EP1226304A1 - Synthetisches leder - Google Patents

Synthetisches leder

Info

Publication number
EP1226304A1
EP1226304A1 EP00960579A EP00960579A EP1226304A1 EP 1226304 A1 EP1226304 A1 EP 1226304A1 EP 00960579 A EP00960579 A EP 00960579A EP 00960579 A EP00960579 A EP 00960579A EP 1226304 A1 EP1226304 A1 EP 1226304A1
Authority
EP
European Patent Office
Prior art keywords
synthetic leather
nonwoven fabric
continuous filaments
polymer
dtex
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Withdrawn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
EP00960579A
Other languages
German (de)
English (en)
French (fr)
Inventor
Rudolf Wagner
Robert Groten
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.)
Carl Freudenberg KG
Original Assignee
Carl Freudenberg KG
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 Carl Freudenberg KG filed Critical Carl Freudenberg KG
Publication of EP1226304A1 publication Critical patent/EP1226304A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/016—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the fineness
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B23/00—Uppers; Boot legs; Stiffeners; Other single parts of footwear
    • A43B23/02—Uppers; Boot legs
    • A43B23/0205—Uppers; Boot legs characterised by the material
    • A43B23/0215—Plastics or artificial leather
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B23/00—Uppers; Boot legs; Stiffeners; Other single parts of footwear
    • A43B23/07—Linings therefor
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B23/00—Uppers; Boot legs; Stiffeners; Other single parts of footwear
    • A43B23/08—Heel stiffeners; Toe stiffeners
    • A43B23/16—Heel stiffeners; Toe stiffeners made of impregnated fabrics, plastics or the like
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/018—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the shape
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/10—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically
    • D04H3/11—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically by fluid jet
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/12—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with filaments or yarns secured together by chemical or thermo-activatable bonding agents, e.g. adhesives, applied or incorporated in liquid or solid form
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/16—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0004—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes

Definitions

  • the invention relates to a synthetic leather, consisting of a nonwoven fabric impregnated and / or coated with a polymer and having basis weights of 100 to 500 g / m 2 and tensile strengths in the longitudinal and transverse directions> 300 N / 5 cm
  • nonwovens made of ultrafine, entangled filaments which have a layer structure and can be processed into synthetic leather by impregnation and / or coating with polymers.
  • Those starting fibers are preferably those of the "island-in-sea" type "in which the ultrafine fibers are released by dissolving the matrix polymer.
  • the use of noticeable starting fibers is also specified
  • Document EP-A 0 624 676 discloses nonwovens made from ultra-fine fibers and processes for their production from bicomponent fibers.
  • the starting polymers of the bicomponent fibers are said to have a melting point difference of 30 to 180 ° C. and are spun as multi-segment fibers
  • Bicomponent fibers are subjected to a point calendering, in which only the fiber component with the lower melting point is melted and is solidified.
  • at least 70% of the nonwoven fabric formed from the multi-segment fibers is split into the ultrafine sub-segment fibers by mechanical action on the fibers.
  • the nonwovens obtained in this way achieve tensile strength values in the longitudinal and transverse directions of up to a maximum of 260 N / 5 cm and can be used as bed linen, scrubber for sanitary products such as handkerchiefs, diapers, padding for sleeping bags, synthetic leather, thermal insulation materials and others.
  • the invention has for its object to provide inexpensive and high tensile synthetic leather and a method for their production.
  • the object is achieved by a synthetic leather which consists of a nonwoven fabric impregnated and / or coated with a polymer and having basis weights of 100 to 500 g / m 2 and tensile strengths in the longitudinal and transverse directions> 300 N / 5 cm, the nonwoven fabric consists of melt-spun, aerodynamically stretched and immediately deposited multi-component continuous filaments with a titer ⁇ 2 dtex and the multi-component continuous filaments after pre-consolidation are at least 90% split and consolidated into super-micro continuous filaments with a titer ⁇ 0.2 dtex.
  • a synthetic leather has high tensile strengths at a comparatively low weight and is therefore inexpensive. Furthermore, it is similar to natural materials in terms of its grip.
  • the synthetic leather is preferably one in which the multicomponent continuous filament is a bicomponent continuous filament made of two incompatible polymers, in particular a polyester and a polyamide.
  • a continuous bicomponent filament has good splittability Super micro continuous filaments and creates a favorable ratio of strength to basis weight.
  • the synthetic leather is preferably one in which the multicomponent continuous filaments have a cross section with an orange-like multisegment structure, the segments alternately each containing one of the two incompatible polymers.
  • the multicomponent continuous filaments have a cross section with an orange-like multisegment structure, the segments alternately each containing one of the two incompatible polymers.
  • this orange-like multi-segment structure of the multi-component continuous filaments other arrangements of the incompatible polymers in the multi-component continuous filament, such as side-by-side or chrysanthemum leaf-like arrangements, are also possible. Such arrangements of the incompatible polymers in the multicomponent continuous filament have proven to be very easy to split.
  • the synthetic leather is preferably also one in which at least one of the incompatible polymers forming the multicomponent filament contains an additive, such as color pigments, permanently acting antistatic agents and / or additives which influence the hydrophilic or hydrophobic properties in amounts of up to 10% by weight.
  • an additive such as color pigments, permanently acting antistatic agents and / or additives which influence the hydrophilic or hydrophobic properties in amounts of up to 10% by weight.
  • the synthetic leather consisting of spun-dyed fibers has a very high high-temperature light fastness. Furthermore, the additives can reduce or avoid static charges and improve the moisture transport properties.
  • a synthetic leather in which the nonwoven is impregnated with 10 to 45 percent by weight of a polymer, based on the starting weight of the nonwoven, is particularly preferred. With the same or even superior strength properties of the synthetic leather, less impregnation of the starting nonwoven is necessary according to the invention than with previously known products.
  • the process according to the invention for the production of a synthetic leather consists in that multicomponent continuous filaments are spun from the melt, aerodynamically stretched and immediately deposited into a nonwoven fabric, pre-consolidation takes place and the nonwoven fabric is solidified by high-pressure fluid jets as in supermicro continuous filaments with a titer ⁇ 0.2 dtex split and then impregnated and / or coated with a polymer.
  • the synthetic leathers thus obtained are very uniform in terms of their thickness, they have an isotropic thread distribution, have no tendency to delaminate and are distinguished by high modulus values.
  • the process for producing the synthetic leather is advantageously carried out in such a way that the solidification and splitting of the multicomponent continuous filaments takes place in that the pre-consolidated nonwoven fabric is subjected to high pressure water jets alternately on both sides.
  • the starting nonwoven fabric for the synthetic leather therefore has a good surface and a degree of splitting of the multi-component continuous filaments> 90%.
  • the process for splitting and solidifying the multicomponent continuous filament is advantageously carried out on an aggregate with rotating sieve drums. Such a unit allows the construction of very compact systems.
  • the non-woven fabric split into super-micro continuous filaments and consolidated with high-pressure fluid jets is impregnated with a polyurethane dissolved in dimethylformamide and the polymer is coagulated in a known manner. It is particularly preferred in the production of the synthetic leather according to the invention that the impregnation with a polymer is carried out with the aid of an aqueous polyurethane latex dispersion and then coagulated. This form of impregnation of the starting nonwoven does not leave any residues on solvents and is therefore environmentally friendly.
  • a method is particularly preferred in which the multicomponent continuous filaments are spin-dyed.
  • the integration of the dyes in the polymer fibers leads to excellent hot light fastness.
  • Writing effect is understood to mean the exposure of microfiber ends on the surface of the synthetic leather, which can be oriented in a visible manner.
  • the synthetic leathers produced according to the invention are particularly suitable for use in the shoe industry as upper material, inner lining, trimming or heel lining. They are still suitable as clothing materials. Because of their good mechanical strength and in the case of spun-dyed products because of their high fastness to hot light, the synthetic leathers according to the invention are suitable for use in automotive interior fittings for the production of dashboards, side panels, hat racks, headlining linings or trunk linings and for the manufacture of upholstered furniture, in particular as upholstery materials suitable for armchairs, sofas or chairs.
  • a filament pile with a basis weight of 160 g / m 2 is produced from a polyester-polyamide (PES-PA) bicomponent filament and subjected to water jet needling at pressures of up to 250 bar on both sides.
  • the bicomponent continuous filaments have a titer of ⁇ 0.2 dtex after the water jet needling, which leads to a simultaneous splitting of the starting filaments.
  • the consolidated nonwoven is subjected to an impregnation with a polyurethane (PUR) dissolved in dimethylformamide (DMF), about 12% by weight of PUR being applied based on the initial weight of the nonwoven.
  • PUR polyurethane
  • DMF dimethylformamide
  • the polymer-impregnated nonwoven fabric obtained is sanded on the surface and, for example, equipped with special silicones to improve the grip.
  • a synthetic leather with a nubuck-like surface is obtained.
  • a filament pile with a basis weight of 110 g / m 2 is produced from a PES-PA bicomponent continuous filament and subjected to water jet needling at pressures of up to 250 bar on both sides.
  • the bicomponent continuous filaments have a titer of ⁇ 0.2 dtex after the water jet needling, which leads to a simultaneous splitting of the starting filaments.
  • the consolidated nonwoven fabric is subjected to an impregnation with an aqueous polyurethane latex dispersion, about 10% by weight of PUR being applied based on the starting weight of the nonwoven fabric.
  • the polyurethane is coagulated by treatment with hot water or saturated steam and then dried and crosslinked at approx. 150 to 160 ° C.
  • the polymer impregnated nonwoven obtained is sanded on the surface and equipped with special silicones to improve the grip, for example.
  • a synthetic leather with a nubuck-like surface is obtained.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Nonwoven Fabrics (AREA)
EP00960579A 1999-10-05 2000-09-01 Synthetisches leder Withdrawn EP1226304A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19947869A DE19947869A1 (de) 1999-10-05 1999-10-05 Synthetisches Leder
DE19947869 1999-10-05
PCT/EP2000/008548 WO2001025530A1 (de) 1999-10-05 2000-09-01 Synthetisches leder

Publications (1)

Publication Number Publication Date
EP1226304A1 true EP1226304A1 (de) 2002-07-31

Family

ID=7924512

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00960579A Withdrawn EP1226304A1 (de) 1999-10-05 2000-09-01 Synthetisches leder

Country Status (22)

Country Link
US (1) US6838043B1 (zh)
EP (1) EP1226304A1 (zh)
JP (1) JP2003511568A (zh)
KR (1) KR20020043605A (zh)
CN (1) CN1174143C (zh)
AU (1) AU772800B2 (zh)
BG (1) BG106564A (zh)
BR (1) BR0014505A (zh)
CA (1) CA2386390A1 (zh)
CZ (1) CZ20021153A3 (zh)
DE (1) DE19947869A1 (zh)
EE (1) EE200200167A (zh)
HU (1) HUP0203698A2 (zh)
IL (1) IL148867A0 (zh)
MX (1) MXPA02002829A (zh)
NO (1) NO20021519L (zh)
PL (1) PL354450A1 (zh)
RU (1) RU2233359C2 (zh)
SK (1) SK4582002A3 (zh)
TR (1) TR200200908T2 (zh)
WO (1) WO2001025530A1 (zh)
ZA (1) ZA200202652B (zh)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10132255A1 (de) * 2001-07-04 2003-01-23 Achter Viktor Gmbh & Co Kg Kunstwildleder und ein Herstellungsverfahren hierfür
DE10258112B4 (de) * 2002-12-11 2007-03-22 Carl Freudenberg Kg Verfahren zur Herstellung eines Flächengebildes aus zumindest teilweise gesplitteten Garnen, Fasern oder Filamenten
DE102005014317A1 (de) * 2005-03-30 2006-10-05 Carl Freudenberg Kg Synthetisches Leder, Verfahren zu dessen Herstellung und dessen Verwendung
TW200738933A (en) * 2006-02-28 2007-10-16 Kuraray Co An artificial leather sheet and the process for preparing thereof
TWI321601B (en) * 2007-08-20 2010-03-11 San Fang Chemical Industry Co Manufacturing method for environment friendly ultra-fine filament products having low resistance to deformation and high physical property
EP2251473A1 (en) * 2009-04-29 2010-11-17 Fiscagomma S.p.A. Label
CN102234938B (zh) * 2010-05-07 2014-09-24 福建兰峰制革有限公司 超纤牛巴革的制造工艺
US20130089718A1 (en) * 2010-06-15 2013-04-11 Lanxess Deutschland Gmbh Cut-to-size format
DE102011056933A1 (de) * 2011-12-22 2013-06-27 Bayerische Motoren Werke Aktiengesellschaft Interieurbauteil für ein Kraftfahrzeug
DE102012018852B4 (de) * 2012-09-25 2016-01-07 Carl Freudenberg Kg Verwendung von Mikrofaser-Vliesstoffen zur Herstellung dekorativer Schichtpressstoffe
US9284663B2 (en) * 2013-01-22 2016-03-15 Allasso Industries, Inc. Articles containing woven or non-woven ultra-high surface area macro polymeric fibers
TWI510357B (zh) * 2013-02-08 2015-12-01 Shu Chieh Wang 用於鞋加強件之複合層狀結構及其製造方法

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DE2539725C3 (de) * 1974-09-13 1979-12-06 Asahi Kasei Kogyo K.K., Osaka (Japan) Auf einer Oberfläche eine Florschicht aufweisendes, wildlederähnliches Kunstleder und Verfahren zu seiner Herstellung
JPS539301A (en) * 1976-07-12 1978-01-27 Mitsubishi Rayon Co Production of leather like sheet structre
US4390566A (en) * 1981-03-09 1983-06-28 Toray Industries, Inc. Method of producing soft sheet
EP0090397B1 (en) * 1982-03-31 1990-01-24 Toray Industries, Inc. Ultrafine fiber entangled sheet and method of producing the same
FR2546536B1 (fr) * 1983-05-25 1985-08-16 Rhone Poulenc Fibres Procede pour le traitement de nappes non tissees et produit obtenu
TW246699B (zh) * 1992-10-05 1995-05-01 Unitika Ltd
FR2749860B1 (fr) * 1996-06-17 1998-08-28 Freudenberg Spunweb Sa Nappe non tissee formee de filaments continus tres fins
JP3187357B2 (ja) * 1997-11-10 2001-07-11 帝人株式会社 皮革様シート状物およびその製造方法

Non-Patent Citations (1)

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Title
See references of WO0125530A1 *

Also Published As

Publication number Publication date
BG106564A (bg) 2002-10-31
US6838043B1 (en) 2005-01-04
CN1377433A (zh) 2002-10-30
EE200200167A (et) 2003-04-15
DE19947869A1 (de) 2001-05-03
SK4582002A3 (en) 2002-08-06
AU7282500A (en) 2001-05-10
WO2001025530A1 (de) 2001-04-12
JP2003511568A (ja) 2003-03-25
BR0014505A (pt) 2002-08-27
HUP0203698A2 (en) 2003-04-28
CA2386390A1 (en) 2001-04-12
CZ20021153A3 (cs) 2002-06-12
PL354450A1 (en) 2004-01-12
IL148867A0 (en) 2002-09-12
ZA200202652B (en) 2005-09-28
TR200200908T2 (tr) 2002-08-21
AU772800B2 (en) 2004-05-06
KR20020043605A (ko) 2002-06-10
RU2233359C2 (ru) 2004-07-27
CN1174143C (zh) 2004-11-03
NO20021519D0 (no) 2002-03-26
NO20021519L (no) 2002-03-26
MXPA02002829A (es) 2003-10-14

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