metallocene polyethylene (C1) with a density between 0.865 and 0.915 and from 10 to 80% by weight of a polymer (C2) which is either a non-metallocene LLDPE or a homo- or copolymerized polypropylene, the mixture of polymers (C1) and (C2) consisting of 90 to 20% by weight of a metallocene polyethylene (C1) with a density between 0.865 and 0.915 and from 10 to 80% by weight of a polymer (C2) which is either a non-metallocene LLDPE or a homo- or copolymerized polypropylene, the mixture of polymers (C1) and
• ⁇ the content of grafted grafting monomer is between 30 and 10 5 ppm; o the MFI or melt flow index (ASTM D 1238 standard, at 190 ° C under 2.16 kg) is between 0, 1 and 30g / 10min - 50 to 95% by weight of a polypropylene ( B) homo or copolymer.
• the invention also relates to a multilayer structure comprising a binder layer as defined above.
• the multilayer structure comprises a metal layer bonded to the binder layer.
• the structure is characterized in that the metal layer is a layer of Al, Fe, Cu, Sn, Ni, Ag, Cr, Au or an alloy containing minus one of these metals mainly.
• the multilayer structure is characterized in that it comprises a layer of polypropylene homopolymer or copolymer, the layer of binder being sandwiched between the metal layer and said layer of polypropylene.
• the multilayer structure is characterized in that it comprises a layer suitable for thermocell comprising either an Ethylene / Propylene / Butylene terpolymer, or an Ethylene / Propylene copolymer or a metallocene PE or their mixtures in this case said mixture includes at least two of the previously listed compounds, the polypropylene being sandwiched between the binder layer and said layer suitable for thermocell
• the invention further relates to a film comprising a multilayer structure as defined above.
• the film is characterized in that it comprises a layer of bi-oriented polypropylene (BOPP) or of bi-oriented polyethylene terephthalate. (BOPET) printed, on which is applied with an adhesive a metallized multilayer film comprising a structure described above, said film being bi-oriented or not and the metal layer of said metallized multilayer film being directly bonded by adhesive to the printed BOPP or BOPET layer
• the invention also relates to the use of the binder to manufacture a multilayer structure defined above.
• the invention relates to an object comprising a multilayer structure as described above
• the object is manufactured with a film as previously described
• the object is a packaging
• FIG. 1 represents an embodiment of a film according to the invention, said metallized cast polypropylene film (abbreviated MCPP) comprising a structure with layers from 1 to A succeeding one another in the following order 'a layer (1) of metal, a layer (2) of mixture of co-grafted PE and LLDPE, of LLDPE and of homo or copolymer PP, a layer (3) of homopolymer or copolymer PP and a layer (A) of polymer suitable for thermocell.
• MCPP metallized cast polypropylene film
• Figure 2 shows in cross section a bag (6) closed by a weld strip (5a), according to the prior art cited above, after a failed opening attempt, said bag being made with a film comprising the following structure a layer (1 1) of metal, a layer (12) of a mixture of syndiotactic PP and butylene / propylene copolymer or of a mixture of syndiotactic PP and homo PP or graft copolymer, a layer (13) of homo PP or copolymer, a layer (14) of ethylene / propylene / butylene terpolymer or of ethylene / propylene copolymer or of metallocene PE.
• FIG. 1 shows in cross section a bag (6) closed by a weld strip (5a), according to the prior art cited above, after a failed opening attempt, said bag being made with a film comprising the following structure a layer (1 1) of metal, a layer (12) of a mixture of syndio
• the packaging, objects of the invention includes a metallized cast PP film (abbreviated as MCPP).
• MCPP metallized cast PP film
• This film can enter into a structure of the type: BOPP or BOPET layer / ink layer / adhesive layer / MCPP film.
• the MCPP film comprises a multilayer structure shown in FIG. 1 and having the following form: layer (1) / layer (2) / layer (3) / layer (4), the composition of which will be given below.
• the layer (1) is a metallic layer applied to a layer (2). It can for example be a sheet or a film of a metal such as Ai, Fe, Cu, Sn, Ni, Ag, Cr, Au or an alloy containing at least one of these metals mainly.
• the layer (3) is a layer of PP.
• the polypropylene of layer (3) can be a homopolymer or a copolymer.
• a comonomer we can cite:
• Alpha olefins advantageously those having from 2 to 30 carbon atoms such as ethylene, 1 -butene, 1 -pentene, 3-methyl-1 -butene, 1 -hexene, 4-methyl- 1 -pentene, 3-methyl-1 -pentene, 1-octene, 1 - decene, 1 -dodecene, 1 -tetradecene, 1 -hexadecene, 1 -octadecene, 1 - eicocene, 1 -dococene, 1 -tetracocene, 1 -hexacocene, 1 -octacocene and 1 triacontene.
• the polypropylene can also be a polypropylene block copolymer.
• the layer (3) comprises a mixture of several polymers in which there is at least one polypropylene comprising at least 50% by moles and preferably at least 75% of propylene.
• the polypropylene of the layer (3) can be a mixture of polypropylene and EPDM or EPR.
• homopolymer PP mention may be made of isotactic PP between 80 and
• the polypropylene homopolymer preferably has an MFI (melt flow index) of between 1, 2 and 30 g / 10 min, preferably between 3 and 8 g / 10 min measured according to ASTM D1 38.
• the layer (4) is a layer suitable for thermocell. It may for example comprise an Ethylene / Propylene / Butylene terpolymer, an Ethylene / Propylene copolymer, a metallocene PE or their mixtures (mixture of at least two of the compounds previously listed).
• the layer (4) comprises a terpolymer mainly comprising propylene as a comonomer.
• the layer (2) is produced with a mixture comprising: - 5% to 50%, preferably 20 to 40% by weight of a mixture (A) and
• the mixture (A) being 95 to 0% by weight (relative to the mixture (A)) of a polyethylene (D) chosen from homo or copolymer polyethylenes and elastomers; the mixture (A) being such that: the content of grafted grafting monomer is between 30 and 10 5 ppm; the MFI or melt flow index (ASTM D 1238 standard, at 190 ° C under 2.16 kg) is between 0.1 and 30g / 10min.
• a polyethylene (D) chosen from homo or copolymer polyethylenes and elastomers
• metallocene polyethylene denotes the polymers obtained by copolymerization of ethylene and alpha olefin such as, for example, propylene, butene, hexene or octene in the presence of a monosite catalyst generally consisting of a atom of a metal which may for example be zirconium or titanium and two cyclic alkyl molecules linked to the metal. More specifically, metallocene catalysts are usually composed of two cyclopentadienic rings linked to the metal. These catalysts are frequently used with aluminoxanes as cocatalysts or activators, preferably methylaluminoxane (MAO). Hafnium can also be used as the metal to which cyclopentadiene is attached. Other metallocenes may include transition metals from groups IVA, VA and VIA. Metals from the lanthanide series can also be used.
• the density of (C1) is between 0.870 and 0.900.
• the polymer (C2) is either a copolymer of ethylene and of an alpha-olefin of the LLDPE type (linear low density polyethylene) which is not of metallocene origin is a homo- or polyptopylene. copolymer with as conrion ⁇ mâ for example alpha-olefins or dienes.
• the polymer (C2) can also be a polypropylene block copolymer.
• the alpha-olefins advantageously have from 3 to 30 carbon atoms.
• alpha-olefins having 3 to 30 carbon atoms include ethylene (only PP comonomer), propylene (only PE comonomer), 1-butene, 1 -pentene, 3-methyl-1 - butene, 1-hexene, 4-methyl-1 -pentene, 3-methyl-1 -pentene, 1-octene, 1-decene, 1-dodecene, 1 -tetradecene, 1 -hexadecene , 1-octadecene, 1-eicocene, 1 -dococene, 1 -tetracocene, I hexacocene, 1 -octacocene and 1 -triacontene.
• These alpha olefins can be used alone or as a mixture of two or more than two.
• the density of (C2) is advantageously between 0.900 and 0.950.
• the MFI of (C2) is between 0.1 and ⁇ g / 10 min (at 190 ° C under 2.1 6 kg).
• the mixture (C1) and (C2) is grafted with a grafting monomer taken from the group of unsaturated carboxylic acids or their functional derivatives.
• unsaturated carboxylic acids are those having 2 to 20 carbon atoms such as acrylic, methacrylic, maleic, fumaric and itaconic acids.
• the functional derivatives of these acids include, for example, anhydrides, ester derivatives, amide derivatives, imide derivatives and metal salts (such as alkali metal salts) of unsaturated carboxylic acids.
• the unsaturated dicarboxylic acids having 4 to 10 carbon atoms and their functional derivatives, particularly their anhydrides, are particularly preferred grafting monomers.
• grafting monomers include, for example, maleic, fumaric, itaconic, citraconic, allylsuccinic, cyclohex-4-ene-1, 2-dicarboxylic, 4-methylcyclohex-4-ene-1, 2-dicarboxylic, bicyc!
• Examples of other grafting monomers include:
• C1 to C8 alkyl esters or glycidyl ester derivatives of unsaturated carboxylic acids such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, monoethyl maleate, diethyl maleate, monomethyl fumarate, dimethyl fumarate, monomethyl itaconate and diethyl itaconafe;
• Amide derivatives of unsaturated carboxylic acids such as acrylamide, methacrylamide, maleic monoamide, maleic diamide, maleic N-monoethylamide, maleic N, N-diethylamide, maleic N-monobutylamide, N, N- maleic dibutylamide, fumaric monoamide, fumaric diamide, fumaric N-monoethylamide, N, fumaric N-diethylamide, fumaric N-monobutylamide and fumaric N, N-dibutylamide; o imide derivatives of unsaturated carboxylic acids such as mayeimide, N-butylmaleimide and N-phenylmaleimide; and o metal salts of unsaturated carboxylic acids such as sodium acrylate, sodium methacrylate, potassium acrylate and potassium methacrylate.
• graft a grafting monomer to the mixture of (C1) and (C2).
• the amount of grafting monomer is chosen appropriately and is between 0.01 to 10%, preferably between
• the amount of the grafted monomer is determined by assaying the functions succinics by IRTF spectroscopy.
• the MFI of (C), that is to say of (C1) and (C2) co-grafted is advantageously 0.1 to 10 g / 10 min.
• Polyethylene (D) it is a polyethylene homopolymer or a copolymer of ethylene with as comonomer a monomer chosen from the alphaolefins defined above for (C2), esters of unsaturated carboxylic acids or vinyl esters saturated carboxylic acids.
• the esters of unsaturated carboxylic acids are, for example, alkyl (meth) acrylates, the alkyl of which has from 1 to 24 carbon atoms. Examples of alkyl acrylate or methacrylate are in particular methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate.
• the vinyl esters of saturated carboxylic acids are, for example, vinyl acetate or propionate.
• the polyethylene (D) can be a high density PE (HDPE), a low density PE (LDPE), a linear low density PE (LLDPE), a very low density PE (VLDPE) or a metallocene PE.
• HDPE high density PE
• LDPE low density PE
• LLDPE linear low density PE
• VLDPE very low density PE
• metallocene PE metallocene PE
• Polyethylene (D) can also be an elastomeric polymer, that is to say it can be (i) an elastomer within the meaning of ASTM D412, which means a material which can be stretched at room temperature twice its length, thus maintained for 5 minutes then return to less than 10% near its initial length after being released or (ii) a polymer not having exactly the preceding characteristics but which can be stretched and return substantially to its initial length.
• ASTM D412 ASTM D412
• SBR styrene butadiene rubber
• SBS block copolymers styrene butadiene styrene
• SEBS block copolymers styrene ethylene butadiene styrene
• SIS block copolymers styrene isoprene styrene
• the polyethylene (D) is an LLDPE of density between 0.900 and 0.935 or else a HDPE of density between 0.935 and 0.950.
• the proportions in the mixture (A) of polymers (C) and (D) are respectively 10 to 30% by weight of (C) for 90 to 70% by weight of (D).
• the polymer (B) in which the mixture (A) is diluted it is a PP copolymer or terpolymer Propylene / Ethylene / Butylene.
• a comonomer we can cite:
• alpha olefins advantageously those having from 2 to 30 carbon atoms such as ethylene, 1 -butene, 1 -pentene, 3-methyl-1 -butene, 1 -hexene, 4-methyl- 1 -pentene, 3-methyl-1 -pentene, 1-octene, 1 - decene, 1 -dodecene, 1 -tetradecene, 1 -hexadecene, 1 -octadecene, 1 - eicocene, 1 -dococene, 1 -tetracocene, 1 -hexacocene, 1-octacocene and 1 triacontene.
• alpha olefins can be used alone or as a mixture of two or more than two.
• the polypropylene can also be a polypropylene block copolymer.
• the polymer (B) comprises a mixture of several polymers in which there is at least one polypropylene comprising at least 50% by moles and preferably at least 75% of propylene.
• the polymer (B) can be a mixture of polypropylene and EPDM or EPR.
• the layers (1), (2), (3) and (4) can have a thickness between 50 and 500 angstroms for the layer (1), between 2 and 6 ⁇ m for the layer (2), between 5 and 30 ⁇ m for the layer (3) and between 2 and 10 ⁇ m for the layer (4).
• the layers (2), (3) and (4) can be laminated together by a coextrusion process before the application of the metal layer (1).
• the layer (1) can be applied by vapor deposition using a technique well known to those skilled in the art, preferably it is deposited under vacuum.
• the metal layer (1) constitutes a good barrier to oxygen and water vapor.
• compositions of layers (2), (3) and (4) can contain the additives usually used during the processing of polyolefins at contents of between 10 ppm and 5% such as antioxidants based on substituted phenolic molecules, UV protective agents, processing agents such as fatty amides, stearic acid and its salts, fluoropolymers known as agents for preventing extrusion defects, anti-fogging agents based on amines , anti-blocking agents such as silica or talc, masterbatches with dyes and nucleating agents.
• Figs. 2 and 3 allow the result of the invention to be clearly seen in relation to the prior art.
• the bags represented in these figures are similar to packets of chips comprising firstly a pocket delimited by a multilayer structure (1 1, 12, 13, 14) in the case of Fig. 2 and a multilayer structure (1 , 2, 3, 4) in the case of Fig.3, the metal layer (1) or (1 1) being in contact with the outside of the pocket while the layer (4) or (14) is in contact with the inside of the pocket.
• the two bags or packages are closed by a weld strip (5a) of the multilayer film which constitutes them, the layer (4) or (14) of each weld edge (5b) delimiting the opening of the bags (6) being welded on herself.
• Film samples from 1 to 8 are produced (see TABLE 1 below) comprising a multilayer structure of the BOPP type (substantially 20 ⁇ m) / ink layer / liquid adhesive layer / MCPP film (substantially 25 ⁇ m).
• the MCPP film is a 4-layer structure, as shown in Fig. 1, respectively:
• the layers (1), (3) and (4) are the same for samples 1 to 8. Only the layer (2) differs by the proportions X and Y expressed in% by weight. We then make sealed sachets and then measure the peel strength in g / 15mm. It is noted that for the compositions comprising 5 to 50% of mixture

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Civil Engineering (AREA)
• Structural Engineering (AREA)
• Laminated Bodies (AREA)
• Wrappers (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Applications Claiming Priority (3)

Publications (1)

Family

ID=32731865

Family Applications (1)

Country Status (17)

Families Citing this family (25)

Family Cites Families (28)

• 2003
  • 2003-02-07 FR FR0301458A patent/FR2850975B1/fr not_active Expired - Fee Related
• 2004
  • 2004-02-06 WO PCT/FR2004/000283 patent/WO2004072200A2/fr active Application Filing
  • 2004-02-06 EP EP04708790A patent/EP1606367A2/fr not_active Withdrawn
  • 2004-02-06 CA CA 2456668 patent/CA2456668C/fr not_active Expired - Fee Related
  • 2004-02-07 CN CNB2004100300892A patent/CN100523108C/zh not_active Expired - Fee Related
  • 2004-02-07 SG SG200400575A patent/SG115614A1/en unknown
  • 2004-02-07 MY MYPI20040369A patent/MY140678A/en unknown
  • 2004-02-07 KR KR1020040008168A patent/KR100629668B1/ko not_active IP Right Cessation
  • 2004-02-08 IL IL160279A patent/IL160279A/en not_active IP Right Cessation
  • 2004-02-09 AU AU2004200499A patent/AU2004200499B2/en not_active Ceased
  • 2004-02-09 TW TW93102928A patent/TW200426024A/zh unknown
  • 2004-02-09 US US10/773,451 patent/US20080131672A1/en not_active Abandoned
  • 2004-02-09 NO NO20040574A patent/NO20040574L/no not_active Application Discontinuation
  • 2004-02-09 NZ NZ531048A patent/NZ531048A/en not_active IP Right Cessation
  • 2004-02-09 MX MXPA04001232A patent/MXPA04001232A/es active IP Right Grant
  • 2004-02-09 BR BRPI0401000 patent/BRPI0401000A/pt not_active IP Right Cessation
  • 2004-02-09 JP JP2004032492A patent/JP2004263171A/ja active Pending
• 2006
  • 2006-04-04 JP JP2006103526A patent/JP2006299258A/ja active Pending

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events