EP0746642B1 - Spinnvorrichtung - Google Patents

Spinnvorrichtung Download PDF

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Publication number
EP0746642B1
EP0746642B1 EP95937712A EP95937712A EP0746642B1 EP 0746642 B1 EP0746642 B1 EP 0746642B1 EP 95937712 A EP95937712 A EP 95937712A EP 95937712 A EP95937712 A EP 95937712A EP 0746642 B1 EP0746642 B1 EP 0746642B1
Authority
EP
European Patent Office
Prior art keywords
spinning
filaments
spinneret
distance
bath liquid
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.)
Expired - Lifetime
Application number
EP95937712A
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German (de)
English (en)
French (fr)
Other versions
EP0746642A1 (de
Inventor
Franz Schwenninger
Friedrich Ecker
Wilhelm Feilmair
Christoph Schrempf
Heinrich Firgo
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.)
Lenzing AG
Original Assignee
Lenzing AG
Chemiefaser Lenzing AG
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 Lenzing AG, Chemiefaser Lenzing AG filed Critical Lenzing AG
Priority to EP98117527A priority Critical patent/EP0887444B1/de
Publication of EP0746642A1 publication Critical patent/EP0746642A1/de
Application granted granted Critical
Publication of EP0746642B1 publication Critical patent/EP0746642B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof

Definitions

  • the invention relates to a spinning device for implementation the amine oxide process according to the dry / wet spinning process with a spinneret, which spin holes for extruding Filaments, a container with spin bath liquid, a bundling element which is in the spinning bath liquid is provided for bundling the extruded filaments, and an air gap, which is the distance between the spinneret and the surface the spinning bath liquid is defined.
  • dope is formed by a molding tool, e.g. a spinneret, in a non-falling for the spinning mass Medium, e.g. Air or an inert gas, is extruded, wherein in the case of using a spinneret filaments are formed which are stretched in this medium and then in a spinning bath liquid (precipitation bath) are carried out in which the filaments coagulate.
  • a molding tool e.g. a spinneret
  • a non-falling for the spinning mass Medium e.g. Air or an inert gas
  • Production is generally used as the amine oxide process cellulosic shaped body using tertiary amine oxides Understood.
  • Cellulose is mixed in one dissolved tertiary amine oxide and water, the solution with a Shaped tool and passed through an aqueous precipitation bath, in which the cellulose is precipitated.
  • amine oxide primarily N-methylmorpholine-N-oxide (NMMO) used.
  • NMMO N-methylmorpholine-N-oxide
  • Other amine oxides are e.g. in EP-A - 0 553 070 described.
  • a process for making malleable Cellulose solutions are e.g. known from EP-A-0 356 419.
  • the implementation of the amine oxide process after Dry / wet spinning is e.g. from DE-A - 29 13 589 known.
  • DD-A-218 121 also relates to a Dry / wet spinning process for the production of cellulosic Fibers from cellulose solutions in tertiary amine oxides. Also According to this method, the cellulose solution is divided into one Air gap, that is the distance between the spinneret and the Surface of the spinning bath liquid, spun, stretched and led into an aqueous precipitation bath. In DD-A - 218 121 mentions that the air gap has no adverse consequences for the Spinning security can be shortened if the cellulose solution a polyalkylene ether is added before spinning. A Small air gap is advantageous because of the risk of Gluing of the freshly extruded filaments is reduced.
  • EP-A-0 574 870 describes a dry / wet spinning process for processing solutions of cellulose in tertiary Amine oxides are described and taken advantage of a small Air gap noted. With this spinning process it is after Information in the description section of this patent application possible, with a small air gap and with a high number of To spin spinning holes per unit area. Despite this In spinning operation, there should be no sticking of the Filaments are coming. It is recommended that you contact the spun filaments with the spinning bath liquid in one Spinning funnel. Co-current with the filaments spinning bath liquid is passed through this spinning funnel. The axis of the spinning funnel is essentially vertical to the level of the spinneret, and the flow of the Spin bath liquid is directed from top to bottom, whereby the flow in general through the free fall of the Spin bath liquid is formed.
  • This known spinning device has the disadvantage that the funnel tube of the spinning funnel due to its relative narrow diameter of the filament bundle to be carried out an upper limit with regard to its total cross section sets that for a large-scale implementation of the Procedure is set unsatisfactorily deep. So it is after Experience of the applicant of the present application at a diameter of 6 mm, as described in EP-A - 0 574 870 a filament bundle is only given as an example consisting of a maximum of 100 filaments through the funnel lead as spin bath liquid through the funnel must be transported. This in turn means that at Using such a spinning funnel only one spinneret can be used with a maximum of 100 spinning holes.
  • the funnel tube must be correspondingly larger be, which in turn makes a lot more spin bath liquid drains and must be circulated.
  • This high throughput Spin bath liquid leads to turbulent flows in the Spin bath, which interferes with the dry / wet spinning process.
  • GB-A-1,017,855 a device for Dry / wet spinning of synthetic polymers is described. Again, the use of a spinning funnel is recommended through which spin bath liquid co-current with the extruded fibers is allowed to flow through. The spinneret is about 0.5 cm above the surface of the spin bath.
  • Another one Measure of the spinnability is the duration during which one can spin without spinning errors, the one force technical assistance. Furthermore, even at Using spinnerets with high hole density an adhesive of freshly extruded filaments in the air gap and a titer that is as constant as possible (small titer fluctuations) can be achieved.
  • a preferred embodiment of the invention Spinning device is characterized in that the Bundling element is designed as a deflecting element which not only bundles the filaments, but also be redirected.
  • the deflecting element is formed that it is not when the filaments are deflected turns.
  • this embodiment is as a deflecting element therefore no rotatable roller or roller is provided. This will achieved that torn filaments are not on the Deflection element are wound. This makes it easier Implementation of the amine oxide process.
  • Another preferred embodiment of the invention Spinning device is characterized in that the angle ⁇ Does not exceed 20 °. It has been shown that for the Spinning safety in the dry / wet spinning process entirely it is crucial that the draft angle ⁇ im Air gap is as small as possible and preferably not 20 ° exceeds. This can reduce the risk of sticking Filaments in the space between the spinneret and the surface of the Spinning baths are minimized and spinning security is increased.
  • Spinning device is that the Containers containing a spin bath liquid with a Lifting device communicates with which the container moved towards and away from the spinneret in the vertical direction can be, whereby the distance 1 is changed, and that the Bundling element is arranged so that the distance h despite this movement remains constant.
  • 1 is a container for receiving Spinning bath liquid called, the surface of the Spin bath liquid is indicated with la.
  • spinning mass is extruded through the spinneret 3 and the extruded filaments 4, 5 over the air gap 1 in the Drawn off spin bath liquid in which they coagulate.
  • the Deflection element 2 which is a non-rotatable, cylindrical Rod, the coagulated filaments are bundled, deflected and pulled off diagonally upwards.
  • air gap 1 the distance of the underside of the spinneret 3 from the surface la of the spinning bath liquid defined.
  • the one defined above Angle that the filaments are perpendicular to the surface of the spinning bath liquid is denoted by ⁇ .
  • the reference number 4 denotes a filament which comes from a spinning hole which is located on the outer edge of a circular ring formed by the spinning holes in the spinneret 3.
  • d 1 is the radius (mm) of the circle that limits the circular ring formed by the spinning holes to the outside. With d 0 the distance of this spinning hole to its neighboring spinning hole 5 is designated, whereby in each case the distance between the respective centers of the two neighboring spinning holes is meant.
  • h is the distance between the deflecting element 2 and the spinneret 7, and 1 is the air gap.
  • Figure 2 essentially shows the spinning device of Figure 1, the same parts being designated by the same reference numerals were.
  • the non-rotatable deflection element 2 is via a rigid arm 6 connected to a fixed element 7, which is not connected to the container 1, so that at The element 7 does not raise or lower the container 1 is moved.
  • the element 7 can for example be a wall be.
  • 2 shows two positions of the container 1 shown, the lower position indicated by dashed lines is.
  • the device for lifting and lowering the container 1 is not shown. From Figure 2 it is clear that by lifting and lowering the container 1 the air gap is shortened or can be extended, with the distance h stays the same.
  • FIG. 3 shows a further embodiment of the spinning device according to the invention.
  • the deflecting element 2 by means of a rigid arm 9 on the floor 8 anchored.
  • the arm 9 protrudes through a corresponding opening 11, which is provided in the container 1. So that no liquid is lost from the container 1 is a jacket for sealing 10 provided, which is simply pushed together when the Container 1 by means of a device, not shown is lowered.
  • Example 1 the influence of the angle ⁇ on the spinnability of Document cellulose solutions.
  • Example 4 documents the advantageous effect of a non-rotatable deflection element on the spinnability.
  • a spinner was used, essentially corresponded to Figure 1, but as a bundling element Spinning funnel according to EP-A - 0 574 870 was used.
  • Spinning nozzle was used those described in WO 95/04173, the Disclosure is incorporated herein by reference is.
  • This previously known spinneret (number of holes: 3960; hole diameter: 100 ⁇ m; outer diameter of the nozzle (outermost row of holes) d 1 : 145 mm) has an essentially rotationally symmetrical nozzle body, which has a supply for cooling gas, a supply for cellulose solutions (13, 5% cellulose; temp .: 120 ° C), a ring-shaped, deep-drawn spinning insert made of precious metal with spinning holes, which spinning insert is trough-shaped in cross-section, and has a baffle plate for directing a cooling gas flow onto cellulose filaments that are extruded from the spinning holes (output: 0.025 g / min), so that the cooling gas stream (24 m 3 / h) strikes the extruded cellulose filaments essentially vertically.
  • the spinning holes are essentially uniformly spaced apart from one another in the spinning insert (hole-hole spacing d 0 : 1000 ⁇ m).
  • the air gap 1 had a length of 15 mm.
  • the air in the air gap had a temperature of 24.5 ° C and a water content of 4.5 g water / kg air.
  • Table 1 shows that up to an angle of approx. 40 ° no reduction in the final withdrawal speed and so that no deterioration in spinnability can be observed is. From an angle of 45 °, however, the maximum final take-off speed clearly. At an angle the solution is no longer spinnable at around 61 °.
  • a spinning device which corresponded to FIG. 2 was used, and the spinning nozzle used was again the one described schematically in WO 95/04173 (number of holes: 28,392; hole diameter: 100 ⁇ m; outer diameter of the nozzle (outermost row of holes) d 1 : 155 mm; hole-hole spacing d 0 : 500 ⁇ m).
  • the cellulose solution used had 13.5% cellulose and pointed a temperature of 120 ° C.
  • the output was 0.025 g / min.
  • the air gap 1 had a length of 20 mm.
  • the air in Air gap had a temperature of 12 ° C and a water content of 5 g water / kg air.
  • the filaments were on a cylindrical, non-rotatable Rod 2 deflected and diagonally upwards out of the spinning bath drawn.
  • the distance h was again varied. Based on the Occurrence of spinning defects (filament tears, extreme The filaments bonded to one another) Spinning security of the solution under the given conditions characterized.
  • a high level of spinning security is given when in one Period of more than 15 minutes practically no spinning defects occur. Occur in a period of 15 minutes or spinning errors already accumulated beforehand, so spinning is in technical scale only under constant technical Help possible.
  • the spinning safety is characterized by a time specification, the specification "> 15 min” in Table 3 below meaning that good spinnability (practically no spinning defects within 15 minutes) was given.
  • An indication of, for example, " ⁇ 10 min” means that massive spinning errors occur before 10 minutes have passed after the start of spinning, which force an interruption in spinning.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Artificial Filaments (AREA)
  • Inorganic Fibers (AREA)
EP95937712A 1994-12-22 1995-11-27 Spinnvorrichtung Expired - Lifetime EP0746642B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP98117527A EP0887444B1 (de) 1994-12-22 1995-11-27 Spinnvorrichtung

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AT2391/94 1994-12-22
AT0239194A ATA239194A (de) 1994-12-22 1994-12-22 Vorrichtung zur durchführung eines trocken-/nassspinnverfahrens
PCT/AT1995/000229 WO1996020300A2 (de) 1994-12-22 1995-11-27 Spinnvorrichtung

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP98117527A Division EP0887444B1 (de) 1994-12-22 1995-11-27 Spinnvorrichtung

Publications (2)

Publication Number Publication Date
EP0746642A1 EP0746642A1 (de) 1996-12-11
EP0746642B1 true EP0746642B1 (de) 1999-04-07

Family

ID=3533492

Family Applications (4)

Application Number Title Priority Date Filing Date
EP95937712A Expired - Lifetime EP0746642B1 (de) 1994-12-22 1995-11-27 Spinnvorrichtung
EP98117527A Expired - Lifetime EP0887444B1 (de) 1994-12-22 1995-11-27 Spinnvorrichtung
EP97119866A Withdrawn EP0832995A3 (de) 1994-12-22 1995-12-19 Vorrichtung zur Durchführung eines Trocken-/Nassspinnverfahrens
EP95940073A Expired - Lifetime EP0746641B1 (de) 1994-12-22 1995-12-19 Vorrichtung zur durchführung eines trocken-/nassspinnverfahrens

Family Applications After (3)

Application Number Title Priority Date Filing Date
EP98117527A Expired - Lifetime EP0887444B1 (de) 1994-12-22 1995-11-27 Spinnvorrichtung
EP97119866A Withdrawn EP0832995A3 (de) 1994-12-22 1995-12-19 Vorrichtung zur Durchführung eines Trocken-/Nassspinnverfahrens
EP95940073A Expired - Lifetime EP0746641B1 (de) 1994-12-22 1995-12-19 Vorrichtung zur durchführung eines trocken-/nassspinnverfahrens

Country Status (36)

Country Link
EP (4) EP0746642B1 (ja)
JP (2) JPH09509704A (ja)
KR (1) KR100430918B1 (ja)
CN (3) CN1068910C (ja)
AR (1) AR000362A1 (ja)
AT (5) ATA239194A (ja)
AU (2) AU703733B2 (ja)
BG (1) BG61849B1 (ja)
BR (2) BR9506857A (ja)
CA (2) CA2183627C (ja)
CO (1) CO4480065A1 (ja)
CR (1) CR5234A (ja)
CZ (2) CZ288127B6 (ja)
DE (6) DE19581437B4 (ja)
FI (2) FI963270A0 (ja)
GB (2) GB2301309A (ja)
HK (1) HK1010401A1 (ja)
HR (1) HRP950610B1 (ja)
HU (1) HU220328B (ja)
IL (1) IL116292A (ja)
MA (1) MA23749A1 (ja)
MX (1) MX9603562A (ja)
MY (1) MY115450A (ja)
NO (2) NO963480L (ja)
NZ (1) NZ295314A (ja)
PE (1) PE4397A1 (ja)
PL (1) PL181190B1 (ja)
RO (1) RO114811B1 (ja)
RU (1) RU2132418C1 (ja)
SK (1) SK284686B6 (ja)
TN (1) TNSN95134A1 (ja)
TR (1) TR199501659A2 (ja)
TW (1) TW293040B (ja)
UY (1) UY24131A1 (ja)
WO (2) WO1996020300A2 (ja)
ZA (1) ZA9510655B (ja)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3470557A1 (de) 2017-10-12 2019-04-17 Lenzing Aktiengesellschaft Spinnvorrichtung und verfahren zum anspinnen einer spinnvorrichtung

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AT405531B (de) 1997-06-17 1999-09-27 Chemiefaser Lenzing Ag Verfahren zur herstellung cellulosischer fasern
DE19954152C2 (de) * 1999-11-10 2001-08-09 Thueringisches Inst Textil Verfahren und Vorrichtung zur Herstellung von Cellulosefasern und Cellulosefilamentgarnen
DE10043297B4 (de) * 2000-09-02 2005-12-08 Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. Verfahren zur Herstellung von Cellulosefasern und Cellulosefilamentgarnen
DE10060879B4 (de) * 2000-12-07 2005-08-04 Zimmer Ag Spinntrichtervorrichtung
DE10062083B4 (de) * 2000-12-13 2008-04-10 Ostthüringische Materialprüfgesellschaft Für Textil Und Kunststoffe Mbh Verfahren zur Herstellung von Celluloseendlosformkörpern
DE10206089A1 (de) 2002-02-13 2002-08-14 Zimmer Ag Bersteinsatz
JP4730306B2 (ja) 2004-06-25 2011-07-20 東レ株式会社 繊維束の製造方法
CN1282773C (zh) * 2005-05-30 2006-11-01 武汉大学 二步凝固浴法制备再生纤维素纤维的方法
DE102005040000B4 (de) * 2005-08-23 2010-04-01 Lenzing Ag Mehrfachspinndüsenanordnung und Verfahren mit Absaugung und Beblasung
AT504144B1 (de) * 2006-08-17 2013-04-15 Chemiefaser Lenzing Ag Verfahren zur herstellung von zellulosefasern aus einer lösung von zellulose in einem tertiären aminoxid und vorrichtung zur durchführung des verfahrens
EP2721202A1 (de) * 2011-06-15 2014-04-23 Trützschler Nonwovens GmbH Spinnbadwanne
KR101339137B1 (ko) * 2011-12-22 2013-12-09 최정호 생분해성 원사 제조장치
CN103668504A (zh) * 2013-12-27 2014-03-26 吴江市华宏纺织丝绸有限公司 一种集丝架
CN104099672A (zh) * 2014-07-14 2014-10-15 苏州盛达织带有限公司 真空喷丝装置
CN104611776A (zh) * 2015-01-17 2015-05-13 海兴材料科技有限公司 复合纺丝外环吹冷却及中心上油装置
CN108291344B (zh) * 2015-11-10 2022-02-25 营养与生物科学美国4公司 非织造葡聚糖网
JP2020100902A (ja) * 2017-03-17 2020-07-02 Ｓｐｉｂｅｒ株式会社 乾湿式紡糸装置
EP3505659A1 (de) * 2018-08-30 2019-07-03 Aurotec GmbH Verfahren und vorrichtung zum filamentspinnen mit umlenkung
EP3674454A1 (en) * 2018-12-28 2020-07-01 Lenzing Aktiengesellschaft Cellulose filament process

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AT402738B (de) * 1993-07-28 1997-08-25 Chemiefaser Lenzing Ag Spinndüse

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3470557A1 (de) 2017-10-12 2019-04-17 Lenzing Aktiengesellschaft Spinnvorrichtung und verfahren zum anspinnen einer spinnvorrichtung
WO2019072776A1 (de) 2017-10-12 2019-04-18 Lenzing Aktiengesellschaft Spinnvorrichtung und verfahren zum anspinnen einer spinnvorrichtung
WO2019072779A1 (de) 2017-10-12 2019-04-18 Lenzing Aktiengesellschaft Spinnvorrichtung und verfahren zum anspinnen einer spinnvorrichtung, sowie anspinnvorrichtung
US11718930B2 (en) 2017-10-12 2023-08-08 Lenzing Aktiengesellschaft Spinning device and method for spinning up a spinning device, and spin-up device
US11795582B2 (en) 2017-10-12 2023-10-24 Lenzing Aktiengesellschaft Spinning device and method for spinning up a spinning device

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FI963269A0 (fi) 1996-08-21
MX9603562A (es) 1997-03-29
TR199501659A3 (ja) 1996-07-21
IL116292A (en) 1999-07-14
DE19581437D2 (de) 1997-08-21
CN1145100A (zh) 1997-03-12
GB9617016D0 (en) 1996-09-25
CA2183627C (en) 2006-09-19
CO4480065A1 (es) 1997-07-09
ATA239194A (de) 1996-02-15
FI963270A (fi) 1996-08-21
CR5234A (es) 2001-11-02
TW293040B (ja) 1996-12-11
EP0887444A1 (de) 1998-12-30
MA23749A1 (fr) 1996-07-01
EP0832995A2 (de) 1998-04-01
EP0746641A1 (de) 1996-12-11
CN1132972C (zh) 2003-12-31
AU3863295A (en) 1996-07-19
TR199501659A2 (tr) 1996-07-21
TNSN95134A1 (fr) 1996-02-06
WO1996020300A2 (de) 1996-07-04
RO114811B1 (ro) 1999-07-30
JPH09509703A (ja) 1997-09-30
UY24131A1 (es) 1996-05-17
DE19581437B4 (de) 2004-04-29
NO963480D0 (no) 1996-08-21
HU9602257D0 (en) 1996-10-28
DE19581487D2 (de) 1997-01-16
CA2183627A1 (en) 1996-07-04
DE59510336D1 (de) 2002-09-26
PE4397A1 (es) 1997-02-19
NO963481D0 (no) 1996-08-21
BR9506857A (pt) 1997-09-23
PL181190B1 (pl) 2001-06-29
AU695715B2 (en) 1998-08-20
EP0887444B1 (de) 2002-08-21
SK284686B6 (sk) 2005-09-08
WO1996019598A2 (de) 1996-06-27
CN1068910C (zh) 2001-07-25
CZ291490B6 (cs) 2003-03-12
NO310034B1 (no) 2001-05-07
ATE166677T1 (de) 1998-06-15
GB9617170D0 (en) 1996-09-25
CA2183230A1 (en) 1996-06-27
IL116292A0 (en) 1996-03-31
ZA9510655B (en) 1996-07-09
NZ295314A (en) 1998-10-28
DE59502340D1 (de) 1998-07-02
BG61849B1 (bg) 1998-07-31
ATE222614T1 (de) 2002-09-15
JPH09509704A (ja) 1997-09-30
HRP950610A2 (en) 1997-06-30
GB2301309A (en) 1996-12-04
BG100793A (en) 1997-09-30
HK1010401A1 (en) 1999-06-17
HU220328B (hu) 2001-12-28
NO963481L (no) 1996-10-22
HRP950610B1 (en) 2001-02-28
ATE178665T1 (de) 1999-04-15
WO1996019598A3 (de) 1996-08-22
SK104496A3 (en) 1997-01-08
NO963480L (no) 1996-10-21
FI963269A (fi) 1996-08-21
WO1996020300A3 (de) 1996-09-06
CN1309197A (zh) 2001-08-22
AU4167596A (en) 1996-07-10
AU703733B2 (en) 1999-04-01
AR000362A1 (es) 1997-06-18
ATA902195A (de) 2000-06-15
CZ230596A3 (en) 1996-11-13
EP0832995A3 (de) 1998-07-15
RU2132418C1 (ru) 1999-06-27
CN1146218A (zh) 1997-03-26
FI963270A0 (fi) 1996-08-21
MY115450A (en) 2003-06-30
DE59505595D1 (de) 1999-05-12
CZ288127B6 (cs) 2001-04-11
EP0746642A1 (de) 1996-12-11
HUT78008A (hu) 1999-05-28
GB2301060A (en) 1996-11-27
PL315840A1 (en) 1996-12-09
KR100430918B1 (ko) 2004-07-19
EP0746641B1 (de) 1998-05-27
BR9506858A (pt) 1997-09-23

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