EP0436893A1 - Procédé et dispositif pour l'application uniforme d'un fluide sur un matériau en bande mouvant - Google Patents

Procédé et dispositif pour l'application uniforme d'un fluide sur un matériau en bande mouvant Download PDF

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Publication number
EP0436893A1
EP0436893A1 EP90124816A EP90124816A EP0436893A1 EP 0436893 A1 EP0436893 A1 EP 0436893A1 EP 90124816 A EP90124816 A EP 90124816A EP 90124816 A EP90124816 A EP 90124816A EP 0436893 A1 EP0436893 A1 EP 0436893A1
Authority
EP
European Patent Office
Prior art keywords
distributor
flow channels
individual
individual flow
material web
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
EP90124816A
Other languages
German (de)
English (en)
Other versions
EP0436893B1 (fr
Inventor
Raimund Dr. Dipl.-Ing. Haas
Hans Heist
Peter Dr. Dipl.-Chem. Lehmann
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.)
Hoechst AG
Original Assignee
Hoechst 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 Hoechst AG filed Critical Hoechst AG
Publication of EP0436893A1 publication Critical patent/EP0436893A1/fr
Application granted granted Critical
Publication of EP0436893B1 publication Critical patent/EP0436893B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B1/00—Nozzles, spray heads or other outlets, with or without auxiliary devices such as valves, heating means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
    • B05C5/02—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work the liquid or other fluent material being discharged through an outlet orifice by pressure, e.g. from an outlet device in contact or almost in contact, with the work
    • B05C5/0254—Coating heads with slot-shaped outlet
    • B05C5/0266—Coating heads with slot-shaped outlet adjustable in length, e.g. for coating webs of different width
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
    • B05C5/02—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work the liquid or other fluent material being discharged through an outlet orifice by pressure, e.g. from an outlet device in contact or almost in contact, with the work
    • B05C5/027—Coating heads with several outlets, e.g. aligned transversally to the moving direction of a web to be coated
    • B05C5/0275—Coating heads with several outlets, e.g. aligned transversally to the moving direction of a web to be coated flow controlled, e.g. by a valve
    • B05C5/0279—Coating heads with several outlets, e.g. aligned transversally to the moving direction of a web to be coated flow controlled, e.g. by a valve independently, e.g. individually, flow controlled

Definitions

  • the invention relates to a method for applying a fluid to a moving material web and a device for this method with a distributor for the fluid.
  • the fluid can be a liquid or a gas.
  • the method enables uniform wetting or rinsing of rapidly moving material webs by means of liquids of all kinds, such as water, acids, alkalis or even solutions, the contents of which are brought into interaction with the material web surface.
  • the material web is generally a carrier tape, for example an aluminum tape.
  • the aluminum carrier material for the production of offset printing plates after degreasing which is carried out with pickling solution, must be rinsed very uniformly with water in order to avoid pickling stains.
  • the carrier material is rinsed with surface-active solutions in further process steps, surface-active ingredients being applied to the material web surface by the wetting.
  • the pretreated Support material coated with light-sensitive substances which are applied to the support surface in the form of a solvent-containing wet film and then the solvents are evaporated, so that the light-sensitive substances remain alone. Uniform wetting is also important in the development of exposed offset printing plates, which are brought into contact with developer solution in developing devices.
  • Rinsing or wetting processes can be carried out in a variety of ways, e.g. by means of spray bars arranged transversely to the material web, which are equipped with specially designed spray nozzles to distribute the rinsing liquid.
  • the number and shape of the spray nozzles per unit width depends on the size of the spray volume flow to be applied, the spray liquid being atomized for fine distribution by the nozzle pressure or fanned out across the width of the material web by special design of the nozzles. This is intended to achieve a continuous wetting of the material web over the width and at the same time a rinsing effect.
  • the disadvantage here is that atomization produces aerosols, which are particularly undesirable when rinsing acid or alkali-treated webs.
  • a further disadvantage of spray bars is that the desired uniform distribution over the width of the material web can only be achieved in a narrowly limited volume flow range of the rinsing liquid supplied. With variable Material web speeds are therefore often not guaranteed to ensure uniform rinsing.
  • the superimposition of the spray cones of the adjacent nozzles leads to undesirable fluctuations in the thickness of the applied liquid film, which can cause non-uniform chemical reactions.
  • the object of the invention is to provide a method and a device for uniformly applying a fluid, in particular a liquid, to a moving material web, which in each case ensure splash-free coating, wetting or rinsing of the material web surface while avoiding aerosol formation.
  • volume flow of the fluid to be applied is guided transversely to the direction of travel of the material web and into a plurality of materials flowing side by side onto the material web
  • Individual volume flows are divided, each of which wets a predetermined web width when it hits the material web, the distance between the individual volume flows being selected so that fluid bridges form between the predetermined web widths, which converge to form a uniformly thick fluid film, which covers the material web in its entire coating width covered.
  • the friction pressure loss of the fluid flow transverse to the direction of travel of the material web is selected so that it is substantially less than the friction pressure loss in the individual volume flows.
  • the loss of frictional pressure along the individual volume flows is expediently greater than the maximum hydrostatic pressure difference between the volume flow transverse to the direction of flow and the outflow cross section of the individual volume flows.
  • turbulent flow conditions are set in the individual volume flows, which, when they strike the moving material web, cause a flushing in addition to the uniform coverage with the fluid.
  • the volume flow of the fluid is guided into a distributor arranged transversely to the direction of travel of the material web, and then a fine distribution of the individual volume flows is arranged by a plurality along the distributor axis Single flow channels enforced.
  • the total volume flow over the web width is divided into a large number of individual volume flows, each of which supplies a certain web width with liquid.
  • a device for applying a fluid to a moving material web, with a distributor for the fluid is characterized in that a multi-jet nozzle consists of the distributor and a multiplicity of individual flow channels and that the single flow channels along a surface line or a slot parallel to the distributor axis and in right angles to the distributor axis, at the same distance from each other, are arranged.
  • the multi-jet nozzle consists of a tubular distributor and a wide slot nozzle, which is connected to the distributor via a plane-parallel channel, and the individual flow channels in the form of capillary tubes protrude into the channel of the wide slot nozzle through a perforated outflow bar which leads into the Bottom of the slot die closes.
  • the multi-jet nozzle consists of a hollow cuboid-shaped distributor and a square-shaped discharge body made of solid material, in which perforations parallel to one another are present as individual flow channels, and connects the discharge body to a side wall of the distributor which has wall bores with which the individual flow channels swear.
  • the multi-jet nozzle can also consist of a tubular distributor alone, in the lateral surface of which individual flow channels are arranged along a surface line as a row of holes in the form of parallel bores.
  • the multi-jet nozzle consists of a hollow tubular distributor with movable pistons as end faces, the pistons carrying sealing rings in circumferential annular grooves, which bear against the inner wall of the distributor, and the pistons are also laterally adjustable in the distributor by means of spindles .
  • a further embodiment of the device is characterized in that a multi-jet nozzle consists of a two-part distributor, that the two halves of the distributor are held together by a screw connection and that one half has a smooth edge surface, while the other half has an edge surface equipped with groove grooves , wherein the groove grooves form individual flow channels for the individual volume flows.
  • the simplest version of a single flow channel is a capillary tube with a circular cross section.
  • any other cross section can also be selected, the tubes with their outlet openings advantageously forming a comb-like configuration when the laminar channel flow is set, and the tubes out of the distribution tube by a certain amount of length stick out. This ensures that the individual volume flows in the form of free-falling liquid jets do not partially contract, even at larger distances from the multi-jet nozzle to the material web, and flow instability cause.
  • the advantage of the invention is that the liquid can be applied very evenly and aerosol-free, especially with large safety distances between the application device and the moving material web.
  • the individual volume flows or the liquid exit jets can be applied to the moving material web in a completely splash-free manner, the liquid jets converging on the moving material web by a suitable choice of the channel division across the width and forming a closed liquid film. This process corresponds to a uniform wetting or a homogeneous coating of the moving material web surface.
  • a further advantage of the invention is given by the fact that, by choosing a defined distribution of the length of the individual flow channels over the width of the material web, a variable exit speed and thus can also achieve variable, but predetermined film thicknesses or a certain rinsing effect.
  • a multi-jet nozzle 1 is shown schematically in a perspective view, the tubular distributor 2 of which is supplied with liquid flowing in in the direction of arrow A via an inlet connection 3.
  • the horizontal inlet connection 3 is aligned, for example, with the distributor axis 9 and is attached to one of the end faces 10 of the distributor 2.
  • the inlet connector can also be aligned perpendicular to the distributor axis 9 and in the center of the run at right angles to a surface line of the circumferential surface of the distributor or be arranged elsewhere along the surface line.
  • the friction pressure loss of the volume flow or the fluid flow along the distributor is substantially lower than the friction pressure loss of the individual flow volumes along the individual flow channels.
  • the frictional pressure loss along the individual flow channels is greater than the maximum hydrostatic pressure difference between the chamber of the distributor and the individual outlet openings or outlet cross sections of the individual flow channels, there is a uniform flow in the individual volume flows and self-filling of the distributor chamber.
  • FIG. 2 shows a perspective view, partially broken away, of the multi-jet nozzle 1 according to FIG. 1.
  • the tubular distributor 2 has an inner diameter D and a width B.
  • the individual flow channels 4 i or capillary tubes projecting into the interior of the tubular distributor 2 have a length 1 and protrude from the peripheral surface 11 of the distributor by an amount z.
  • Figure 3 shows in axial section II of Figure 2 the basic arrangement of the capillary tubes.
  • the two outer capillary tubes 4 1 and 4 n protrude by an amount x between 6 and 12 mm further into the interior of the distributor than the other capillary tubes, so that automatic venting of the multi-jet nozzle 1 is achieved at these points, since the upper openings of the two outer capillary tubes protrude from the resulting liquid level a in the distributor 2.
  • Section II-II shows in detail the arrangement of the capillary tubes in the peripheral surface 11 of the distributor 2, for example by an interference fit.
  • the distance y of the outflow openings of the two outer single flow channels 4 1 and 4 n from the material web in the form of a carrier tape 5 is, for example, 9 to 17 mm, while the distance y of the outflow openings of the other equally long single flow channels from the carrier tape 5 is only 3 to 5 mm.
  • the division t of the individual flow channels 4 i is in the range from 1.5 to 7 mm.
  • FIG. 4 shows a perspective view of a partially broken-open second embodiment of the multi-jet nozzle 1, with a slot die 23 and single flow channels 4 i embedded therein in the form of capillary tubes, the index i meaning any capillary tube between 1 and the total number n.
  • the capillary tubes are sealed on the underside of the slot die 23 by a perforated outflow bar 14 against a plane-parallel channel 15 of the slot die 23.
  • the slot die 23 has a cuboid shape and extends on the underside over the width B of the tubular distributor 2.
  • FIG. 5 shows a section III-III transverse to the axis of the multi-jet nozzle in FIG. 4.
  • the capillary tubes protrude from the underside of the outflow bar 14 and extend in the slot 15 of the slot nozzle 23 to close to the connection opening of the distributor 2.
  • one slot half of the slot nozzle can also be equipped with flow channels on one side in such a way that grooves or grooves are milled with a certain pitch t and a channel system of single flow channels is created when the two slot halves are joined without an additional gap.
  • This embodiment is shown in the drawing in FIG. 10.
  • the individual flow channels 4 i protrude like a comb from the outflow bar 14. If the distance between the outflow openings of the individual flow channels 4 i and the carrier tape (not shown) is kept small, for example in the order of magnitude of 1 to 5 mm, the individual volume flows emerging are preferably to be set in a laminar manner. Instead of the capillary tubes, perforations can also be made in the outflow bar 14, in which case the outflow bar 14 must have a corresponding wall thickness. In such an embodiment, turbulent flow conditions preferably occur in the individual volume flows, which are used at larger distances between the outflow opening of the individual flow channels and the carrier tape.
  • FIG. 6 shows a perspective view of a third embodiment of the multi-jet nozzle 1 with a hollow, cuboid-shaped distributor 16, the side wall 24 of which contains wall bores 18 along a surface line 26.
  • a square-shaped discharge body attached to the side wall 24 17 made of solid material is perforated and has perforations or individual flow channels 19 which are aligned with the wall bores 18.
  • the wall bores 18 together with the individual flow channels 19 of the outflow body form the flow channels for wide, constant metering of the liquid.
  • the arrangement of the outflow tubes can also be aligned parallel to the direction of travel of the carrier material, so that the outflow jets strike the material web in the form of a parabola.
  • Figure 7 shows the section along the line IV-IV in the third embodiment and clearly shows that the distributor is cuboid and hollow, while the discharge body is made of solid material, in which the single flow channels 19 are arranged, which with the wall holes 18 in the side wall 24 of the distributor 16 are aligned.
  • FIG. 1 A fourth embodiment of the multi-jet nozzle 1 in section is shown in FIG.
  • This embodiment consists of a tubular distributor 2, in the lateral surface 20 of which there are individual flow channels 21 along a surface line, which are configured, for example, as a row of holes made of mutually parallel bores.
  • This embodiment is preferably used for homogeneous coatings with very small distances between the multi-jet nozzle 1 and the moving material web 5.
  • the outflowing liquid jets immediately form contiguous in the wetting gap Liquid bridges and a closed film curtain, as indicated in Figure 8.
  • the closed film curtain leads to a uniform, coherent film covering on the carrier tape 5.
  • FIG. 9 shows in longitudinal section a fifth embodiment of a multi-jet nozzle 1 with a continuously adjustable coating or rinsing width B.
  • the liquid flows in the middle of a tubular distributor 22 via an inlet nozzle 38 into the distributor chamber and through individual flow channels 4 i in the form of capillary tubes, on the carrier tape 5 to be acted upon.
  • the distributor 22 is designed, for example, as a circularly symmetrical tube with honed and tempered inner wall 29 and is closed on both sides by displaceable pistons 25, 25, which carry sealing rings 27 in circumferential grooves 28.
  • the annular grooves 28 are located opposite the inner wall 29 against which the sealing rings 27, for example O-rings, bear.
  • the pistons 25 are laterally displaceable via spindles 30. By positioning the pistons 25, any coating width B can be set on the carrier tape 5.
  • the capillary tubes are flush with the inner wall 29 of the distributor 22 and protrude on the outside of the distributor wall.
  • FIG. 10 shows a view of a sixth embodiment of a multi-jet nozzle 31, which consists of a two-part distributor 37 exists.
  • the two halves 33, 34 of the distributor of the multi-jet nozzle 31 are held together without a gap by a screw connection 32.
  • the liquid flows through an inlet nozzle 36 in the direction of arrow A into the interior of the multi-jet nozzle 31.
  • one half 33 has a smooth edge surface
  • the other half 34 has a groove surface which is provided with groove grooves and which has a multiplicity of individual flow channels 35 for the exit of the liquid from the multi-jet nozzle 31 onto the carrier tape 5 form.
  • the inlet connector 36 is attached at right angles to the distributor axis and laterally on the grooved half 34.

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  • Coating Apparatus (AREA)
  • Treatment Of Fiber Materials (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Nozzles (AREA)
EP90124816A 1990-01-09 1990-12-19 Procédé et dispositif pour l'application uniforme d'un fluide sur un matériau en bande mouvant Expired - Lifetime EP0436893B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4000405 1990-01-09
DE4000405A DE4000405A1 (de) 1990-01-09 1990-01-09 Verfahren und vorrichtung zum gleichmaessigen aufbringen eines fluids auf eine bewegte materialbahn

Publications (2)

Publication Number Publication Date
EP0436893A1 true EP0436893A1 (fr) 1991-07-17
EP0436893B1 EP0436893B1 (fr) 1995-04-12

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ID=6397765

Family Applications (1)

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EP90124816A Expired - Lifetime EP0436893B1 (fr) 1990-01-09 1990-12-19 Procédé et dispositif pour l'application uniforme d'un fluide sur un matériau en bande mouvant

Country Status (8)

Country Link
US (1) US5264036A (fr)
EP (1) EP0436893B1 (fr)
JP (1) JPH04313363A (fr)
KR (1) KR0179025B1 (fr)
BR (1) BR9100052A (fr)
CA (1) CA2033539A1 (fr)
DE (2) DE4000405A1 (fr)
ES (1) ES2070989T3 (fr)

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DE4212548C1 (en) * 1992-04-15 1993-09-23 Licentia Patent-Verwaltungs-Gmbh, 60596 Frankfurt, De Application of hot melting adhesive on carrier - uses broad slot nozzle comprising several adjacent feed channels which can be timely cut off one after the other
FR2692819A1 (fr) * 1992-06-30 1993-12-31 Chemicals M Perfectionnements au dispositif enducteur et/ou imprégnateur d'un produit liquide ou pâteux sur une nappe de matériau en défilement continu.
FR2692818A1 (fr) * 1992-06-30 1993-12-31 Chemicals M Dispositif enducteur et/ou imprégnateur d'un produit liquide ou pâteux sur une nappe de matériau en défilement continu.
EP0605080A1 (fr) * 1992-12-28 1994-07-06 Yasui Seiki Co., Ltd. Dispositif de revêtement
DE4313880A1 (de) * 1993-04-28 1994-11-03 Koch Marmorit Gmbh Verfahren und Vorrichtung zum gesteuerten Auftragen von Klebern
DE10012344A1 (de) * 2000-03-14 2001-09-20 Voith Paper Patent Gmbh Vorhang-Auftragsverfahren
EP1253241A3 (fr) * 2001-04-27 2004-02-04 Giesecke & Devrient GmbH Procédé et dispositif pour insérer des éléments de sécurité dans une bande de papier
WO2013090575A1 (fr) * 2011-12-13 2013-06-20 3M Innovative Properties Company Rêvetement de contact grâce à l'utilisation d'un collecteur doté de tubes capillaires
CN104279672A (zh) * 2014-10-17 2015-01-14 中山市蓝水能源科技发展有限公司 一种水蓄冷中的布水箱
WO2015149864A1 (fr) * 2014-04-04 2015-10-08 Hewlett-Packard Indigo B.V. Application de fluide
US9981285B2 (en) 2011-12-05 2018-05-29 Akzo Nobel Chemicals International B.V. Device for dosing an additive solution

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JP4551117B2 (ja) * 2004-04-28 2010-09-22 株式会社アトマックス 微粒子噴霧装置
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DE102006020780A1 (de) * 2006-05-03 2007-11-15 Fleissner Gmbh Vorrichtung zum Aufbringen mindestens eines in einem Sammelbehälter aufgenommenen Farbstoffs aus Textilgut
JP4920365B2 (ja) * 2006-10-13 2012-04-18 日本エンバイロ工業株式会社 処理槽
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BRPI0820852B1 (pt) 2007-12-17 2019-11-05 Basf Se processo para a produção de compósitos, e, aparelhagem para a aplicação das misturas de reação líquidas a uma camada externa
USD594348S1 (en) 2008-06-24 2009-06-16 Colgate-Palmolive Company Multiple product package
JP4825256B2 (ja) * 2008-10-31 2011-11-30 日本碍子株式会社 スラリー吐出装置及びスラリーの吐出方法
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CN102580888A (zh) * 2012-03-13 2012-07-18 南京瀚宇彩欣科技有限责任公司 涂布头
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WO2014081051A1 (fr) * 2012-11-21 2014-05-30 엔젯 주식회사 Système à plusieurs buses mobile et procédé de fabrication d'électrode transparente à l'aide dudit système
US20140263759A1 (en) * 2013-03-14 2014-09-18 Millport Associates S.A. Nozzle system and method for manufacturing composite sandwich panels
JP6142268B2 (ja) * 2013-05-28 2017-06-07 兵神装備株式会社 吐出幅可変装置、及び吐出装置
US10357795B2 (en) * 2015-08-26 2019-07-23 3M Innovative Properties Company Method and apparatus for forming articles with non-uniformly patterned coatings
CN107921458B (zh) * 2015-08-26 2021-03-05 3M创新有限公司 用于形成带有不均一不连续的图案化涂层的制品的方法和设备
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DE4212548C1 (en) * 1992-04-15 1993-09-23 Licentia Patent-Verwaltungs-Gmbh, 60596 Frankfurt, De Application of hot melting adhesive on carrier - uses broad slot nozzle comprising several adjacent feed channels which can be timely cut off one after the other
FR2692819A1 (fr) * 1992-06-30 1993-12-31 Chemicals M Perfectionnements au dispositif enducteur et/ou imprégnateur d'un produit liquide ou pâteux sur une nappe de matériau en défilement continu.
FR2692818A1 (fr) * 1992-06-30 1993-12-31 Chemicals M Dispositif enducteur et/ou imprégnateur d'un produit liquide ou pâteux sur une nappe de matériau en défilement continu.
EP0577539A1 (fr) * 1992-06-30 1994-01-05 Société Anonyme : M. CHEMICALS Dispositif enducteur et/ou imprégnateur d'un produit liquide ou pâteux sur une nappe de matériau en défilement continu
EP0605080A1 (fr) * 1992-12-28 1994-07-06 Yasui Seiki Co., Ltd. Dispositif de revêtement
DE4313880A1 (de) * 1993-04-28 1994-11-03 Koch Marmorit Gmbh Verfahren und Vorrichtung zum gesteuerten Auftragen von Klebern
DE10012344A1 (de) * 2000-03-14 2001-09-20 Voith Paper Patent Gmbh Vorhang-Auftragsverfahren
EP1253241A3 (fr) * 2001-04-27 2004-02-04 Giesecke & Devrient GmbH Procédé et dispositif pour insérer des éléments de sécurité dans une bande de papier
US9981285B2 (en) 2011-12-05 2018-05-29 Akzo Nobel Chemicals International B.V. Device for dosing an additive solution
WO2013090575A1 (fr) * 2011-12-13 2013-06-20 3M Innovative Properties Company Rêvetement de contact grâce à l'utilisation d'un collecteur doté de tubes capillaires
US9192960B2 (en) 2011-12-13 2015-11-24 3M Innovative Properties Company Contact coating by use of a manifold provided with capillary tubes
WO2015149864A1 (fr) * 2014-04-04 2015-10-08 Hewlett-Packard Indigo B.V. Application de fluide
CN106573267A (zh) * 2014-04-04 2017-04-19 惠普印迪戈股份公司 流体施加
US9937515B2 (en) 2014-04-04 2018-04-10 Hp Indigo B.V. Fluid application
US10464097B2 (en) 2014-04-04 2019-11-05 Hp Indigo B.V. Fluid application
CN106573267B (zh) * 2014-04-04 2020-02-14 惠普印迪戈股份公司 流体施加
CN104279672A (zh) * 2014-10-17 2015-01-14 中山市蓝水能源科技发展有限公司 一种水蓄冷中的布水箱

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BR9100052A (pt) 1991-10-22
CA2033539A1 (fr) 1991-07-10
US5264036A (en) 1993-11-23
EP0436893B1 (fr) 1995-04-12
KR0179025B1 (ko) 1999-03-20
JPH04313363A (ja) 1992-11-05
ES2070989T3 (es) 1995-06-16
DE4000405A1 (de) 1991-07-11
DE59008895D1 (de) 1995-05-18
KR910014152A (ko) 1991-08-31

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