EP1448701A1 - Procede pour reduire la tenacite de pieces moulees en matiere plastique destinees a etre usinees par voie mecanique et utilisation de ces pieces moulees - Google Patents

Procede pour reduire la tenacite de pieces moulees en matiere plastique destinees a etre usinees par voie mecanique et utilisation de ces pieces moulees

Info

Publication number
EP1448701A1
EP1448701A1 EP02782964A EP02782964A EP1448701A1 EP 1448701 A1 EP1448701 A1 EP 1448701A1 EP 02782964 A EP02782964 A EP 02782964A EP 02782964 A EP02782964 A EP 02782964A EP 1448701 A1 EP1448701 A1 EP 1448701A1
Authority
EP
European Patent Office
Prior art keywords
molded parts
polyolefin
amorphous polyolefin
copolymer
partially crystalline
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Withdrawn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
EP02782964A
Other languages
German (de)
English (en)
Inventor
Ekkehard Beer
Wolfram Goerlitz
Dirk Heukelbach
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.)
Topas Advanced Polymers GmbH
Original Assignee
Ticona GmbH
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 Ticona GmbH filed Critical Ticona GmbH
Publication of EP1448701A1 publication Critical patent/EP1448701A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43K—IMPLEMENTS FOR WRITING OR DRAWING
    • B43K19/00—Non-propelling pencils; Styles; Crayons; Chalks
    • B43K19/14—Sheathings
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • C08L23/0823—Copolymers of ethene with aliphatic cyclic olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the disadvantage here is the high toughness of such polymers. Although this is desirable for many applications, it is disadvantageous when machining the plastic, since this material property does not automatically lead to chip breakage during processing. The lifted chip is therefore often caught on the machined part and must be removed in a further step. This often leaves sharp edges that increase the risk of injury. This is a considerable disadvantage in the production of writing utensils such as pencils, but in particular of sharpenable cosmetic pencils such as eyeliner. According to the current state of the art, this desired embrittlement can be brought about by adding additives, such as, for example, inorganic and / or organic fillers, in particular mineral fillers. However, the disadvantage here is the increase in the viscosity of the resulting plastic molding composition and greater stress on the cutting tool at its cutting edge. This becomes dull faster and the tool has a shorter service life.
  • the object of the present invention was to overcome the disadvantages of the prior art with simple means. This object is achieved by a process for reducing the toughness of molded parts made of plastic, characterized in that at least one partially crystalline polymer and at least one amorphous polyolefin are melted and mixed in a heatable mixing unit, which resulting mixture is processed into a plastic molding compound, and the plastic molding compound is processed into molded parts.
  • Polymers do not mix homogeneously, which increases the brittleness of the base material.
  • the degree of brittleness can be adjusted as desired by using amorphous polyolefins with certain glass temperatures. By choosing the glass temperatures, an adjustment to the melting and
  • Softening behavior of the partially crystalline polymer can be performed. This facilitates later processing, since then when the plastic molding compound is melted for processing, the additive used according to the invention, the amorphous polyolefin, also melts.
  • Another object of the invention is the use of the molded parts produced by the method according to the invention for machining.
  • Suitable materials are, for example, partially crystalline polyolefins.
  • Such materials are described, for example, in Saechtling, Kunststoff-Taschenbuch, Hanser-Verlag, 27th edition 1998 on pages 375 to 413, to which reference is made.
  • these are polymers of ethylene or ⁇ -olefins such as propene, n-butene, isobutene or higher ⁇ -olefins or copolymers made therefrom.
  • polyesters in particular thermoplastic polyester, and mixtures thereof.
  • These contain polymerized units which are derived from esters of at least one aromatic dicarboxylic acid, in particular terephthalic acid, isophthalic acid or 2,6-naphthalenedicarboxylic acid, and of at least one aliphatic diol, in particular ethylene glycol, 1,3-propanediol, 1,4-butanediol, or which contain polymerized tetrahydrofuran units, polyethylene glycol.
  • suitable polyesters are described in Ullmann's Encyclopedia of Ind. Chem., Ed. Barbara Elvers, Vol. A24, Polyester section (pp.
  • Polyesters such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) and copolyesters which contain butylene terephthalate and butylene isophthalate units are preferred.
  • the polyesters can also be modified by copolymerizing aliphatic dicarboxylic acids, such as, for example, glutaric acid, adipic acid or sebacic acid, or by polymerizing in polyglycols, such as, for example, diethylene glycol or triethylene glycol, or other, higher molecular weight
  • polyesters can also contain other polymerized units which can be derived from hydroxycarboxylic acids, preferably from hydroxybenzoic acid or from hydroxynaphthalene carboxylic acid.
  • Suitable polyamides are described, for example, in Saechtling,
  • X and Y may be the same or different and represent an aromatic or aliphatic radical.
  • the aromatic radicals are generally substituted in the meta or para position.
  • Aliphatic radicals are mostly unbranched, linear or cyclic radicals, although materials with branched radicals can also be produced and used.
  • the aliphatic radicals are preferably linear, unbranched and have 4 to 13 Carbon atoms.
  • Particularly preferred polyamides are materials, where X symbolizes a linear, aliphatic radical with 4, 7, 8 or 10 carbon atoms and Y represents a linear, aliphatic radical with 4 or 6 carbon atoms.
  • a polyamide in which X is a phenyl radical substituted in the para or meta position and Y is a linear, aliphatic radical with 6 carbon atoms or a 2,2-dimethyl-4-methylhexyl radical.
  • n is an integer greater than 1, preferably between 2 and 1000, in particular between 80 and 100.
  • Z is 5, 10 or 11 and n is greater than 1, but is preferably between 2 and 1000, in particular between 80 and 100.
  • n is greater than 1, but is preferably between 2 and 1000, in particular between 80 and 100.
  • polycarbonates are not partially crystalline, the same problem arises with these polymers, namely the poor chip breakage due to the toughness of the polymer, which can be remedied in the same way by mixing with at least one amorphous polyolefin.
  • Polycarbonates are described, for example, in Saechtling, Kunststoff-Taschenbuch, 27th edition 1998, Hanser Verlag, on pages 479 to 485.
  • Polycarbonates can be prepared, for example, by reaction of bisphenol A with phosgene, or by melt condensation of diphenyl carbonate with bisphenol A.
  • Possible comonomers are bisphenol TMC and bisphenol S (dihydroxydiphenyl sulfide). The flame resistance of such materials can be improved by using halogenated bisphenol derivatives, in particular bromine-containing bisphenol derivatives.
  • Suitable polycarbonates usually have the general formula
  • n is greater than 1 and is preferably between 2 and 10,000.
  • Polycarbonates in which n is dimensioned such that the average molecular weight does not exceed 30,000 g / mol are particularly preferred.
  • These materials can contain bisphenol units which can be substituted on the aromatic ring, for example with bromine, or which carry different aliphatic radicals on the carbon atom which connects the aromatic rings (for example bisphenol TMC-containing polycarbonates), or in which the aromatic rings also are connected to a heteroatom, such as sulfur (materials containing bisphenol S).
  • amorphous polyolefins are understood to mean those polyolefins which, despite an irregular arrangement of the molecular chains, are solids at room temperature. Their degree of crystallinity is generally below 5%, preferably below 2%, or is 0%, determined by X-ray diffractometry. Amorphous polymers whose glass transition temperature Tg is in the range from -50 to 250 ° C., preferably 0 to 220 ° C., in particular 40 to 200 ° C., are particularly suitable. In general, the amorphous polyolefin has an average molecular weight Mw in the range from 1,000 to 10,000,000, preferably 5,000 to 5,000,000, in particular 5,000 to 1,200,000.
  • the cycloolefin copolymers described here have viscosity numbers between 5 and 5,000 ml / g according to DIN 53728. Viscosity numbers between 5 and 2,000 ml / g are preferred, viscosity numbers between 5 and 1,000 ml / g are particularly preferred.
  • the refractive index of the amorphous polymer is generally in the range from 1.3 to 1.7, preferably 1.4 to 1.6.
  • Amorphous polyolefins which can be used particularly advantageously are
  • Cycloolefin copolymers and cycloolefinic polymers are known per se and are described in EP-A-0407 870, EP-A-0 485 893, EP-A-0 503 422 and DE-A-40 36 264, to which reference is expressly made here.
  • the cycloolefin polymers used are composed of one or more cycloolefins, the cycloolefins generally being substituted and unsubstituted cycloalkenes and / or polycycloalkenes, such as, for example, bi-, tri- or tetracycloalkenes.
  • the cycloolefin polymers can also be branched. Products of this type can have a comb or star structure. Copolymers of ethylene and / or an ⁇ -polyolefin with one or more cyclic, bicyclic and / or polycyclic olefins are advantageous.
  • the amorphous polyolefin of at least one of the cyclic or polycyclic olefins of the formulas I to VII is particularly advantageous
  • radicals R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 of the formulas I to VI can be the same or different, and H, C6-C20-aryl, C1-C20- Alkyl, F, Cl, Br, I mean, n is an integer from 0 to 5, and m is an integer from 2 to 10.
  • a copolymer of ethylene and norbornene can be used with particular advantage as the amorphous polyolefin.
  • the cycloolefin polymers are preferably produced with the aid of transition metal catalysts which are described in the abovementioned documents. Among them, the production processes according to EP-A-0 407 870 and EP-A-0 485 893 are preferred because these processes
  • the regulation of the molecular weight takes place in the production through the use of hydrogen, a targeted selection of the catalyst and the reaction conditions.
  • a plastic whose toughness has been reduced by the process according to the invention contains at least 50% by weight, preferably 90 to 75% by weight, in particular 95 to 75% by weight, of the partially crystalline polymer.
  • the semi-crystalline polymer and the amorphous polyolefin can in principle be mixed in any suitable mixing unit. Suitable mixing units and processes are described in: Saechtling, Kunststoff-Taschenbuch, Hanser-Verlag, 27th edition 1998, on pages 202 to 217, to which reference is made.
  • the mixing can be carried out, for example, in kneaders, Brabender kneaders being given here only by way of example.
  • the mixing unit consists of at least one screw machine.
  • extruders in particular twin-screw extruders, are used as screw machines.
  • melt temperatures are in the ranges customary for the partially crystalline polymers used in each case; eg with LDPE this is advantageous from 160 to 260 ° C, with HDPE from 260 to 300 ° C, with polypropylene mostly from 220 to 270 ° C.
  • the molded parts can be produced by any suitable method. Suitable processes are described in Saechtling, Kunststoff-Taschenbuch, Hanser-Verlag, 27th edition 1998 on pages 201 to 369, to which reference is made. Manufacture by injection molding, injection molding, extrusion or compression molding are advantageous. A method in which the melting and mixing as well as the shaping take place in one work step is particularly advantageous. In such a method, the production of the molded parts and the mixing of the amorphous and the partially crystalline polyolefin are carried out in a single device. For example, the mixing can be carried out in the same extruder with which the extrusion of the molded part is carried out, or also in an injection molding device.
  • Machining is understood to mean the machining processes described in Dubbel's Taschenbuch des Maschinenbau, Springer-Verlag, 12th edition 1963, second volume, on pages 631 to 660, to which reference is made. Methods that can be carried out using the devices described there are also suitable. Advantageous methods are turning, planing, drilling, sawing, milling, grinding, broaching, chiseling, in particular thread and gear milling and cutting, fine turning, drilling and milling.
  • Shaped parts according to the invention are, for example, lead carriers for make-up pencils, such as a pencil for applying eyeliner and the like, or pencils consisting of a graphite lead or the like inside and outside of the partially crystalline polymer, the toughness of which has been reduced by the method according to the invention.
  • These pencils can be manufactured in all conceivable geometries and shapes Sharpen without edges.
  • Comparative example Test specimens were extruded from pure polypropylene. Due to the high toughness of the polypropylene, the chip was difficult to break off and a sharp edge is created.

Abstract

La présente invention concerne un procédé pour réduire la ténacité de pièce moulées en matière plastique. Ce procédé est caractérisé en ce qu'il consiste à faire fondre au moins un polymère semi-cristallin et au moins une polyoléfine amorphe sous forme d'agrégat mixte pouvant être chauffé, à le mélanger, à façonner le mélange résultant sous forme de matière plastique à mouler , puis à façonner cette matière plastique à mouler sous forme de pièces moulées. Ces pièces moulées présentent de meilleures propriétés dans le cadre d'un usinage.
EP02782964A 2001-10-25 2002-10-19 Procede pour reduire la tenacite de pieces moulees en matiere plastique destinees a etre usinees par voie mecanique et utilisation de ces pieces moulees Withdrawn EP1448701A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10152146A DE10152146A1 (de) 2001-10-25 2001-10-25 Verfahren zur Reduzierung der Zähigkeit mechanisch zu bearbeitender Formteile aus Kunststoff sowie deren Verwendung
DE10152146 2001-10-25
PCT/EP2002/011741 WO2003035743A1 (fr) 2001-10-25 2002-10-19 Procede pour reduire la tenacite de pieces moulees en matiere plastique destinees a etre usinees par voie mecanique et utilisation de ces pieces moulees

Publications (1)

Publication Number Publication Date
EP1448701A1 true EP1448701A1 (fr) 2004-08-25

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP02782964A Withdrawn EP1448701A1 (fr) 2001-10-25 2002-10-19 Procede pour reduire la tenacite de pieces moulees en matiere plastique destinees a etre usinees par voie mecanique et utilisation de ces pieces moulees

Country Status (7)

Country Link
US (1) US20040262814A1 (fr)
EP (1) EP1448701A1 (fr)
JP (1) JP2005506427A (fr)
KR (1) KR20040063914A (fr)
CA (1) CA2464630A1 (fr)
DE (1) DE10152146A1 (fr)
WO (1) WO2003035743A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2501551C (fr) 2002-10-11 2012-12-11 University Of Connecticut Polyclooctene reticule
AU2003277332B2 (en) 2002-10-11 2009-03-12 University Of Connecticut Shape memory polymers based on semicrystalline thermoplastic polyurethanes bearing nanostructured hard segments
US7794494B2 (en) 2002-10-11 2010-09-14 Boston Scientific Scimed, Inc. Implantable medical devices
ATE498648T1 (de) 2002-10-11 2011-03-15 Univ Connecticut Mischungen von amorphen und semikristallinen polymeren mit formgedächtniseigenscchaften
US7976936B2 (en) 2002-10-11 2011-07-12 University Of Connecticut Endoprostheses
US7524914B2 (en) 2002-10-11 2009-04-28 The University Of Connecticut Shape memory polymers based on semicrystalline thermoplastic polyurethanes bearing nanostructured hard segments
US8043361B2 (en) 2004-12-10 2011-10-25 Boston Scientific Scimed, Inc. Implantable medical devices, and methods of delivering the same

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4063828A (en) * 1971-01-26 1977-12-20 Teijin Limited Plastic pencils
US4579903A (en) * 1984-12-19 1986-04-01 General Electric Company Copolyester-carbonate composition
DE3922546A1 (de) * 1989-07-08 1991-01-17 Hoechst Ag Verfahren zur herstellung von cycloolefinpolymeren
DE59209354D1 (de) * 1991-03-09 1998-07-09 Targor Gmbh Verfahren zur Herstellung chemisch einheitlicher Cycloolefincopolymere
AU652623B2 (en) * 1991-03-18 1994-09-01 Hoechst Aktiengesellschaft Binary alloys on the basis of polyether amides and cycloolefin polymers
TW330160B (en) * 1992-04-08 1998-04-21 Hoechst Ag Supported catalyst, process for its preparation and its use for the preparation of vinyl acetate
US5763532A (en) * 1993-01-19 1998-06-09 Exxon Chemical Patents, Inc. Blends of polypropylene and elastic alpha-olefin/cyclic olefin copolymers
US6831137B2 (en) * 1997-06-17 2004-12-14 Ems Inventa Ag Impact resistant transparent polyamide alloys
JP2000021244A (ja) * 1998-06-30 2000-01-21 Nippon Zeon Co Ltd コネクタ用絶縁部材の製造方法
DE19841234C1 (de) * 1998-09-09 1999-11-25 Inventa Ag Reversible thermotrope Kunststoff-Formmasse, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19951729A1 (de) * 1999-10-27 2001-05-03 Bayer Ag Polycarbonatblendzusammensetzungen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03035743A1 *

Also Published As

Publication number Publication date
WO2003035743A1 (fr) 2003-05-01
JP2005506427A (ja) 2005-03-03
DE10152146A1 (de) 2003-05-22
CA2464630A1 (fr) 2003-05-01
US20040262814A1 (en) 2004-12-30
KR20040063914A (ko) 2004-07-14

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