CA2425382A1 - Cable with recyclable covering - Google Patents

Cable with recyclable covering Download PDF

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Publication number
CA2425382A1
CA2425382A1 CA002425382A CA2425382A CA2425382A1 CA 2425382 A1 CA2425382 A1 CA 2425382A1 CA 002425382 A CA002425382 A CA 002425382A CA 2425382 A CA2425382 A CA 2425382A CA 2425382 A1 CA2425382 A1 CA 2425382A1
Authority
CA
Canada
Prior art keywords
cable
copolymer
equal
olefin
propylene
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.)
Granted
Application number
CA002425382A
Other languages
French (fr)
Other versions
CA2425382C (en
Inventor
Luca Castellani
Gaia Dell'anna
Cristiana Scelza
Enrico Albizzati
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.)
Prysmian Cavi e Sistemi Energia SRL
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of CA2425382A1 publication Critical patent/CA2425382A1/en
Application granted granted Critical
Publication of CA2425382C publication Critical patent/CA2425382C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/20—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils
    • H01B3/22—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils hydrocarbons
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • 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
    • 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
    • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • 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
    • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • Y10T428/2942—Plural coatings
    • Y10T428/2947—Synthetic resin or polymer in plural coatings, each of different type

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Insulating Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Insulated Conductors (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention describes a cable with recyclable covering, particularly for transporitng or distributing medium or high voltage energy, in which at least one covering layer is based on thermoplastic polymer material comprising a propylene homopolymer or a copolymer of propylene with ethylene or an .prop.-olefin other than propylene in mixture with a dielectric liquid. The cable of the invention possesses superior mechanical and electrical properties, including high dielectric strength, in particular enabling it to be used at high operating temperature.

Claims (51)

1. A cable (1) comprising at least one electrical conductor (2) and at least one extruded covering layer (3, 4, 5) based on a thermoplastic polymer material in admixture with a dielectric liquid, wherein:

- said thermoplastic material comprises a propylene homopolymer or a copolymer of propylene with at least one olefin comonomer selected from ethylene and an .alpha.-olefin other than propylene, said homopolymer or copolymer having a melting point greater than or equal to 140°C and a melting enthalpy of from 30 to 100 J/g;

- said dielectric liquid comprises at least one diphenyl ether, non-substituted or substituted with at least one linear or branched, aliphatic, aromatic or mixed aliphatic and aromatic C1-C30 hydrocarbon radical.
2. A cable as claimed in claim 1, wherein the propylene homopolymer or copolymer has a melting point of from 145 to 170°C.
3. A cable as claimed in claim 1 or 2, wherein the propylene homopolymer or copolymer has a melting enthalpy of from 30 to 85 J/g.
4. A cable as claimed in any one of the preceding claims, wherein the propylene homopolymer or copolymer has a flexural modulus, measured at room temperature, of from 30 to 1400 MPa.
5. A cable as claimed in any one of the preceding claims, wherein the propylene homopolymer or copolymer has a flexural modulus, measured at room temperature, of from 60 to 1000 MPa.
6. A cable as claimed in any one of the preceding claims, wherein the propylene homopolymer or copolymer has a melt flow index, measured at 230°C, of from 0.05 to 10.0 dg/min.
7. A cable as claimed in any one of the preceding claims, wherein the propylene homopolymer or copolymer has a melt flow index, measured at 230°C, of from 0.5 to 5.0 dg/min.
8. A cable as claimed in any one of the preceding claims, wherein the olefin comonomer is present in a quantity of less than or equal to 15 mol%.
9. A cable as claimed in any one of the preceding claims, wherein the olefin comonomer is present in a quantity of less than or equal to 10 mol%.
10. A cable as claimed in any one of the preceding claims, wherein the olefin comonomer is ethylene or an .alpha.-olefin of formula CH2=CH-R, where R is a linear or branched C2-C10 alkyl.
11. A cable as claimed in any one of the preceding claims, wherein the .alpha.-olefin is selected from 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and the like, or combinations thereof.
12. A cable as claimed in any one of the preceding claims, wherein the thermoplastic material is selected from:
(a) a propylene homopolymer or a copolymer of propylene with at least one olefin comonomer selected from ethylene and an .alpha.-olefin other than propylene, having a flexural modulus of from 30 to 900 MPa.
(b) a heterophase copolymer comprising a thermoplastic phase based on propylene and an elastomeric phase based on ethylene copolymerized with an .alpha.-olefin, in which the elastomeric phase is present in a quantity of at least 45 wt% on the total weight of the heterophase copolymer.
13. A cable as claimed in the preceding claim, wherein the propylene homopolymer or copolymer under a) has a flexural modulus of from 50 to 400 MPa.
14. A cable as claimed in claim 12 or 13, wherein the propylene homopolymer or copolymer under a) has:
a melting point of from 140 to 165°C;
a melting enthalpy of from 30 to 80 J/g;
a fraction soluble in boiling diethyl ether in an amount of less than or equal to 12 wt%, having a melting enthalpy of less than or equal to 4 J/g;
a fraction soluble in boiling n-heptane in an amount of from 15 to 60 wt%, having a melting enthalpy of from 10 to 40 J/g; and a fraction insoluble in boiling n-heptane in an amount of from 40 to 85 wt%, having a melting enthalpy of greater than or equal to 45 J/g.
15. A cable as claimed in any one of claims from 12 to 14, wherein the propylene homopolymer or copolymer of a) has:
a fraction soluble in boiling diethyl ether in an amount of from 1 to 10 wt%, having a melting enthalpy of less than or equal to 2 J/g;
a fraction soluble in boiling n-heptane in an amount of from 20 to 50 wt%, having a melting enthalpy of from 15 to 30 J/g; and a fraction insoluble in boiling n-heptane in an amount of from 50 to 80 wt%, having a melting enthalpy of from 50 to 95 J/g.
16. A cable as claimed in claim 12, wherein the .alpha.-olefin included in the elastomeric phase of the heterophase copolymer under b) is propylene.
17. A cable as claimed in the preceding claim, wherein the elastomeric phase consists of an elastomeric copolymer of ethylene and propylene comprising from 15 to 50 wt% of ethylene and from 50 to 85 wt% of propylene on the weight of the elastomeric phase.
18. A cable as claimed in any one of the preceding claims, wherein the base thermoplastic material is the propylene homopolymer or copolymer in mechanical mixture with a low crystallinity polymer having a melting enthalpy of less than or equal to 30 J/g, and a quantity of less than or equal to 70 wt%
on the total weight of the thermoplastic material.
19. A cable as claimed in the preceding claim, wherein the low crystallinity polymer is in a quantity of from 20 to 60 wt% on the total weight of the thermoplastic material.
20. A cable as claimed in claim 18 or 19, wherein the low crystallinity polymer is a copolymer of ethylene with a C3-C12 .alpha.-olefin.
21. A cable as claimed in claim 18 or 19, wherein the low crystallinity polymer is a copolymer of ethylene with an .alpha.-olefin and a diene.
22. A cable as claimed in claim 20 or 21, wherein the ethylene copolymer is selected from (i) a copolymer having the following monomer composition: 35-90 mol%
of ethylene; 10-65 mol% of .alpha.-olefin; 0-10 mol% of a diene;
(ii) a copolymer having the following monomer composition: 75-97 mol%
of ethylene; 3-25 mol% of .alpha.-olefin; 0-5 mol% of a diene.
23. A cable as claimed in the preceding claim, wherein the ethylene copolymer is selected from a copolymer having the following monomer composition: 90-95 mol% of ethylene; 5-10 mol% of .alpha.-olefin; 0-2 mol% of a diene.
24. A cable as claimed in any one of claims from 20 to 23, wherein the .alpha.-olefin is selected from propylene, 1-hexene and 1-octene.
25. A cable as claimed in any one of claims from 20 to 24, wherein the diene has from 4 to 20 carbon atoms.
26. A cable as claimed in any one of claims from 20 to 25, wherein the diene is selected from a conjugated or non-conjugated linear diolefin, and a monocyclic or polycyclic diene.
27. A cable as claimed in any one of claims from 20 to 26, wherein the diene is selected from 1,3-butadiene, 1,4-hexadiene, 1,6-octadiene, 1,4-cyclohexadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, or their mixtures and the like.
28. A cable as claimed in any one of the preceding claims, wherein the hydrocarbon radical has from 1 to 24 carbon atoms.
29. A cable as claimed in any one of the preceding claims, wherein the dielectric liquid comprises at least one diphenyl ether having the following structural formula:

where R1 and R2 are equal or different and represent hydrogen, a phenyl group non-substituted or substituted by at least one alkyl group, or an alkyl group non-substituted or substituted by at least one phenyl.
30. A cable as claimed in the preceding claim, wherein the alkyl group has from 1 to 20 carbon atoms.
31. A cable as claimed in any one of the preceding claims, wherein the dielectric liquid is selected from phenyl toluyl ether, 2,3'-ditoluyl ether, 2,2'-ditoluyl ether, 2,4'-ditoluyl ether, 3,3'-ditoluyl ether, 3,4'-ditoluyl ether, 4,4'-ditoluyl ether, octadecyl diphenyl ether either as pure isomers or in mixture with each other.
32. A cable as claimed in any one of the preceding claims, wherein the ratio of number of aryl carbon atoms to number of total carbon atoms of the dielectric liquid is greater than or equal to 0.4.
33. A cable as claimed in any one of the preceding claims, wherein the ratio of number of aryl carbon atoms to number of total carbon atoms of the dielectric liquid is greater than or equal to 0.7.
34. A cable as claimed in any one of the preceding claims, wherein the diphenyl ether has a dielectric constant, at 25°C, of less than or equal to 8.
35. A cable as claimed in any one of the preceding claims, wherein the diphenyl ether has a dielectric constant, at 25°C, of less than or equal to 4.
36. A cable as claimed in any one of the preceding claims, wherein the dielectric liquid has a kinematic viscosity at 20°C of between 1 and 100 mm2/s.
37. A cable as claimed in any one of the preceding claims, wherein the dielectric liquid has a kinematic viscosity at 20°C of between 3 and 50 mm2/s.
38. A cable as claimed in any one of the preceding claims, wherein the diphenyl ether has a hydrogen absorption capacity of greater than or equal to mm3/min.
39. A cable as claimed in the preceding claim, wherein the hydrogen absorption capacity is greater than or equal to 50 mm3/min.
40. A cable as claimed in any one of the preceding claims, wherein an epoxy resin is added to the dielectric liquid in a quantity of less than or equal to wt% on the weight of the liquid.
41. A cable as claimed in any one of the preceding claims, wherein the weight ratio of dielectric liquid to base polymer material is from 1:99 to 25:75.
42. A cable as claimed in any one of the preceding claims, wherein the weight ratio of dielectric liquid to base polymer material is from 2:98 to 20:80.
43. A cable as claimed in any one of the preceding claims, wherein the weight ratio of dielectric liquid to base polymer material is from 3:97 to 15:85.
44. A cable as claimed in any one of the preceding claims, wherein the base polymer material is selected from propylene homopolymers or copolymers comprising at least 40 wt% of amorphous phase, on the total polymer weight.
45. A cable as claimed in any one of the preceding claims, wherein the extruded covering layer is a layer (4) with electrical insulation properties.
46. A cable as claimed in any one of claims from 1 to 44, wherein the extruded covering layer is a layer (3, 5) with semiconductive properties.
47. A cable as claimed in the preceding claim, wherein a conductive filler is dispersed in the layer with semiconductive properties.
48. A cable as claimed in any one of the preceding claims, wherein at least one layer with electrical insulation properties and at least one layer with semiconductive properties are present.
49. A polymer composition comprising a thermoplastic polymer material in admixture with a dielectric liquid in accordance with any one of claims from 1 to 44.
50. Use of a polymer composition as claimed in claim 49, as base polymer material for the preparation of a covering layer (4) with electrical insulation properties.
51. Use of a polymer composition as claimed in claim 49, as base polymer material for the preparation of a covering layer (3,5) with semiconductive properties.
CA002425382A 2000-09-28 2001-08-22 Cable with recyclable covering Expired - Lifetime CA2425382C (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP00121110 2000-09-28
EP00121110.1 2000-09-28
US23673500P 2000-10-02 2000-10-02
PCT/EP2001/009700 WO2002027731A1 (en) 2000-09-28 2001-08-22 Cable with recyclable covering

Publications (2)

Publication Number Publication Date
CA2425382A1 true CA2425382A1 (en) 2002-04-04
CA2425382C CA2425382C (en) 2010-01-12

Family

ID=29762590

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002425382A Expired - Lifetime CA2425382C (en) 2000-09-28 2001-08-22 Cable with recyclable covering

Country Status (14)

Country Link
EP (1) EP1323171B1 (en)
JP (1) JP4875282B2 (en)
KR (1) KR100777011B1 (en)
CN (1) CN1229821C (en)
AR (1) AR037079A1 (en)
AT (1) ATE285112T1 (en)
AU (2) AU8403001A (en)
BR (1) BR0114264B1 (en)
CA (1) CA2425382C (en)
DE (1) DE60107864T2 (en)
ES (1) ES2234874T3 (en)
HU (1) HU229633B1 (en)
NZ (1) NZ525495A (en)
WO (1) WO2002027731A1 (en)

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WO2002047092A1 (en) 2000-12-06 2002-06-13 Pirelli S.P.A. Process for producing a cable with a recyclable coating
WO2004066317A1 (en) * 2003-01-20 2004-08-05 Gabriele Perego Cable with recycable covering layer
JP2007515742A (en) * 2003-07-25 2007-06-14 ピレリ・アンド・チ・ソチエタ・ペル・アツィオーニ A continuous method of manufacturing electrical cables
AU2005337789B2 (en) 2005-10-25 2012-09-13 Prysmian Cavi E Sistemi Energia S.R.L. Energy cable comprising a dielectric fluid and a mixture of thermoplastic polymers
WO2008058572A1 (en) * 2006-11-15 2008-05-22 Prysmian S.P.A. Energy cable
WO2009000326A1 (en) 2007-06-28 2008-12-31 Prysmian S.P.A. Energy cable
CN102822257B (en) 2010-01-29 2014-03-12 普睿司曼股份公司 Energy cable
RU2539359C1 (en) * 2010-11-25 2015-01-20 Призмиан С.П.А. Power cable containing thermoplastic and electric insulating layer with voltage stabiliser
BR112013014593B1 (en) 2010-12-23 2019-12-10 Prysmian Spa process for making a power cord, and apparatus for making a power cord
US9576703B2 (en) 2010-12-23 2017-02-21 Prysmian S.P.A. Energy cable having stabilized dielectric resistance
US20140255692A1 (en) * 2011-08-04 2014-09-11 Gabriele Perego Energy cable having a thermoplastic electrically insulating layer
US9697927B2 (en) 2011-12-23 2017-07-04 Prysmian S.P.A. Cable comprising an element indicating water infiltration and method using said element
US10297372B2 (en) 2012-05-18 2019-05-21 Prysmian S.P.A Process for producing an energy cable having a thermoplastic electrically insulating layer
ES2749509T3 (en) * 2012-05-18 2020-03-20 Prysmian Spa Procedure for producing a power cable featuring a thermoplastic layer of electrical insulation
EP2711938B1 (en) * 2012-09-25 2014-11-26 Nexans Silicone multilayer insulation for electric cable
KR102003567B1 (en) * 2013-02-14 2019-07-24 한국전력공사 Power cable
KR102003568B1 (en) * 2013-02-14 2019-07-24 한국전력공사 Power cable
US10662323B2 (en) 2013-08-12 2020-05-26 Nkt Hv Cables Ab Thermoplastic blend formulations for cable insulations
WO2016005791A1 (en) 2014-07-08 2016-01-14 Prysmian S.P.A. Energy cable having a thermoplastic electrically insulating layer
EP3234013B1 (en) 2014-12-17 2018-11-28 Prysmian S.p.A. Energy cable having a cold-strippable semiconductive layer
CN108350583B (en) 2015-09-25 2020-09-08 普睿司曼股份公司 Aluminum power cable coated with tetrazolium compound corrosion inhibitor
DK3365952T3 (en) 2015-10-23 2020-06-15 Prysmian Spa Assembly for electrical cables with thermoplastic insulation and method of manufacture thereof
EP3549144A1 (en) 2016-11-30 2019-10-09 Prysmian S.p.A. Power cable
US20200126687A1 (en) 2016-12-27 2020-04-23 Prysmian S.p. A. Electric cable having a protecting layer
FR3068038B1 (en) * 2017-06-21 2020-09-18 Nexans POLYMERIC COMPOSITION INCLUDING A POLAR DIELECTRIC LIQUID
DK3695424T3 (en) * 2017-10-12 2022-09-12 Prysmian Spa Electric cable with improved thermoplastic insulation layer
KR102603200B1 (en) * 2017-12-27 2023-11-16 주식회사 엘지화학 Polypropylene resin composition for insulating material of power cable
US20220112367A1 (en) * 2018-06-13 2022-04-14 Nexans Polymer composition comprising a dielectric liquid of improved polarity
KR102097237B1 (en) * 2019-06-19 2020-04-07 엘에스전선 주식회사 Power cable
KR102097238B1 (en) * 2019-06-19 2020-04-07 엘에스전선 주식회사 Power cable
JP6800362B1 (en) 2020-03-30 2020-12-16 古河電気工業株式会社 Power cable and manufacturing method of power cable

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Also Published As

Publication number Publication date
AU8403001A (en) 2002-04-08
ATE285112T1 (en) 2005-01-15
CN1229821C (en) 2005-11-30
CN1466766A (en) 2004-01-07
DE60107864T2 (en) 2005-12-22
BR0114264B1 (en) 2011-10-18
JP2004510299A (en) 2004-04-02
DE60107864D1 (en) 2005-01-20
BR0114264A (en) 2004-01-06
CA2425382C (en) 2010-01-12
HUP0303679A3 (en) 2010-01-28
AR037079A1 (en) 2004-10-20
KR100777011B1 (en) 2007-11-16
HU229633B1 (en) 2014-03-28
WO2002027731A1 (en) 2002-04-04
NZ525495A (en) 2004-07-30
KR20040030420A (en) 2004-04-09
HUP0303679A2 (en) 2004-03-01
AU2001284030B2 (en) 2006-01-12
JP4875282B2 (en) 2012-02-15
EP1323171A1 (en) 2003-07-02
ES2234874T3 (en) 2005-07-01
EP1323171B1 (en) 2004-12-15

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Effective date: 20210823