EP1613797B1 - Monofilaments et rubans produits d'un polyethylene catalyse par metallocene - Google Patents

Monofilaments et rubans produits d'un polyethylene catalyse par metallocene Download PDF

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Publication number
EP1613797B1
EP1613797B1 EP04726183A EP04726183A EP1613797B1 EP 1613797 B1 EP1613797 B1 EP 1613797B1 EP 04726183 A EP04726183 A EP 04726183A EP 04726183 A EP04726183 A EP 04726183A EP 1613797 B1 EP1613797 B1 EP 1613797B1
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EP
European Patent Office
Prior art keywords
indenyl
metallocene
unsubstituted
substituted
ind
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.)
Expired - Lifetime
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EP04726183A
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German (de)
English (en)
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EP1613797A1 (fr
Inventor
Eric Maziers
Vincent Stephenne
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TotalEnergies Onetech Belgium SA
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Total Research and Technology Feluy SA
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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/42—Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments
    • D01D5/426—Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments by cutting films
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/42—Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
    • 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
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core

Definitions

  • This invention relates to the field of monofilaments and stretched tapes prepared with metallocene-produced polyethylene.
  • Monofilaments are uniaxially oriented wire-like polymer strands having a circular cross section. They are manufactured by melt spinning process and their size ranges from 0.1 to 2.5 mm in diameter, depending upon the end use application. Polyethylene, polypropylene, nylon and polyesters are commonly used as raw materials for making monofilaments.
  • Stretched tapes are prepared from a primary film produced either by a blown or by a cast film process.
  • the film can be cut into tapes and then oriented or reversely, oriented and then cut into tapes.
  • the orientation is carried out by stretching the film or tapes while passing through an air oven or on a hot plate at a temperature below the melting point.
  • the stretching is carried out by passing the film or tapes over two sets of rollers placed respectively before and after the air oven/hot plate and operating at different speeds, the speed of the second set of rellers being larger than that of the first set of rollers.
  • the polymer preferably used in the market for these applications is a high density polyethylene (HDPE) prepared with a Ziegler-Natta catalyst, said HDPE having a MI2 smaller than 1 g/10min such as for example Solvay Eltex A4009MFN1325 resin or Basell Hostalen GF 7740 F1, GF7740 F2, GF7740 F3, GF7750 M2 grades or the polyethylene resins disclosed in GB-0023662 .
  • the molecular weight distribution MWD of these resins is quite broad which means that the resins may include very long as well as very short chains.
  • JP 11-201,176 A discloses a shrinkable packaging material obtained by weaving a flat yam comprising an ethylene- ⁇ -olefin copolymer having a 0.90 - 0.93 g/cm 3 density and produced by using a metallocene catalyst.
  • PE polycrystalline polyethylene
  • PP polypropylene
  • raffia is defined as woven monofilaments or woven stretched tapes.
  • the stretched tapes and monofilaments prepared with polyethylene exhibit a higher elongation at rupture, a greater flexibility and a lower tendency to fibrillation than those prepared from polypropylene. These properties are advantageous for example in the production of woven tape fabrics.
  • the products prepared from polyethylene however suffer from the disadvantage their tenacity is much lower than that of the products prepared from polypropylene. Tenacity increases as a function of molecular weight, density, degree of orientation of the chains/crystallites and increases with narrowing of the molecular weight distribution. Impact strength increases with decreasing density, increasing molecular weight and decreasing molecular weight distribution.
  • the present invention provides monofilaments or stretched tapes, unwoven or woven into raffia prepared from metallocene-produced polyethylene (mPE) resin having long chain branches, and a density of from 0.930 to 0.950 g/cm 3 , wherein the metallocene component is a bis-indenyl represented by the general formula R" (Ind) 2 MQ 2 (I) wherein (Ind) is an indenyl or an hydrogenated indenyl, substituted or unsubstituted, R" is a structural bridge between the two indenyls to impart stereorigidity that comprises a C 1 -C 4 alkylene radical, a dialkyl germanium or silicon or siloxane, or a alkyl phosphine or amine radical, which bridge is substituted or unsubstituted; Q is a hydrocarbyl radical having from 1 to 20 carbon atoms or a halogen, and M is a group IVb transition metal or vanadium.
  • the preferred metallocene catalyst component is based on a terahydroindenyl component or on a constrained geometry component, more preferably on a terahydroindenyl component.
  • the invention also provides a process for preparing the above mentioned raffia or stretched tapes with a metallocene-produced polyethylene that comprises the steps of:
  • the primary film can first be cut into strips and then oriented by stretching.
  • the present invention also provides a process for preparing the above mentioned raffia or stretched tapes that comprises the steps of
  • the film can be either a blown film or a cast film. Film production is easier with processed material having high melt strength such as polyethylene having long chain branches and/or very long linear chains. Metallocene catalyst systems based on tetrahydroindenyl components or on constrained geometry components are particularly useful for preparing polyethylene resins having long branches.
  • the resins prepared with a terahydroindenyl catalyst component provide a very stable bubble thereby leading to films having a uniform thickness and presenting no or very little creases. Uneven thickness and creases are points of weakness when the film is cut into tapes and stretched.
  • the resins prepared with a terahydroindenyl catalyst component have a stable elongational viscosity leading to a stable and regular thickness.
  • resins having long branches keep good mechanical properties, such as traction resistance and tenacity, at densities smaller than those of linear resins having equivalent mechanical properties.
  • Working at low densities has the advantage of providing material that has improved flexibility, low fusion temperature and good processability.
  • Orientation of the primary film or of the cut tapes is carried out by stretching while passing through an air oven or over a hot plate, maintained at a temperature below the melting temperature. Stretching of the primary film or of the cut tapes is done by passing said film or tapes over two sets of rollers (goddet rollers) placed respectively before and after the air oven/hot plate, and operating at different speeds.
  • the stretch ratio S2/S1 is defined by the ratio of the speed of roller 2, S2 to the speed of roller 1, S1 wherein S2 is larger than S1.
  • Stretching at such high temperature results in chain/crystals orientation with a simultaneous increase of crystallinity. These structural changes lead to an increase of tensile strength and concurrently to a reduction of elongation.
  • the tensile strength increases with increasing stretch ratio and with increasing stretching temperature. It is preferred that the stretching temperature is as close as possible-to but smaller than the melting temperature.
  • typical values for the stretch ratio are of from 5.0 to 7.0.
  • the typical stretching temperatures depend upon the melting temperature of the polyethylene resins: they must be lower than but as close as possible to the melting temperature. Typically, they are from 5 to 70 °C lower than the melting temperature of the resin, preferably they are from 10 to 50 °C lower than the melting temperature of the resin.
  • the drawn tapes are annealed immediately after the stretching operation in order to minimise shrinkage that could occur as a result of residual stresses in the oriented tapes.
  • Annealing is done by heating the stretched tapes while they are being transferred from the second goddet rollers onto a third roller having a speed S3 that is smaller than the speed of roller 2, S2.
  • speed S3 is about 95 % of speed S2.
  • the annealing ratio AR is defined as (S2-S3)/S2) at a temperature slightly inferior to the stretching temperature.
  • the annealing temperature is from 5 to 10 °C lower than the stretching temperature.
  • Polymers that do not include either very long linear chains or long chain branched molecules have a better stretchability.
  • the low density polyethylene (LDPE) having long chain branches cannot be stretched beyond a certain degree, whereas the purely linear polyethylene chains usually obtained with a Ziegler-Natta catalyst have a high degree of stretchability.
  • the metallocene used to prepare the high density polyethylene is a bis-indenyl represented by the general formula: R" (Ind) 2 MQ 2 (I) wherein (Ind) is an indenyl or an hydrogenated indenyl, substituted.
  • R" is a structural bridge between the two indenyls to impart stereorigidity that comprises a C 1 -C 4 alkylene radical, a dialkyl germanium or silicon or siloxane, or a alkyl phosphine or amine radical, which bridge is substituted or unsubstituted;
  • Q is a hydrocarbyl radical having from 1 to 20 carbon atoms or a halogen, and M is a group IVb transition metal or Vanadium.
  • each indenyl or hydrogenated indenyl compound may be substituted in the same way or differently from one another at one or more positions in the cyclopentadienyl ring, the cyclohexenyl ring and the bridge.
  • each substituent on the indenyl may be independently chosen from those of formula XR v in which X is chosen from group IVA, oxygen and nitrogen and each R is the same or different and chosen from hydrogen or hydrocarbyl of from 1 to 20 carbon atoms and v+1 is the valence of X.
  • X is preferably C.
  • the cyclopentadienyl ring is substituted, its substituent groups must be so bulky as to affect coordination of the olefin monomer to the metal M.
  • Substituents on the cyclopentadienyl ring preferably have R as hydrogen or CH 3 . More preferably, at least one and most preferably both cyclopentadienyl rings are unsubstituted.
  • both indenyls are unsubstituted and the most preferred catalyst component is a tetrahydroindenyl.
  • R" is preferably a C1-C4 alkylene radical (as used herein to describe a difunctional radical, also called alkylidene), most preferably an ethylene bridge (as used herein to describe a difunctional radical, also called ethylidene), which is substituted or unsubstituted.
  • the metal M is preferably zirconium, hafnium, or titanium, most preferably zirconium.
  • Each Q is the same or different and may be a hydrocarbyl or hydrocarboxy radical having 1 to 20 carbon atoms or a halogen.
  • Suitable hydrocarbyls include aryl, alkyl,alkenyl,alkylaryl or arylalkyl.
  • Each Q is preferably halogen.
  • metallocenes used in the present invention one can cite bis tetrahydro-indenyl compounds and bis indenyl compounds as disclosed for example in WO 96/35729 or bis(cyclopentadienyl) compounds.
  • the most preferred metallocene catalyst is isopropylidene-bis(4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride.
  • the metallocene may be supported according to any method known in the art.
  • the support used in the present invention can be any organic or inorganic solids, particularly porous supports such as talc, inorganic oxides, and resinous support material such as polyolefin.
  • the support material is an inorganic oxide in its finely divided form.
  • alumoxane is used to ionise the catalyst during the polymerization procedure, and any alumoxane known in the art is suitable.
  • the preferred alumoxanes comprise oligomeric linear and/or cyclic alkyl alumoxanes represented by the formula : And wherein n is 1-40, preferably 10-20, m is 3-40, preferably 3-20 and R is a C 1 -C 8 alkyl group and preferably methyl. Methylalumoxane is preferably used.
  • aluminiumalkyl(s) can be used as cocatalyst in the reactor.
  • the aluminiumalkyl is represented by the formula AlR x can be used wherein each R is the same or different and is selected from halides or from alkoxy or alkyl groups having from 1 to 12 carbon atoms and x is from 1 to 3.
  • Especially suitable aluminiumalkyl are trialkylaluminium, the most preferred being triisobutylaluminium (TIBAL).
  • the catalyst may be prepolymerised prior to introducing it in the reaction zone and/or prior to the stabilization of the reaction conditions in the reactor.
  • the polyethylene resin of the present invention has a density ranging from 0.930 to 0.950 g/cm 3 , preferably, from 0.930 to 0.940 g/cm 3 and most preferably about 0.935 g/cm 3 .
  • the melt index MI2 is within the range 0.1 to 5 g/10 min, preferably in the range 0.2 to 1.5 g/10 min.
  • the density is measured following the method of standard test ASTM D 1505 at 23 °C and the melt index MI2 is measured following the method of standard test ASTM D 1238 at 190 °C and under a load of 2.16 kg.
  • the metallocene-prepared polyethylenes produce very strong stretched tapes and raffia products, mainly because of their narrow molecular weight distribution and because they have long chain branches.
  • the final products have improved tensile and elongation properties properties and simulteneously they have improved flexibility and processing properties.
  • Resin R1 is a medium density polyethylene resin prepared with isopropylidene (tetrahydroindenyl) zirconium dichloride. It had a density of 0.934 g/cm 3 and a melt index MI2 of 0.9 g/10 min. It was additivated as follows:
  • the final products, whether unwoven or woven (nets) obtained from the metallocene-produced resin R1 had a high tenacity, an excellent elongation at rupture and a very high break strength. It also had a soft touch and a high flexibility.
  • the titre is measured in tex or g/km: this is a measure of the linear mass of a filament or fibre.
  • the raffia products prepared according to the present invention has thus improved properties with respect to those of the prior art.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Claims (7)

  1. Monofilaments ou bandes étirées, non tissés ou tissés en un raphia, préparés à partir d'une résine de polyéthylène produite avec un métallocène ayant des ramifications à longue chaîne et une masse volumique de 0,930 à 0,950 g/cm3, dans lesquels le composant métallocène est un bis-indényle représenté par la formule générale :

            R"(Ind)2MQ2     (I)

    dans laquelle (Ind) est un indényle ou un indényle hydrogéné, substitué ou non substitué, R" est un pont structurel entre les deux indényles servant à conférer une stéréorigidité qui comprend un radical alkyléne en C1 à C4, un dialkyl-germanium ou silicium ou siloxane, ou un radical alkyl-phosphine ou amine, le pont étant substitué ou non substitué ; Q est un radical hydrocarbyle ayant de 1 à 20 atomes de carbone ou un halogène, et M est un métal de transition du Groupe IVb ou le vanadium.
  2. Monofilaments ou bandes étirées selon la revendication 1, dans lesquels la masse volumique de la résine de polyéthylène est de 0, 930 à 0,940 g/cm3 et de préférence d'environ 0,935 g/cm3 et l'indice de fusion MI2 est situé dans la plage allant de 0,1 à 5 g/10 min, de préférence dans la plage allant de 0,2 à 1,5 g/10 min.
  3. Procédé pour préparer les bandes étirées de la revendication 1 ou de la revendication 2, qui comprend les étapes consistant à :
    a) disposer d'une résine de polyéthylène moyenne densité produite avec un métallocène, ayant des ramifications à longue chaîne, le composant métallocène étant un bis-indényle représenté par la formule générale :

            R"(Ind)2MQ2     (I)

    dans laquelle (Ind) est une indényle ou un indényle hydrogéné, substitué ou non substitué, R" est un pont structurel entre les deux indényles servant à conférer une stéréorigidité qui comprend un radical alkylène en C1 à C4, un dialkyl-germanium ou silicium ou siloxane, ou un radical alkyl-phosphine ou amine, le pont étant substitué ou non substitué ; Q est un radical hydrocarbyle ayant de 1 à 20 atomes de carbone ou un halogène, et M est un métal de transition du Groupe IVb ou le vanadium ;
    b) produire un film à partir de la résine de polyéthylène de l'étape a) ;
    c) orienter le film obtenu dans l'étape b) par étirage ;
    d) découper en bandes le film étiré de l'étape c) ;
    e) éventuellement recuire les bandes étirées.
  4. Procédé pour préparer les bandes étirées de la revendication 1 ou de la revendication 2, qui comprend les étapes consistant à :
    a) disposer d'une résine de polyéthylène moyenne densité produite avec un métallocène, ayant des ramifications à longue chaîne, le composant métallocène étant un bis-indényle représenté par la formule générale :

            R"(Ind)2MQ2     (I)

    dans laquelle (Ind) est un indényle ou un indényle hydrogéné, substitué ou non substitué, R" est un pont structurel entre les deux indényles servant à conférer une stéréorigidité qui comprend un radical alkylène en C1 à C4, un dialkyl-germanium ou silicium ou siloxane, ou un radical alkyl-phosphine ou amine, le pont étant substitué ou non substitué ; Q est un radical hydrocarbyle ayant de 1 à 20 atomes de carbone ou un halogène, et M est un métal de transition du Groupe IVb ou le vanadium ;
    b) produire un film à partir de la résine de polyéthylène de l'étape a) ;
    c) découper en bandes le film obtenu dans l'étape b) ;
    d) orienter les bandes de film obtenues dans l'étape c) par étirage ;
    e) éventuellement recuire les bandes étirées.
  5. Procédé selon la revendication 3 ou 4, dans lequel la température d'étirage est inférieure de 10 à 70°C au point de fusion de la résine.
  6. Procédé selon la revendication 5, dans lequel la température d'étirage est inférieure de 15 à 50°C au point de fusion de la résine.
  7. Procédé selon l'une quelconque des revendications 3 à 6, dans lequel la température de recuit, si un recuit est effectué, est inférieure de 5 à 10°C à la température d'étirage.
EP04726183A 2003-04-16 2004-04-07 Monofilaments et rubans produits d'un polyethylene catalyse par metallocene Expired - Lifetime EP1613797B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP04726183A EP1613797B1 (fr) 2003-04-16 2004-04-07 Monofilaments et rubans produits d'un polyethylene catalyse par metallocene

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP03076128A EP1469104A1 (fr) 2003-04-16 2003-04-16 Polyéthylène pour fibres obtenu avec un catalyseur métallocène
EP04726183A EP1613797B1 (fr) 2003-04-16 2004-04-07 Monofilaments et rubans produits d'un polyethylene catalyse par metallocene
PCT/EP2004/050479 WO2004092459A1 (fr) 2003-04-16 2004-04-07 Polyethylene produit a partir de metallocenes pour des applications de fibres

Publications (2)

Publication Number Publication Date
EP1613797A1 EP1613797A1 (fr) 2006-01-11
EP1613797B1 true EP1613797B1 (fr) 2013-03-06

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EP03076128A Withdrawn EP1469104A1 (fr) 2003-04-16 2003-04-16 Polyéthylène pour fibres obtenu avec un catalyseur métallocène
EP04726183A Expired - Lifetime EP1613797B1 (fr) 2003-04-16 2004-04-07 Monofilaments et rubans produits d'un polyethylene catalyse par metallocene

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP03076128A Withdrawn EP1469104A1 (fr) 2003-04-16 2003-04-16 Polyéthylène pour fibres obtenu avec un catalyseur métallocène

Country Status (6)

Country Link
US (1) US20070178303A1 (fr)
EP (2) EP1469104A1 (fr)
JP (1) JP4767839B2 (fr)
KR (1) KR101333394B1 (fr)
CN (1) CN100434575C (fr)
WO (1) WO2004092459A1 (fr)

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JP5668689B2 (ja) 2009-11-09 2015-02-12 旭硝子株式会社 ポリテトラフルオロエチレン水性乳化液及びその製造方法、該水性乳化液を用いて得られるポリテトラフルオロエチレン水性分散液、ポリテトラフルオロエチレンファインパウダー並びに延伸多孔体
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EP3827117B1 (fr) 2018-07-26 2022-10-12 Dow Global Technologies LLC Procédés d'emballage rétractable de deux ou plus articles
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CN1774528A (zh) 2006-05-17
US20070178303A1 (en) 2007-08-02
EP1613797A1 (fr) 2006-01-11
KR20060010750A (ko) 2006-02-02
KR101333394B1 (ko) 2013-11-28
JP4767839B2 (ja) 2011-09-07
CN100434575C (zh) 2008-11-19
WO2004092459A1 (fr) 2004-10-28
EP1469104A1 (fr) 2004-10-20

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