EP1232302A1 - Verfahren zur herstellung gefärbter aus polyester und polyamid bestehender textiler materialien - Google Patents
Verfahren zur herstellung gefärbter aus polyester und polyamid bestehender textiler materialienInfo
- Publication number
- EP1232302A1 EP1232302A1 EP00979485A EP00979485A EP1232302A1 EP 1232302 A1 EP1232302 A1 EP 1232302A1 EP 00979485 A EP00979485 A EP 00979485A EP 00979485 A EP00979485 A EP 00979485A EP 1232302 A1 EP1232302 A1 EP 1232302A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- dyes
- polyester
- polyamide
- dye
- dyed
- 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- Withdrawn
Links
- 239000004952 Polyamide Substances 0.000 title claims abstract description 18
- 229920002647 polyamide Polymers 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 title claims abstract description 15
- 239000004753 textile Substances 0.000 title claims abstract description 13
- 229920006149 polyester-amide block copolymer Polymers 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 239000000975 dye Substances 0.000 claims abstract description 27
- 239000000984 vat dye Substances 0.000 claims abstract description 22
- 239000000986 disperse dye Substances 0.000 claims abstract description 16
- 229920000728 polyester Polymers 0.000 claims abstract description 7
- 239000000049 pigment Substances 0.000 claims abstract description 6
- 238000004043 dyeing Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 239000004745 nonwoven fabric Substances 0.000 claims description 13
- 102000002151 Microfilament Proteins Human genes 0.000 claims description 9
- 108010040897 Microfilament Proteins Proteins 0.000 claims description 9
- 210000003632 microfilament Anatomy 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 5
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 5
- 238000004040 coloring Methods 0.000 claims description 4
- 239000000988 sulfur dye Substances 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 230000002829 reductive effect Effects 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000008139 complexing agent Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- XUMBMVFBXHLACL-UHFFFAOYSA-N Melanin Chemical compound O=C1C(=O)C(C2=CNC3=C(C(C(=O)C4=C32)=O)C)=C2C4=CNC2=C1C XUMBMVFBXHLACL-UHFFFAOYSA-N 0.000 description 2
- 229920001410 Microfiber Polymers 0.000 description 2
- 239000000980 acid dye Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 2
- 239000003658 microfiber Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical compound OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- -1 Dispersol ® Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010016 exhaust dyeing Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
- D06P3/243—Polyamides; Polyurethanes using vat or sulfur dyes, indigo
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/34—Material containing ester groups
- D06P3/52—Polyesters
- D06P3/54—Polyesters using dispersed dyestuffs
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/82—Textiles which contain different kinds of fibres
- D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
- D06P3/8214—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing ester and amide groups
Definitions
- the invention relates to a process for the production of dyed textile materials consisting of polyester and polyamide.
- Dyeing process for polyester and polyamide fibers are known from the literature (see Ullmann's Encyclopedia of Industrial Chemistry, 6 th Edition, 1998). Disperse dyes are preferred for the dyeing of polyester fibers and acid dyes for the dyeing of polyamide fibers.
- polyester / polyamide-microfiber mixtures are known from the literature (brochure from Sandoz Chemical AG).
- the invention has for its object to provide a method that allows the production of dyed, made of polyester and polyamide, textile materials that allows a fastness to washing for medium and deep shades up to at least 60 ° C.
- the object is achieved by a process in which the textile material is dyed with polyester-dyeing disperse dye or with pigments, excess dye is removed and the dyeing of the polyamide component is carried out with the aid of vat dyes, leuco vat dyes, sulfur dyes or soluble sulfur dyes, the dyes mentioned above being used if it is necessary in order to achieve solubility of the same, encapsulated and, after being drawn up, oxidatively converted into the real dyes.
- wash fastnesses of up to at least 60 ° C are achieved even for medium and deep shades.
- no special aftertreatment is necessary to achieve these color fastnesses, and savings in terms of chemicals and the water required to carry out the process are thereby achieved.
- the coloring of the polyamide portion is preferably carried out with the aid of
- vat dyes made. The vat dyes have proven to be the most stable in terms of their light, wet fastness (fastness to washing, water and sweat).
- a process is particularly preferred in which the polyester portion is first colored with disperse dyes, followed by reductive cleaning at about 80 ° C. and then the polyamide portion is colored. This advantageous variant of the method leads to a higher wet fastness of the colored materials.
- Another preferred variant of the process is that the dyeing is carried out in a dye bath, the excess polyester-dyeing disperse dye being removed simultaneously with the vatting with the aid of reducing agents such as sodium dithionite, glucose or sodium sulfide.
- the dyeing in only one dye bath improves the economics of dyeing, since fewer chemicals, water and only one installation are required.
- Nonwovens are preferably used as textile materials in the process. In this way, these inexpensive materials can be refined using dyeing technology.
- Micro, staple fiber or spunbonded nonwovens are advantageously used as textile materials.
- the dyeing difficulties known with these microfiber nonwovens were surprisingly overcome.
- Microfilament nonwovens consisting of spun-dyed polyester and / or polyamides are particularly preferred. With these microfilament nonwovens, both light and wet color fastness are further increased.
- a microfilament nonwoven fabric consisting of 35 wt .-% polyamide and 65 wt .-% polyester is, in a two-stage exhaust with disperse dyes such as Dispersol ®, and vat dyes, such as Indanthren ®, dyed.
- disperse dyes such as Dispersol ®
- vat dyes such as Indanthren ®
- the dispersol dyes specified in Table 1 are suspended in a first bath with 1 g / l of a dispersant, Setamol ® WS, 0.5 g of a complexing agent, such as Trilon ® TA powder.
- the pH of the dispersion is adjusted to pH 4.5 to 5 with acetic acid.
- the liquor ratio is 1:10.
- the dyeing takes place over 45 min at 130 ° C.
- vat dyes also given in Table 1.
- the dye is dispersed together with 2 ml / l of a protective colloid, such as Dekol ® SN, and 0.5 g / l of a complexing agent, such as Trilon ® TA, and with 2.0 ml / l of 38 ° Be and 2.0 sodium hydroxide solution g / l sodium dithionite fogged.
- the dyeing is carried out at 80 ° C for 30 min.
- the mixture is then cooled to 60 ° C. and oxidized at 60 ° C. for a further 10 minutes.
- 50% hydrogen peroxide solution or a nitrobenzenesulfonic acid is used. Saline. Excess dye is washed out with water.
- Example 2 A microfilament nonwoven fabric according to Example 1 is dyed with a mixture of the disperse and vat dyes given in Table 1 in a one-pot process. Both the disperse dye and the vat dye are dispersed together with 1 g / l dispersant (Setamol ® WS), 0.5 g / l of a complexing agent (Trilon ® TA powder) and 2 ml / l of a protective colloid (Dekol ® SN) adjusted to a pH of 4.5 to 5 with acetic acid. The liquor ratio is 1:10. The dyeing takes place at 130 ° C for 45 min. It is then cooled to 80.degree.
- 1 g / l dispersant Setamol ® WS
- Trilon ® TA powder 0.5 g / l of a complexing agent
- Dekol ® SN ml / l of a protective colloid
- the dyebath is then cooled to 60 ° C. and oxidized at 60 ° C. for a further 10 minutes.
- the dyed microfilament nonwoven fabric is rinsed with water to remove excess dye.
- a microfilament nonwoven fabric according to Example 1 is a two-stage exhaust dyeing with vat dyes, such as Indanthren ®, and a subsequent disperse dye staining with dyes such as Dispersol ® subjected.
- the combined disperse dyes and vat dyes are given in Table 1.
- the dye baths are composed as in Example 1, with the difference that the dyeing is carried out first with the vat dyes.
- a microfilament nonwoven according to Example 1 is dyed in a padding process using the thermosol pad-steam process with disperse and vat dyes.
- the composition of the padding liquor corresponds to the dyebath composition according to Example 2.
- the dye is padded at 100 ° C., dried for 2 minutes and fixed at 215 ° C. for 60 s.
- To develop the vat dye 2 ml / l sodium hydroxide solution 38 ° Be and 2 g / l of a reducing agent, namely sodium dithionite (concentrated hydrosulfite ® ), are padded. Finally, steaming is carried out at 102 ° C. for 60 s and rinsed with water after oxidation.
- a microfilament nonwoven fabric is printed with pigment (70 g / l
- the pigment and the leuco vat dye are in a binder system consisting of water, 9.0 g / l of a defoamer (Respumit ® 3300), 9.0 g / l of a running aid (Emulsifier ® VA02), 110.0 g / l of a binder (Acramin ® CLW), 30.0 g / l of a thickener (Acraconz ® BN) and 9.0 g / l of a melanin resin crosslinker (Cassurit ® HML) are mixed to form a printing paste.
- the printing paste is applied to the nonwoven using printing templates. Then dried at 130 ° C for 1 min and the pigment fixed at 160 ° C for 1 min.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Coloring (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19956780 | 1999-11-25 | ||
| DE19956780A DE19956780A1 (de) | 1999-11-25 | 1999-11-25 | Verfahren zur Herstellung gefärbter aus Polyester und Polyamid bestehender textiler Materialien |
| PCT/EP2000/009804 WO2001038628A1 (de) | 1999-11-25 | 2000-10-06 | Verfahren zur herstellung gefärbter aus polyester und polyamid bestehender textiler materialien |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1232302A1 true EP1232302A1 (de) | 2002-08-21 |
Family
ID=7930313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP00979485A Withdrawn EP1232302A1 (de) | 1999-11-25 | 2000-10-06 | Verfahren zur herstellung gefärbter aus polyester und polyamid bestehender textiler materialien |
Country Status (18)
| Country | Link |
|---|---|
| US (1) | US6802873B1 (de) |
| EP (1) | EP1232302A1 (de) |
| JP (1) | JP2003515012A (de) |
| KR (1) | KR20020060238A (de) |
| CN (1) | CN1391623A (de) |
| AR (1) | AR026565A1 (de) |
| AU (1) | AU1695501A (de) |
| BR (1) | BR0015798A (de) |
| CA (1) | CA2396631A1 (de) |
| CZ (1) | CZ20021803A3 (de) |
| DE (1) | DE19956780A1 (de) |
| EA (1) | EA004691B1 (de) |
| HU (1) | HUP0203027A2 (de) |
| MX (1) | MXPA02003661A (de) |
| PL (1) | PL357240A1 (de) |
| SK (1) | SK6802002A3 (de) |
| TR (1) | TR200201388T2 (de) |
| WO (1) | WO2001038628A1 (de) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10107057A1 (de) * | 2001-02-13 | 2002-08-22 | Freudenberg Carl Kg | Verfahren zur Verbesserung der Farbechtheiten von aus Kunststoffen bestehenden textilen Materialien |
| DE10129366B4 (de) * | 2001-06-20 | 2009-06-10 | Freudenberg, Carl | Mit Pigmenten gefärbter und/oder bedruckter Vliesstoff, Verfahren zu dessen Herstellung und diese umfassende Textilien |
| EP1382730A1 (de) * | 2002-07-15 | 2004-01-21 | Paul Hartmann AG | Kosmetisches Wattepad |
| US7537621B1 (en) | 2005-07-27 | 2009-05-26 | Hbi Branded Apparel Enterprises, Llc | Method for dyeing a nonwoven fabric and apparel formed therefrom |
| TWI324196B (en) * | 2006-12-06 | 2010-05-01 | Taiwan Textile Res Inst | Spunbond non-woven containing bamboo charcoal and method for fabricating the same |
| KR100977677B1 (ko) | 2009-01-16 | 2010-08-24 | 김문탁 | 나일론/폴리에스터 분할형 복합사가 포함된 섬유직물의 분할강화 및 고수축 가공방법 |
| CN101612417B (zh) * | 2009-07-14 | 2012-11-14 | 湖北琪美医疗科技有限公司 | 染色医用敷料的制作方法 |
| CN101906726B (zh) * | 2010-08-19 | 2012-10-24 | 中国纺织科学研究院 | 一种改性聚酯的染色方法 |
| JP6001398B2 (ja) * | 2012-09-28 | 2016-10-05 | 東海染工株式会社 | ポリアリレート繊維の染色方法 |
| CN103215726B (zh) * | 2013-04-22 | 2015-07-15 | 苏州志向纺织科研股份有限公司 | 一种锦涤斜纹竖条面料的制作方法 |
| KR101985468B1 (ko) * | 2014-09-29 | 2019-06-03 | 코오롱인더스트리 주식회사 | 멜란지 외관을 가지는 인공피혁의 염색방법 |
| CN105200821B8 (zh) * | 2015-11-13 | 2017-10-17 | 苏州瑞众新材料科技有限公司 | 一种生物质聚酯与聚酰胺混纺纤维面料的染色方法 |
| WO2020196902A1 (ja) * | 2019-03-27 | 2020-10-01 | 日華化学株式会社 | 液状還元剤組成物及び還元洗浄方法 |
| KR102422533B1 (ko) * | 2021-05-28 | 2022-07-20 | 최인규 | 착색 및 번아웃을 동시에 실시하는 가공방법 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3493316A (en) * | 1966-05-09 | 1970-02-03 | Allied Chem | Dyed fiber products |
| KR940007030B1 (ko) * | 1991-12-11 | 1994-08-03 | 동양나이론 주식회사 | 폴리에스테르-폴리아미드 복합섬유의 염색방법 |
| JPH07279064A (ja) * | 1994-03-31 | 1995-10-24 | Toyobo Co Ltd | ポリエステル繊維/ポリアミド繊維混用繊維製品およびその染色方法 |
-
1999
- 1999-11-25 DE DE19956780A patent/DE19956780A1/de not_active Ceased
-
2000
- 2000-10-06 SK SK680-2002A patent/SK6802002A3/sk unknown
- 2000-10-06 EA EA200200603A patent/EA004691B1/ru not_active IP Right Cessation
- 2000-10-06 MX MXPA02003661A patent/MXPA02003661A/es unknown
- 2000-10-06 EP EP00979485A patent/EP1232302A1/de not_active Withdrawn
- 2000-10-06 JP JP2001539959A patent/JP2003515012A/ja active Pending
- 2000-10-06 KR KR1020027006607A patent/KR20020060238A/ko not_active Ceased
- 2000-10-06 CA CA002396631A patent/CA2396631A1/en not_active Abandoned
- 2000-10-06 US US10/130,652 patent/US6802873B1/en not_active Expired - Fee Related
- 2000-10-06 HU HU0203027A patent/HUP0203027A2/hu not_active Application Discontinuation
- 2000-10-06 AU AU16955/01A patent/AU1695501A/en not_active Abandoned
- 2000-10-06 BR BR0015798-8A patent/BR0015798A/pt not_active IP Right Cessation
- 2000-10-06 CN CN00816095A patent/CN1391623A/zh active Pending
- 2000-10-06 PL PL00357240A patent/PL357240A1/xx not_active Application Discontinuation
- 2000-10-06 CZ CZ20021803A patent/CZ20021803A3/cs unknown
- 2000-10-06 WO PCT/EP2000/009804 patent/WO2001038628A1/de not_active Ceased
- 2000-10-06 TR TR2002/01388T patent/TR200201388T2/xx unknown
- 2000-11-21 AR ARP000106146A patent/AR026565A1/es not_active Application Discontinuation
Non-Patent Citations (1)
| Title |
|---|
| See references of WO0138628A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| MXPA02003661A (es) | 2003-10-14 |
| WO2001038628A1 (de) | 2001-05-31 |
| TR200201388T2 (tr) | 2002-09-23 |
| AU1695501A (en) | 2001-06-04 |
| SK6802002A3 (en) | 2003-01-09 |
| EA004691B1 (ru) | 2004-06-24 |
| US6802873B1 (en) | 2004-10-12 |
| EA200200603A1 (ru) | 2003-02-27 |
| CN1391623A (zh) | 2003-01-15 |
| JP2003515012A (ja) | 2003-04-22 |
| PL357240A1 (en) | 2004-07-26 |
| CA2396631A1 (en) | 2001-05-31 |
| DE19956780A1 (de) | 2001-06-13 |
| BR0015798A (pt) | 2002-07-23 |
| AR026565A1 (es) | 2003-02-19 |
| HUP0203027A2 (en) | 2003-03-28 |
| CZ20021803A3 (cs) | 2002-09-11 |
| KR20020060238A (ko) | 2002-07-16 |
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