EP1051298A1 - Folie zum einwickeln von objekten - Google Patents

Folie zum einwickeln von objekten

Info

Publication number
EP1051298A1
EP1051298A1 EP99900945A EP99900945A EP1051298A1 EP 1051298 A1 EP1051298 A1 EP 1051298A1 EP 99900945 A EP99900945 A EP 99900945A EP 99900945 A EP99900945 A EP 99900945A EP 1051298 A1 EP1051298 A1 EP 1051298A1
Authority
EP
European Patent Office
Prior art keywords
film
polyester
assembly according
mole
layers
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.)
Withdrawn
Application number
EP99900945A
Other languages
English (en)
French (fr)
Inventor
Daniel Meilhon
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.)
Soplaril SA
Original Assignee
Soplaril SA
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 Soplaril SA filed Critical Soplaril SA
Publication of EP1051298A1 publication Critical patent/EP1051298A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D75/00Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes, or webs of flexible sheet material, e.g. in folded wrappers
    • B65D75/04Articles or materials wholly enclosed in single sheets or wrapper blanks
    • B65D75/06Articles or materials wholly enclosed in single sheets or wrapper blanks in sheets or blanks initially folded to form tubes
    • B65D75/10Articles or materials wholly enclosed in single sheets or wrapper blanks in sheets or blanks initially folded to form tubes with the ends of the tube closed by twisting
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion 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
    • B29C48/09Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B29C48/10Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/36Layered products comprising a layer of synthetic resin comprising polyesters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001Combinations of extrusion moulding with other shaping operations
    • B29C48/0018Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion 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
    • B29C48/07Flat, e.g. panels
    • B29C48/08Flat, e.g. panels flexible, e.g. films

Definitions

  • the invention relates to an assembly comprising a solid and its packaging, said packaging comprising at least one film comprising at least one foil and / or a fold, said film comprising at least one layer comprising at least one polyester.
  • the invention relates directly to the field of packaging food materials such as candies such as chocolates, candies, boiled or caramel sugars, "chewing gum", lollipops, but also that of any other solid object "' such as soaps, cheeses in portions, culinary additives in doses such as broths in cubes
  • Figures 1 and 2 show, by way of example, candies after wrapping in the context of the present invention.
  • the packaging in question in the present application can therefore be a film directly marrying most, if not almost all, of the surface of the packaged solid, the latter generally being made up of a single element (as opposed for example to a powder made up of several elements in the form of particles), as is the case for example for a candy.
  • the assembly may include
  • the candies can be wrapped using polyvinyl chloride (PVC) or cellophane films.
  • PVC polyvinyl chloride
  • Cellophane is made by a complex process making it expensive and its producers are fewer and fewer. There is therefore a need for substitutes for these two materials, in particular in the field of films for wrapping solid objects such as candies.
  • a film suitable for wrapping a solid must meet several technical criteria.
  • the film must be suitable for wrapping, that is to say " it must keep the shape which was given to it during wrapping with the lowest possible tendency to return to its shape d origin, that is to say of flat film.
  • This property makes it possible to avoid having to use an adhesive or a glue, for example at the level of the tightest zone of a foil, that is to say that is, between the packaged solid and the foil itself, to keep the package in the shape it has been given.
  • a film for wrapping solid objects must also be easy to handle by the machines responsible for wrapping said objects, from which the highest possible rates are expected, for example 50 to 1500 objects wrapped per minute and per machine.
  • the film must therefore also be easy to cut. Indeed, before wrapping an object, it is necessary to cut the surface of film useful for wrapping said object, generally from a reel of said film.
  • the film, before wrapping the object, before and after mechanical cutting, must remain flat and must not show any tendency to roll up on itself. Indeed, such a trend could disrupt the production chain and lead to its blocking.
  • the film may have to have a good gloss and / or suitable transparency, and / or good suitability for food contact and / or satisfactory organoleptic properties.
  • the film must be able to exhibit good printability and / or metallization.
  • the film must also be easy to manufacture from its basic materials.
  • a single-material film made of biaxially oriented high density polyethylene or biaxially oriented polypropylene does not satisfactorily meet the specifications of the application in particular because its capacity for wrapping is low.
  • the film according to the invention addresses the above-mentioned problems.
  • the film according to the invention makes it possible to package a solid by a package comprising at least one foil and / or a fold without the need for an adhesive or glue.
  • the film according to the invention allows the production of a packaging kept closed around an object by the mere production of at least one foil (also called "stranding") and / or at least one fold, without it do not necessarily need to use a cold or hot seal at any point of the packaging after wrapping the object.
  • reinforcements such as for example bendable rods which may be metallic, so as to maintain the packaging around its content thanks to the non-elastic folds exerted on said rods.
  • the film used in the context of the present invention comprises at least one layer comprising at least one polyester. It can therefore be an essentially monolayer film or a multilayer film. This film generally has a thickness ranging from 5 to 1 00 ⁇ m and more generally from 10 to 60 ⁇ m.
  • the film is said to be essentially monolayer if its manufacture only required the extrusion of a single thermoplastic material even if, if necessary, it received, after said extrusion, the usual finishing layers such as a metallization layer and / or printing and / or coating with an antistatic agent.
  • the film is said to be multilayer in the context of the present application if it comprises at least two layers of different thermoplastic materials.
  • the film comprises a plane of symmetry which is parallel thereto, said symmetry applying both to the geometry and to the composition of the film.
  • the film is multilayer and comprises at least two layers of different composition, the film necessarily comprises at least three layers. 4
  • the sum of the mass of the layers comprising a polyester can represent at least 20% by weight of the mass of the film.
  • the film may consist of at least three main layers, one of which, with a composition different from the other two, is in the middle of the film, so that it includes the plane of symmetry of the film.
  • three main layers is meant that the sum of the mass of these three layers constitutes at least 80% of the total mass of the film and that each of these three layers obtained from a thermoplastic material constitutes at least 10% by weight of the total mass of the film.
  • the middle layer may comprise at least one polyolefin and the other two, substantially identical, layers may comprise at least one polyester.
  • the film comprising at least three main layers in the sense given above has an excellent tearability (substantially linear tear) in all directions, in particular both in the direction of the coextrusion and in the direction perpendicular to the coextrusion . This film is therefore also particularly suitable for applications requiring good tearability in the direction perpendicular to the direction of coextrusion.
  • the layer comprises at least 60% by weight of said material.
  • the film comprises at least one layer comprising at least one polyester and at least one layer comprising at least one polyolefin.
  • the film according to the invention comprises at least one layer of polyester, said film being essentially monolayer, or said film being multilayer and comprising in this case at least one layer comprising at least one polyolefin.
  • polyolefin a polymer of at least one olefin, the term polymer having to be taken in the broad sense, so that it covers the notions of homopolymer, copolymer, terpolymer, interpolymer, or a blend of polymers.
  • olefin there may be mentioned ethylene, propylene, butene, hexene, 1-octene.
  • polyolefin a polymer of propylene or ethylene is preferred, the latter being more preferred.
  • the polymer of at least one olefin can 5 therefore be derived from the polymerization of at least one olefin with at least one other monomer, which may be an olefin or another monomer such as for example vinyl acetate, maleic anhydride or an acrylic ester.
  • the middle layer is advantageously based on a polymer of ethylene.
  • This ethylene polymer can be such that at least 80% of the monomer units constituting it is ethylene.
  • polyester is meant a polymer comprising at least one ester function as a repeating unit, the term polymer here also covering the concepts of homopolymer, copolymer, terpolymer, interpolymer and mixture of polymers.
  • the polyester can be derived from the condensation of terephthalic acid and at least one diol.
  • the polyester can be chosen from amorphous or semi-crystalline polyesters.
  • amorphous is meant that the polyester has less than 15% of crystallinity and preferably less than 10% of crystallinity.
  • amorphous and semi-crystalline polyesters can be produced by methods known in themselves.
  • amorphous polyesters are usually made by melt phase techniques ("melt phase techniques" in English) and crystalline polyesters are usually made by a combination of melt and solid phase polycondensation procedures.
  • the polyester is amorphous.
  • a polyester is usually prepared by polycondensation of one or more diacid (s) (also called dibasic acid) with one or more diol (s) (also called glycol (s)). It is recalled that a polyester obtained from a polycondensation medium comprising terephthalic acid and ethylene glycol is usually called “polyethylene terephthalate” and usually designated by the abbreviation "PET”.
  • a preferred polyester is a copolymer which can be obtained from the condensation (also called polycondensation) of terephthalic acid with ethylene glycol and a diol comprising at least three carbon atoms.
  • Such a polyester is usually called “polyethylene terephthalate glycol” and usually designated by the abbreviation "PETG”. 6
  • the polycondensation medium comprises terephthalic acid, ethylene glycol, a diol comprising at least three carbon atoms and, where appropriate, other diacids and / or other diols.
  • a particularly suitable polyester is a copolymer resulting from the copolymerization (in fact polycondensation) of terephthalic acid with ethylene glycol and cyclohexane dimethanol, in particular when it is amorphous.
  • the polycondensation medium comprises terephthalic acid, ethylene glycol, cyclohexane dimethanol, and where appropriate other diacids and / or other diols, the final polyester being more particularly suitable when it is amorphous.
  • the diacid component of the polyester can comprise 70 to 100% by mole of terephthalic acid and 0 to 30% by mole of another acid chosen from isophthalic acid, naphthalenedicarboxylic acid, acid 1, 4- cyclohexanedicarboxylic or mixtures thereof.
  • the diacid component contains from 80 to 100% by mole of terephthalic acid and 0 to 20% by mole of isophthalic acid.
  • the diacid component can be modified by a small amount, namely up to 10 mol%, of a diacid containing 4 to 40 carbon atoms such as an isomer of naphthalenedicarboxylic acid or their mixtures, the isomers 1 , 4-, 1, 5-, 2,6- and 2,7- being preferred, or such as a cis, trans isomer or a mixture of cis / trans isomers of 1,4-cyclohexanedicarboxylic acid, or such as sulfoisophthalic acid.
  • a diacid containing 4 to 40 carbon atoms such as an isomer of naphthalenedicarboxylic acid or their mixtures, the isomers 1 , 4-, 1, 5-, 2,6- and 2,7- being preferred, or such as a cis, trans isomer or a mixture of cis / trans isomers of 1,4-cyclohexanedicarboxylic acid, or such as sulfo
  • the diol component of the polyester can be derived from diols (that is to say glycols) comprising 2 to 10 carbon atoms and their mixtures.
  • the diol component contains 2 to 99 mol% of 1,4-cyclohexanedimethanol and 1 to 98 mol% of ethylene glycol, and more preferably 25 to 40 mol% of 1,4 cyclohexanedimethanol and 75 to 60 mol% of ethylene glycol.
  • the diol component can be modified by up to 20 mol% of other glycols such as diethylene glycol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 8-octanediol, 2,2,4-trimethyl-1, 3-pentanediol, propylene glycol, 1, 3-propylenediol.
  • other glycols such as diethylene glycol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 8-octanediol, 2,2,4-trimethyl-1, 3-pentanediol, propylene glycol, 1, 3-propylenediol.
  • the polyester can be chosen from those whose intrinsic viscosity ranges from 0.4 to 1.5 dL / g, and preferably from 0.6 to 1.2 dL / g, said viscosity being determined at 25 ° C. using 0 , 25 g of polymer per 100 ml of a solvent composed of 60% by weight of phenol and 40% by weight of tetrachloroethane. 7
  • the middle layer can represent 40 to 80% by weight of the mass of the film.
  • the middle layer is based on an ethylene polymer and represents from 40 to 80 % by weight of the mass of the film
  • each of the other two layers being based on a polyester which is a copolymer resulting from the condensation of terephthalic acid with ethylene glycol and a diol comprising at least three carbon atoms , each of these two other layers representing from 10 to 30% of the mass of the film, said polyester preferably being amorphous, and said diol comprising at least three carbon atoms which may be cyclohexanedimethanol.
  • the film may comprise one or more binders, promoters of adhesion of interfaces, between the different layers.
  • binders are generally present between the layers of the film at a rate of 1 to 5 ⁇ m.
  • binder s
  • the materials constituting at least one of the layers of the film so as to increase the compatibility and therefore the adhesion of said layer to at least 1 'one of the layers which is juxtaposed to it.
  • a binder can be present in the chosen layer, at a rate of 10 to 40% by weight.
  • at least one of the ingredients (binder and / or thermoplastic resin) useful in the manufacture of the film may contain at least one adjuvant or additive, such as a dye or pigment, antioxidant, anti-UV agent, agent slippery, anti-blocking agent, incorporated in a usual manner and known to those skilled in the art, taking into account the ingredient chosen.
  • At least one slip agent can be incorporated into at least one ingredient of the film, prior to its preparation by extrusion or coextrusion. If the film is multilayer, the slip agent is preferably incorporated in the outermost coextruded layers.
  • Such an agent 8 slip can for example be chosen from amides of fatty acids ⁇ such as erucamide and can be introduced at a rate of 200 to 5000 ppm in the thermoplastic material from which the layer or layers of the film containing this slip agent will be derived. In general, such a slip agent is incorporated into the film if it is not intended to metallize or print it.
  • At least one antiblocking agent can be incorporated into at least one ingredient of the film, prior to its preparation by extrusion or coextrusion.
  • the anti-blocking agent is preferably introduced so as to be present towards the external layers of the film, for example the two outermost layers having been coextruded, but lying just below the or non-coextruded layers, that is to say printing and / or metallization and / or coating with an antistatic agent, if the latter are provided.
  • This anti-blocking agent has the function of reducing the tendency of the film to adhere to itself when it is wound in a reel, so as to facilitate its unwinding.
  • Such an antiblocking agent generally comprises particles of mineral filler such as silica and can be incorporated within at least one of the layers in the form of a master batch of mineral filler / thermoplastic resin.
  • the anti-blocking agent comprises a mineral filler
  • the anti-blocking agent can be incorporated in at least one layer so that the mineral filler is present in said layer at a rate of 1 000 to 1 000 ppm.
  • antistatic properties can be applied to the film on the basis of principles known to those skilled in the art, that is to say, either by adding at least one antistatic agent in at least one of the ingredients (resin and / or binder) entering into the composition of the film, prior to the manufacture of the latter, either by coating the film on its external layers using a solution of an antistatic agent, or also by 9 any other appropriate means.
  • Antistatic agents of the family of " alkylamines are known to those skilled in the art.
  • the coating with an antistatic agent corresponds to a final surface treatment of the film, so that it results in the production of the outer layers of the film.
  • This coating with an antistatic agent is therefore carried out in particular after the possible printing step.
  • a coating with an antistatic agent it is not necessary to use a coating with an antistatic agent if the film has been metallized.
  • a corona treatment can be applied to the film according to the invention, on the basis of the principles known to those skilled in the art.
  • the film is essentially monolayer or produced so that its outermost coextruded layers contain at least one polyester, a satisfactory metallization result is obtained even in the absence of corona treatment.
  • the film used in the context of the invention can for example be obtained by extrusion or coextrusion in a flat die (often called “cast” extrusion) or by extrusion or coextrusion blow molding (also called “tubular”).
  • extrusion applies to the production of a monolayer film
  • coextrusion applies to the production of a film comprising at least two layers.
  • a flat film is extruded or coextruded and continuously deposited on a chill roll also called "chill-roll".
  • the film After extrusion or coextrusion in a flat die, the film preferably undergoes monoaxial or biaxial stretching (respectively producing a mono or biorirection) on the basis of the principles known to those skilled in the art.
  • a monoaxial stretching is carried out in the direction of extrusion or coextrusion ("machine direction"), while a biaxial stretching is carried out both in the direction of extrusion or coextrusion and in the direction perpendicular to the extrusion or coextrusion.
  • machine direction direction of extrusion or coextrusion
  • biaxial stretching is carried out both in the direction of extrusion or coextrusion and in the direction perpendicular to the extrusion or coextrusion.
  • Mono or bi-orientation has the particular effect of increasing the " density of the film and of reducing its resistance to the flow threshold.
  • the stretching or the bi-stretching can be carried out continuously or "in recovery”, that is to say after rewinding and temporary storage of the film just after the latter has been extruded or coextruded or has already undergone a first stretching .
  • the film is extruded or coextruded in the form of a cylindrical bubble obtained by inflation from an annular die.
  • the draw rate can range from 2 to 50 and preferably from 10 to 30, the inflation rate can range from 1 to 10 and preferably from 1.5 to 3, the air gap can range from 0, 5 to 5 mm and preferably 0.8 to 1.6 mm.
  • the drawing speed can range from 10 to 150 m / min, and preferably from 30 to 60 m / min.
  • PETG Polyethylene terephthalate glycol Eastman Eastar
  • the film was produced by tubular coextrusion under the following conditions:
  • MDPE / HDPE / terpolymer 180 ° C
  • the film obtained has a width of 800 mm and a total thickness of 28 ⁇ m and a density of approximately 1.1.
  • a 60 mm x 90 mm rectangle is cut from the film and a candy is wrapped manually by making a foil by turning the film 1/2 of a time with one hand relative to the candy held by the other hand.
  • the foil does not show a marked tendency to go back.
  • a rectangle of 60 mm x 90 mm is cut from a biaxially oriented polypropylene film and a candy is wrapped in the same manner as for Example 1. We can see that the foil has a marked tendency to go back.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Packging For Living Organisms, Food Or Medicinal Products That Are Sensitive To Environmental Conditiond (AREA)
  • Packages (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
EP99900945A 1998-01-29 1999-01-18 Folie zum einwickeln von objekten Withdrawn EP1051298A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9800983 1998-01-29
FR9800983A FR2774078B1 (fr) 1998-01-29 1998-01-29 Film pour l'enveloppement d'objets
PCT/FR1999/000086 WO1999038685A1 (fr) 1998-01-29 1999-01-18 Film pour l'enveloppement d'objets

Publications (1)

Publication Number Publication Date
EP1051298A1 true EP1051298A1 (de) 2000-11-15

Family

ID=9522323

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99900945A Withdrawn EP1051298A1 (de) 1998-01-29 1999-01-18 Folie zum einwickeln von objekten

Country Status (15)

Country Link
EP (1) EP1051298A1 (de)
JP (1) JP2002501863A (de)
CN (1) CN1295516A (de)
AU (1) AU751843B2 (de)
BR (1) BR9908135A (de)
CA (1) CA2318460A1 (de)
FR (1) FR2774078B1 (de)
HU (1) HUP0100264A3 (de)
IL (1) IL137271A (de)
NO (1) NO20003726L (de)
NZ (1) NZ505864A (de)
PL (1) PL341862A1 (de)
RU (1) RU2213665C2 (de)
TR (1) TR200002187T2 (de)
WO (1) WO1999038685A1 (de)

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Also Published As

Publication number Publication date
RU2213665C2 (ru) 2003-10-10
CA2318460A1 (fr) 1999-08-05
CN1295516A (zh) 2001-05-16
IL137271A0 (en) 2001-07-24
AU2059599A (en) 1999-08-16
NO20003726D0 (no) 2000-07-20
FR2774078B1 (fr) 2000-03-03
NZ505864A (en) 2002-04-26
HUP0100264A2 (hu) 2001-06-28
IL137271A (en) 2004-07-25
NO20003726L (no) 2000-09-29
JP2002501863A (ja) 2002-01-22
HUP0100264A3 (en) 2003-02-28
FR2774078A1 (fr) 1999-07-30
TR200002187T2 (tr) 2000-11-21
WO1999038685A1 (fr) 1999-08-05
AU751843B2 (en) 2002-08-29
PL341862A1 (en) 2001-05-07
BR9908135A (pt) 2000-11-28

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