US20050042447A1 - Composite yarn, method for obtaining same and resulting textile structure - Google Patents

Composite yarn, method for obtaining same and resulting textile structure Download PDF

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Publication number
US20050042447A1
US20050042447A1 US10/499,810 US49981004A US2005042447A1 US 20050042447 A1 US20050042447 A1 US 20050042447A1 US 49981004 A US49981004 A US 49981004A US 2005042447 A1 US2005042447 A1 US 2005042447A1
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US
United States
Prior art keywords
yarn
composite yarn
coating
polymer
polymer material
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.)
Abandoned
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US10/499,810
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English (en)
Inventor
Isabelle Conesa
Philippe Berge
Laurence Pollet
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.)
Chavanoz Industrie SARL
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Chavanoz Industrie SARL
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 Chavanoz Industrie SARL filed Critical Chavanoz Industrie SARL
Publication of US20050042447A1 publication Critical patent/US20050042447A1/en
Assigned to CHAVANOZ INDUSTRIE reassignment CHAVANOZ INDUSTRIE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BERGE, PHILIPPE, CONESA, ISABELLE, POLLET, LAURENCE
Priority to US12/585,662 priority Critical patent/US9045845B2/en
Abandoned legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
    • D02G3/36—Cored or coated yarns or threads
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
    • D02G3/40—Yarns in which fibres are united by adhesives; Impregnated yarns or threads
    • D02G3/404—Yarns or threads coated with polymeric solutions
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
    • D02G3/40—Yarns in which fibres are united by adhesives; Impregnated yarns or threads
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • 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

Definitions

  • the present invention relates to a composite yarn for technical or industrial use, that can be assembled into all types of textile structure, especially textile webs suitable for meeting any particular application or specification, for example for the manufacture of blinds or curtains. More particularly, the invention relates to composite yarns that can be obtained by coating.
  • such a yarn is obtained by coating, in one or more layers, the core with a plastisol comprising the chlorinated polymer material, for example polyvinyl chloride, and the plasticizer, and then by gelling the plastisol around the core.
  • a plastisol comprising the chlorinated polymer material, for example polyvinyl chloride, and the plasticizer, and then by gelling the plastisol around the core.
  • the regulations applicable to such fabrics in the German Federal Republic define various classes that are characterized in particular by the specimen length destroyed by fire, and by the temperature of the combustion smoke, said classes being identified by the letters B 1 to B 3 , the letter B 1 characterizing the best fire behavior that can be obtained by a material containing organic matter.
  • the regulations applicable in France also define various classes according to the NF 1601 and NF P 92503 standards, on the one hand, characterized especially by the emission of smoke and identified by the letters F 0 to F 5 , F 3 being the best behavior that can be obtained by a material containing a halogenated polymer, and, on the other hand, characterized in particular by the residual ignition temperature of the fabric and identified by the letters M 0 to M 4 , the letter M 1 identifying the best fire behavior that can in general be obtained by a material containing organic matter.
  • a fire-retarding filler comprising a chlorinated polyethylene, a compound chosen in particular from antimony and aluminum oxides and/or hydroxides, and preferably another compound chosen from zinc salts, including zinc borate, and tin-based products, for example zinc stannate.
  • Document FR-A-2 448 554 has proposed, again for a matrix based on polyvinyl chloride and also incorporating a stabilizer, a plasticizer consisting of a phosphoric ester, and an alumina hydroxide filler, a fire-retarding filler comprising an antimony oxide, optionally combined with a zinc borate.
  • None of the fire-retarding fillers proposed above is suitable for improving to the desired extent the fire behavior of a composite yarn as considered above, and without degrading its other properties, for example mechanical properties.
  • the subject of the present invention is a coated composite yarn exhibiting, overall and intrinsically, improved fire behavior, thus favoring the dissipation of heat and making it possible to greatly reduce the random phenomenon of flame propagation measured by fire tests according to the NF P 92 503 standard on any fabric obtained from the composite yarn according to the invention.
  • the temperature withstand properties are improved owing to the uniform distribution of the fibers within the polymer coating material that allows the heat to be dissipated since, when the fibers are grouped together, they constitute a preferential conduction path that promotes heat propagation.
  • the subject of the invention is a composite yarn consisting of a continuous yarn, obtained by spinning fibers made of an organic or inorganic material or natural fibers, such as flax or cotton fibers, and of a polymer material, characterized in that the constituent fibers of said continuous yarn are uniformly distributed within said polymer material in such a way that each of said fibers is coated by said polymer material.
  • This composite yarn can be used by itself or as a core for the manufacture of composite yarns obtained by a second coating with a polymer material.
  • the subject of the present invention is also a coated composite yarn that can be obtained by a process for coating with a polymer material, characterized in that it comprises a core consisting of a composite yarn as defined above and in that the polymer material formed around the core and the constituent polymer material of the core are of the same nature.
  • this composite yarn can be used as a core for the manufacture of fire-retarded composite yarns obtained by coating with polymers containing fire-retarding fillers.
  • the subject of the present invention is also a coated fire-retarded composite yarn that can be obtained by a process for coating with a polymer material containing a fire-retarding filler, characterized in that it comprises a core consisting of a composite yarn as defined above and in that the polymer material formed around the core and the constituent polymer material of the core are of the same nature.
  • said coating can be carried out using a liquid monomer or polymer preparation; for example, a liquid polymer preparation is obtained by melting a polymer or by dispersing a polymer, for example in the form of a plastisol; and, for example, a liquid monomer preparation consists of a liquid monomer that will polymerize through the effect of heat or by irradiation, for example UV irradiation.
  • a liquid monomer preparation is obtained by melting a polymer or by dispersing a polymer, for example in the form of a plastisol
  • a liquid monomer preparation consists of a liquid monomer that will polymerize through the effect of heat or by irradiation, for example UV irradiation.
  • the invention also relates to a process for manufacturing a composite yarn, characterized in that a continuous yarn, obtained by spinning fibers made of an organic or inorganic material or natural fibers, is subjected to a process for mechanically opening the yarn that allows said fibers to be separated, simultaneously with or prior to its coating by a polymer material.
  • the invention furthermore relates to a process for manufacturing a composite yarn, characterized in that a continuous yarn, obtained by spinning fibers made of an organic or inorganic material or natural fibers, is subjected to a process for mechanically opening the yarn that allows said fibers to be separated, simultaneously with or prior to a primary coating with a liquid monomer preparation or a polymer preparation in the liquid state, and in that the composite yarn obtained is subjected to a second coating with a liquid monomer or polymer preparation.
  • the monomer or polymer of the second coating is of the same nature as the monomer or polymer of the first coating.
  • the invention furthermore relates to a process for manufacturing a fire-retarded composite yarn, characterized in that a continuous yarn, obtained by spinning fibers made of an organic or inorganic material or natural fibers, is subjected to a process for mechanically opening the yarn that allows said fibers to be separated, simultaneously with or prior to a primary coating with a liquid monomer preparation or polymer preparation in the liquid state that does not contain a fire-retarding filler, and in that the composite yarn obtained is subjected to a second coating with a liquid monomer preparation or polymer preparation in the liquid state containing a fire-retarding filler.
  • mechanically opening is understood to mean any process for opening the fibers, simultaneously with or prior to the coating operation, such as splaying the fibers, by applying an air jet or a water jet, an ultrasonic treatment, the application of mechanical pressure, for example to flatten the yarn, or any process for separating the fibers in order to allow the polymer material to penetrate the constituent fibers of said yarn.
  • the yarn according to the invention exhibits none of the desheathing and shading phenomena observed in the yarns of the prior art.
  • liquid monomer or polymer preparation is understood to mean any liquid formulation based on monomers or polymers.
  • formulation is understood to mean any compound comprising at least one product, for example a dispersion, solution or mixture of monomers and/or oligomers.
  • polymer dispersion is understood to mean any polymer preparation in the divided state containing additives in an organic liquid or otherwise.
  • plastisol is understood to mean a dispersion of polymers, fillers and other additives, in a finely divided state, in a plasticizer.
  • polymer material it is possible to use chlorinated polymers, silicones, polyurethanes, acrylics, ethylene/vinyl acetate EVA copolymers and ethylene-propylene-diene monomer EPDM terpolymers.
  • chlorinated polymer material it is possible to use, according to the invention, any PVC resin that can be plasticized and especially one that can be employed in the form of a plastisol.
  • chlorinated polymer material is understood to mean a pure chlorinated polymer or a copolymer of vinyl chloride copolymerized with other monomers, or else a chlorinated polymer that is alloyed with other polymers.
  • olefins such as for example ethylene
  • vinyl esters of saturated carboxylic acids such as vinyl acetate, vinyl butyrate or maleates
  • halogenated vinyl derivatives such as for example vinylidene chloride
  • acrylic or methacrylic acid esters such as butyl acrylate.
  • chlorinated polymer mention may in particular be made of polyvinyl chloride, and also superchlorinated PVCs, polyvinylidene chlorides and chlorinated polyolefins.
  • the chlorinated polymer material according to the present invention has a halogen weight content of between 40 and 70%.
  • silicone polymer material organopolysiloxanes and more particularly polysiloxane resins and elastomers with or without a diluent.
  • polyurethane polymer material any material formed from a hydrocarbon chain containing the urethane or —NHCOO— unit.
  • the continuous yarn this itself consists of one or more continuous filaments or fibers. Its chemical nature may be organic, for example made of polyester, polyamide, polyvinyl, or acrylic, of natural origin, such as flax or cotton, or inorganic, for example made of glass or silica, it being understood that its melting point must be above that at which the polymer material is processed.
  • the fire-retarding filler is chosen from the group formed by zinc borate, aluminum hydroxide, antimony trioxide and zinc hydroxystannate, molybdenum compounds, halogenated derivatives, compounds containing active halogens, phosphorus compounds, and intumescent systems.
  • fillers may be incorporated and distributed within the liquid monomer or polymer preparation, in addition to the fire-retarding filler, for example a pigmenting filler, silica, talc, glass beads and/or a stabilizer.
  • a pigmenting filler silica, talc, glass beads and/or a stabilizer.
  • the total composition by weight of the composite yarn, in terms of inorganic materials, is obviously modified or affected.
  • the invention also makes it possible to limit the weight of fire-retarding filler, in proportions not exceeding 50% of the plastic matrix. Above 50%, the properties, especially mechanical properties, of the composite yarn are impaired.
  • FIG. 1 shows in cross section a fire-retarded composite yarn of the prior art.
  • FIG. 2 shows in cross section a fire-retarded composite yarn according to the invention.
  • the secondary coating 3 is also uniformly distributed in the composite yarn according to the invention.
  • the degree of application is the amount of impregnation of the yarn—it is defined by the following formula: weight ⁇ ⁇ of ⁇ ⁇ the ⁇ ⁇ coated ⁇ ⁇ yarn - weight ⁇ ⁇ of ⁇ ⁇ the ⁇ ⁇ yarn weight ⁇ ⁇ of ⁇ ⁇ the ⁇ ⁇ coated ⁇ ⁇ yarn ⁇ 100 ;
  • LOI represents the Limited Oxygen Index—it is determined according to the NF G 07128 standard.
  • This dissipation optimization makes it possible overall to reduce the content of fire-retardant fillers in the coated fire-retarded composite yarn.
  • a halogen-free coated fire-retarded composite yarn according to the invention was obtained by coating a mineral yarn/continuous glass fiber/continuous glass filament according to the process of the invention, that is to say by mechanically opening the yarn, by splaying it, simultaneously with or prior to the coating operation with a liquid polymer preparation based on a silicone polymer.
  • the coating formulation was defined by a viscosity between 500 and 10 000 mPa.s and preferably between 1 000 and 5 000 mPa.s, measured at 25° C. using a Brookfield RVT viscometer at 20 rpm with a No. 4 spindle.
  • the coating was carried out with a formulation comprising the following products: Silicone 100 phr Solvent/water 0 to 50 phr Fillers (pigment, fire retardant, etc.) 0 to 20 phr Crosslinking agent 2 to 6 phr Additives 0 to 5 phr Additives 0 to 5 phr.
  • the silicones used were, for example:
  • the diluents were chosen from toluene, xylene, white spirit and water.
  • the fillers consisted for example of FIREBREAK ZB zinc borate, aluminum hydroxide (Omya), SH5n alumina, promoter such as ELASTOSIL 45568 VP or HF86 (Wacker), retarder HTV-SB (Wacker), water-repellent agent WS60E (Wacker) or glass beads (Sovitec), RAL pigmentary paste from Wacker.
  • Second coating 30% degree of application 100 phr 9050/30P from Dow Corning (3 000 cP viscosity) Second coating, 30% degree of application 100 phr 9050/30P SILASTIC (Dow Corning) 2 phr
  • SILICOLEASE UV POLY 200 100 parts SILICOLEASE UV CATA 211 (Rhodia) 2 to 5 parts
  • Second coating SILICOLEASE UV POLY 200 (Rhodia) 100 parts SILICOLEASE UV CATA 211 (Rhodia) 2 to 5 parts Fire-retarding fillers Pigment.
  • the fabrics obtained with a composite yarn according to the invention require no subsequent treatment in order to improve their fire behavior.
  • a composite yarn according to the invention exhibits no defibrillation on cutting, it is more hydrophobic and it is “softer” to the touch; the textiles obtained by weaving are stain-resistant.
  • a composite yarn according to the present invention can be incorporated into any textile structure, or assembled as any required textile structure, whether two-dimensional (webs, fabrics, etc.) or three-dimensional (for example braids).
  • the composite yarn may firstly be cut and divided into elementary yarns, which can be intermingled and fastened to one another, in the form of nonwoven textile structures, for example mats.
  • the intermingled elementary yarns may be fastened by impregnation with a suitable adhesive substance, or by the thermal melting of the polymer material of the sheath.
  • the composite yarn may then be assembled on itself in any suitable knitted textile structure, but it may also be assembled with other yarns, whether or not according to the present invention, in order to constitute various two-dimensional or three-dimensional structures; in the latter case, these may be meshes in which the yarns according to the present invention are interlaced with and fastened to other yarns, whether or not according to the present invention, and fabrics in which the composite yarns according to the invention are woven with other warp and/or weft yarns, again whether or not according to the invention.
  • a very particular application of the present invention relates to the production of technical fabrics intended for the production or manufacture of both interior and exterior blinds or curtains.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Woven Fabrics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Reinforced Plastic Materials (AREA)
US10/499,810 2001-12-28 2002-12-27 Composite yarn, method for obtaining same and resulting textile structure Abandoned US20050042447A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US12/585,662 US9045845B2 (en) 2001-12-28 2009-09-21 Composite yarn, method for obtaining same and resulting textile structure

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0117047A FR2834302B1 (fr) 2001-12-28 2001-12-28 Fil composite, procede d'obtention et structure textile obtenue
FR0117047 2001-12-28
PCT/FR2002/004577 WO2003056082A2 (fr) 2001-12-28 2002-12-27 Fil composite, procede d'obtention et structure textile obtenue

Related Child Applications (1)

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US12/585,662 Continuation-In-Part US9045845B2 (en) 2001-12-28 2009-09-21 Composite yarn, method for obtaining same and resulting textile structure

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US10/499,810 Abandoned US20050042447A1 (en) 2001-12-28 2002-12-27 Composite yarn, method for obtaining same and resulting textile structure

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US (1) US20050042447A1 (ko)
EP (1) EP1458910B1 (ko)
JP (1) JP4272530B2 (ko)
KR (1) KR100903989B1 (ko)
CN (1) CN1608153B (ko)
AT (1) ATE369448T1 (ko)
AU (1) AU2002364347B2 (ko)
BR (1) BR0215350B1 (ko)
CA (1) CA2470453A1 (ko)
DE (1) DE60221707T2 (ko)
DK (1) DK1458910T3 (ko)
ES (1) ES2291533T3 (ko)
FR (1) FR2834302B1 (ko)
HK (1) HK1072280A1 (ko)
WO (1) WO2003056082A2 (ko)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070048523A1 (en) * 2003-11-25 2007-03-01 Chavanoz Industrie Composite yarn comprising a filament yarn and a matrix comprising a foamed polymer
US20100089017A1 (en) * 2001-12-28 2010-04-15 Chavanoz Industrie Composite yarn, method for obtaining same and resulting textile structure
US20120142241A1 (en) * 2010-07-08 2012-06-07 Springs Creative Products Group, Llc Coated fire barriers made from corespun yarns - coated fibers comprising the sheath of the corespun yarns
GB2579362A (en) * 2018-11-28 2020-06-24 Louver Lite Ltd Coating composition
US11530497B2 (en) 2018-04-20 2022-12-20 Mermet Composite yarn, manufacturing process and textile surface comprising such a yarn

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* Cited by examiner, † Cited by third party
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JP4835074B2 (ja) * 2005-09-05 2011-12-14 日東紡績株式会社 樹脂被覆ガラス繊維織物及び樹脂被覆ガラス繊維束並びにこれらの製造方法
FR2939152B1 (fr) 2008-12-01 2011-05-06 Porcher Ind Fil composite photoluminescent, procede d'obtention et structure textile obtenue
JP5432019B2 (ja) * 2010-03-25 2014-03-05 宇部エクシモ株式会社 難燃性ネット状物、網糸用未硬化状線状物の製造方法、及び難燃性ｆｒｐネット本体の製造方法
KR101513780B1 (ko) * 2012-05-21 2015-04-22 (주)엘지하우시스 보푸라기 방지용 원사 및 이를 이용한 우븐 바닥장식재
KR102239700B1 (ko) * 2014-04-22 2021-04-13 메르메 난연성 원사를 제조하는 신규한 방법
WO2019202151A1 (en) 2018-04-20 2019-10-24 Mermet Composite yarn, manufacturing process and textile surface comprising such a yarn
CN113957578B (zh) * 2020-07-21 2023-05-09 上海赛立特安全用品股份有限公司 一种无机非金属纤维增强单丝、包覆线及其制备方法和用途

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US2224274A (en) * 1938-08-26 1940-12-10 Milton A Powers Fabric material
US2392805A (en) * 1943-10-11 1946-01-15 Owens Corning Fiberglass Corp Glass fiber strand
US3298854A (en) * 1962-02-02 1967-01-17 Owens Corning Fiberglass Corp Method of coating yarn
US3508990A (en) * 1965-10-24 1970-04-28 Owens Corning Fiberglass Corp Method of producing a multi-element glass cord construction
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US5462803A (en) * 1993-05-21 1995-10-31 Comm/Scope Dual layer fire-resistant plenum cable
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US6255594B1 (en) * 1997-04-10 2001-07-03 Plastic Insulated Cables Limited Communications cable
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100089017A1 (en) * 2001-12-28 2010-04-15 Chavanoz Industrie Composite yarn, method for obtaining same and resulting textile structure
US9045845B2 (en) 2001-12-28 2015-06-02 Chavanoz Industrie Composite yarn, method for obtaining same and resulting textile structure
US20070048523A1 (en) * 2003-11-25 2007-03-01 Chavanoz Industrie Composite yarn comprising a filament yarn and a matrix comprising a foamed polymer
US7718259B2 (en) * 2003-11-25 2010-05-18 Chavanoz Industrie Composite yarn comprising a filament yarn and a matrix comprising a foamed polymer
WO2011033130A1 (en) * 2009-09-21 2011-03-24 Chavanoz Industrie Composite yarn, method for obtaining same and resulting textile structure
CN102575389A (zh) * 2009-09-21 2012-07-11 纱环劳仕工业公司 复合纱线、获得该复合纱线的方法和形成的纺织结构体
US20120142241A1 (en) * 2010-07-08 2012-06-07 Springs Creative Products Group, Llc Coated fire barriers made from corespun yarns - coated fibers comprising the sheath of the corespun yarns
US11530497B2 (en) 2018-04-20 2022-12-20 Mermet Composite yarn, manufacturing process and textile surface comprising such a yarn
US12091782B2 (en) 2018-04-20 2024-09-17 Mermet Composite yarn, manufacturing process and textile surface comprising such a yarn
GB2579362A (en) * 2018-11-28 2020-06-24 Louver Lite Ltd Coating composition
GB2579362B (en) * 2018-11-28 2023-04-05 Louver Lite Ltd Coating composition

Also Published As

Publication number Publication date
JP2005513299A (ja) 2005-05-12
HK1072280A1 (en) 2005-08-19
KR20040071760A (ko) 2004-08-12
KR100903989B1 (ko) 2009-06-25
BR0215350B1 (pt) 2014-11-18
ES2291533T3 (es) 2008-03-01
WO2003056082A2 (fr) 2003-07-10
ATE369448T1 (de) 2007-08-15
DE60221707T2 (de) 2008-05-15
BR0215350A (pt) 2004-12-14
EP1458910A2 (fr) 2004-09-22
DK1458910T3 (da) 2008-01-02
CN1608153A (zh) 2005-04-20
CA2470453A1 (fr) 2003-07-10
DE60221707D1 (de) 2007-09-20
WO2003056082A3 (fr) 2004-01-22
FR2834302B1 (fr) 2005-05-06
AU2002364347A1 (en) 2003-07-15
JP4272530B2 (ja) 2009-06-03
AU2002364347B2 (en) 2008-01-31
EP1458910B1 (fr) 2007-08-08
CN1608153B (zh) 2010-08-18
FR2834302A1 (fr) 2003-07-04

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