EP0694088B1 - Process for producing a base mould for electrolycally producing seamless rotary screen printing stencils, in particular of nickel - Google Patents
Process for producing a base mould for electrolycally producing seamless rotary screen printing stencils, in particular of nickel Download PDFInfo
- Publication number
- EP0694088B1 EP0694088B1 EP95908917A EP95908917A EP0694088B1 EP 0694088 B1 EP0694088 B1 EP 0694088B1 EP 95908917 A EP95908917 A EP 95908917A EP 95908917 A EP95908917 A EP 95908917A EP 0694088 B1 EP0694088 B1 EP 0694088B1
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- EP
- European Patent Office
- Prior art keywords
- indentations
- grid
- sensitive layer
- process according
- base mould
- Prior art date
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- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000010022 rotary screen printing Methods 0.000 title claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 26
- 229910052759 nickel Inorganic materials 0.000 title claims description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 238000007373 indentation Methods 0.000 claims abstract 15
- 239000011231 conductive filler Substances 0.000 claims abstract 3
- 238000007650 screen-printing Methods 0.000 claims description 11
- 238000005530 etching Methods 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 3
- 229920003002 synthetic resin Polymers 0.000 claims description 2
- 239000000057 synthetic resin Substances 0.000 claims description 2
- 230000000063 preceeding effect Effects 0.000 claims 2
- 229910010293 ceramic material Inorganic materials 0.000 claims 1
- 239000000945 filler Substances 0.000 claims 1
- 239000011159 matrix material Substances 0.000 description 48
- 238000000576 coating method Methods 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 230000002093 peripheral effect Effects 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- 210000001331 nose Anatomy 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/14—Forme preparation for stencil-printing or silk-screen printing
- B41C1/142—Forme preparation for stencil-printing or silk-screen printing using a galvanic or electroless metal deposition processing step
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/10—Moulds; Masks; Masterforms
Definitions
- the invention relates to a method for producing a Mother matrix for the galvanic generation of seamless Rotary screen printing stencils, especially made of Nickel, being a metallic mother matrix base body with a cylindrical outer surface on its outer circumference with depressions distributed in a regular grid is provided that a round or polygonal Have an outline and a regular network between them grid webs remain, and the depressions then with an electrically non-conductive Filling compound filled flush to the height of the grid bars are then repeated by galvanic application of metal and axially pulling off the resulting Sleeve screen printing stencils can be generated.
- mother matrices are used for the above Previously used for so-called moletting manufactured.
- the desired one is made using a molette Deepening grid in the outer surface of the mother matrix base body indented.
- the Molette is a relatively small roller on the circumference of the mother matrix base body along a helix below strong pressure force is unrolled.
- the molette carries arranged on its peripheral surface in the desired grid Projections that are a negative image of the desired Show recesses for the mother matrix.
- the depressions that can be produced by the mettling can only truncated pyramid or truncated cone with relative be flat inclined flanks. This leads to the disadvantage that the lying in the wells electrically non-conductive filling compound at the edges of the depressions becomes very thin and breaks out easily there. Later galvanic application of metal to the mother matrix The screen printing stencil is then formed when peeling off the finished galvanized template to damage through the surface of the mother matrix Stencil protruding metal noses, which are in could form the breakouts of the filling compound.
- the mother matrix is made of relatively soft copper, over which, for example, nickel is preferred
- Screen printing stencil material is relatively hard to form themselves despite the chrome plating, which is only very thin can be slight striations in the longitudinal direction of the mother matrix, their usability on relatively few production runs for the production of screen printing stencils limit.
- the invention has the advantage that all the mettling tools and not the devices required for this are more needed. This will save a lot in terms of technical, personnel and time Effort reached. Because the outline of the depressions and the grid in which these depressions are arranged are now electronically stored, the Outline shape of the wells and their distribution within of the grid made very precisely and with little Effort changed and adapted to the respective needs without, as was previously required, would be to produce new filleting tools.
- the depressions get a contour that improves Hold the electrically non-conductive filling compound offers.
- the wells are not now more truncated cones or with flanks Are truncated pyramids, but viewed in cross section rather get the shape of oval bowls.
- This keeps the filling mass within the wells also in whose edge areas have a comparatively large thickness, so that breakouts of the filling compound are avoided.
- the later electroplating of the screen printing stencil form what better quality stencils results and damage to the mother matrix when axially pulling off the template avoids. This gives the mother matrix has a longer service life, which in the Practice can be two to three times as long as this previously used mother matrices was accessible.
- an ultraviolet laser beam is used as the beam or a thermal laser beam or an electron beam is used.
- the mentioned rays can be comparatively easily generate and focus so that, in cooperation with a correspondingly selected coating with a suitable Sensitivity, deepening and grid with a high Resolution and accuracy as well as large MESH numbers let generate.
- nickel Since no mechanical Press the depressions into the mother matrix base body more takes place, this no longer has to be relative soft copper, but can also consist of one harder metal exist, this preferably nickel is.
- the metal nickel offers the advantage of a high Hardness, high strength and a high structural density. It also has good electrical conductivity and is easy to galvanize. As a result, a Chromium plating of the surface of the mother matrix is eliminated, what is the recycling of mother matrices that can no longer be used facilitated.
- Another by using Nickel more accessible as a material for the mother matrix The advantage is that the nickel surface of the Mother die automatically through the formation of a nickel oxide layer protects, but remains electrically conductive. At the same time, this nickel oxide layer ensures that the screen printing stencil galvanized onto the mother die slightly pull off the mother matrix leaves, because the nickel oxide layer on the mother matrix as Release agent works.
- a mother matrix base body can as a mother matrix base body also a hollow cylindrical one Nickel sleeve are used. This is straightforward possible because of the elimination of mechanical Pressure forces between the Molette and the base matrix body the latter does not have a particularly high mechanical stability must have more. The use also allows a hollow cylindrical nickel sleeve easier handling and a lighter and cheaper one Transport or shipping between the manufacturer of the mother matrix and generally not the same Manufacturer of screen printing stencils.
- the electrically non-conductive filling compound a curable synthetic resin or a curable ceramic Mass used.
- These materials offer the advantage that on the one hand it was initially still a viscous mass can be introduced into the recesses and that they are on the other side after hardening very firm in the wells adhere and have high strength and surface quality.
- these materials are after curing also by mechanical methods, e.g. Rotate or loops, editable without them coming out of the Loosen depressions or break out at the edge of the depressions.
- the wells are preferably made with a regular generated hexagonal outline; the deepening continues preferably honeycomb in a hexagonal grid distributed.
- This has the advantage that the screen printing stencils produced on this mother die high strength and stability with low weight and have a good web-to-passage ratio. Because of the electronic storability of the outline form the wells and their distribution in the grid is of course, every freedom in the design of this Given parameters.
- FIG. 1 to 5 of the drawing show a section from the peripheral area of a mother matrix base body during various process steps; the figure 6 the drawing shows a section of the peripheral area a finished mother matrix.
- the mother matrix base body 1 made of metal and has a cylindrical outer surface 10 on.
- the base body 1 can be a cylinder or hollow cylindrical sleeve.
- a sensitive is on the lateral surface 10 of the base body 1
- Coating 2 in the form of a comparatively thin Layer applied, which is exaggerated in the drawing is shown in bold.
- this coating 2 can it is a photo, thermo or electro sensitive material act as is known per se. Also order process for achieving such coatings a uniform layer thickness are known and need not to be explained in more detail here.
- Figure 2 of the drawing shows the mother matrix base body 1 during a process step in which of a laser 30 which controls a laser beam 3 emits an exposure of the sensitive coating 2, here with the negative image of the desired wells he follows.
- the mother matrix base body 1 and the laser 30 in two directions relative to one another, preferably the axial direction and the circumferential direction moved, so that gradually the entire peripheral surface of the mother matrix base body 1 is covered.
- the Beam 3 in accordance with electronically stored data on and off to the positive or negative image to expose a desired grid onto the coating 2, depending on whether this is photopositive or photonegative responds.
- the coating 2 by the Exposure in areas 20 changed so that they are for a subsequent chemical and / or physical Removal process becomes insoluble. Between the exposed areas 20 remain unexposed areas 21 which Correspond to areas in which later specializations in the base body 1 are to be generated.
- Figure 3 of the drawing shows the mother matrix base body 1 after going through the removal process in which the unexposed areas 21 of the coating 2 are removed have been. Now the coating remains 2 only the exposed ones on the lateral surface 10 Areas 20 that have a grid-like pattern from protruding webs form outside, each regular Include hexagons.
- a suitable Removal process of the remaining part 20 of the coating 2 also removed, after which the mother matrix base body the surface shape shown in Figure 5 having. This is characterized by a grid of recesses 11 hexagonal in outline, between which are webs 12 distributed webs. The outer The surface of the webs 12 corresponds to the lateral surface 10 of the base body 1.
- Figure 6 of the drawing finally shows the finished mother matrix 1 ', in which the recesses 11 are now complete with a filling compound 4 up to the level of the upper edge the webs 12 and thus up to the original lateral surface 10 of the mother matrix base body 1 filled are.
- the mother matrix is on the lateral surface 10 1 'in the desired distribution areas different electrical properties formed, namely electrically in the area of the surface of the filling compound 4 non-conductive areas and in the area of the surface the webs 12 electrically conductive areas.
- This screen printing sleeve thus formed can then in the axial direction of the mother die 1 ', i.e. parallel to Shell surface 10, deducted from the mother die 1 ' become.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Printing Plates And Materials Therefor (AREA)
- Manufacture Or Reproduction Of Printing Formes (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Adornments (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung einer Muttermatrize für die galvanische Erzeugung von nahtlosen Rotations-Siebdruckschablonen, insbesondere aus Nickel, wobei ein metallischer Muttermatrizen-Grundkörper mit zylindrischer Mantelfläche auf seinem Außenumfang mit in einem regelmäßigen Raster verteilten Vertiefungen versehen wird, die einen runden oder mehreckigen Umriß aufweisen und zwischen denen ein regelmäßiges Netz bildende Rasterstege verbleiben, und wobei die Vertiefungen anschließend mit einer elektrisch nichtleitenden Füllmasse bündig bis zur Höhe der Rasterstege verfüllt werden, wonach dann wiederholt durch galvanisches Auftragen von Metall und axiales Abziehen der so entstandenen Hülse Siebdruckschablonen erzeugbar sind.The invention relates to a method for producing a Mother matrix for the galvanic generation of seamless Rotary screen printing stencils, especially made of Nickel, being a metallic mother matrix base body with a cylindrical outer surface on its outer circumference with depressions distributed in a regular grid is provided that a round or polygonal Have an outline and a regular network between them grid webs remain, and the depressions then with an electrically non-conductive Filling compound filled flush to the height of the grid bars are then repeated by galvanic application of metal and axially pulling off the resulting Sleeve screen printing stencils can be generated.
In der Praxis werden Muttermatrizen für den genannten Verwendungszweck bisher durch das sogenannte Molettieren hergestellt. Dabei wird mittels einer Molette das gewünschte Vertiefungsraster in die Mantelfläche des Muttermatrizen-Grundkörpers eingedrückt. Die Molette ist eine relativ kleine Walze, die auf dem Umfang des Muttermatrizen-Grundkörpers entlang einer Schraubenlinie unter starker Andruckkraft abgerollt wird. Die Molette trägt auf ihrer Umfangsfläche in dem gewünschten Raster angeordnete Vorsprünge, die ein Negativbild der gewünschten Vertiefungen für die Muttermatrize darstellen.In practice, mother matrices are used for the above Previously used for so-called moletting manufactured. The desired one is made using a molette Deepening grid in the outer surface of the mother matrix base body indented. The Molette is a relatively small roller on the circumference of the mother matrix base body along a helix below strong pressure force is unrolled. The molette carries arranged on its peripheral surface in the desired grid Projections that are a negative image of the desired Show recesses for the mother matrix.
Nachteilig erfordert dieses bekannte Verfahren einen hohen maschinellen, personellen und zeitlichen Aufwand. Insbesondere ist es sehr schwierig und nur mit großer Erfahrung möglich, die Molette so auf dem Außenumfang des Muttermatrizen-Grundkörpers abzurollen, daß die über den Außenumfang des Muttermatrizen-Grundkörpers verlaufende Schraubenlinie in Längs- und Umfangsrichtung des Muttermatrizen-Grundkörpers gesehen keinen Versatz im Rasterbild aufweist. Außerdem ist die Herstellung von Moletten sehr aufwendig, da hierfür umfangreiche mechanische Bearbeitungsschritte erforderlich sind. Jede Rasteränderung macht auch die Fertigung einer geänderten Molette nötig. Ein weiterer Nachteil ist darin zu sehen, daß das Material des Muttermatrizen-Grundkörpers relativ weich sein muß, damit durch die Molette überhaupt die gewünschten Vertiefungen eingedrückt oder eingewalzt werden können. Aus diesem Grund kann bisher praktisch nur Kupfer für den Muttermatrizen-Grundkörper verwendet werden, der oberflächlich mit einer dünnen Verchromung versehen ist. Zur Stabilitätserhöhung, die wegen des Abrollens der Molette mit hoher Andruckkraft benötigt wird, muß der Muttermatrizen-Grundkörper zudem einen stabilen Stahlkern aufweisen, was die Muttermatrize insgesamt sehr schwer und damit schwierig handhabbar und transportierbar macht.This known method disadvantageously requires one high mechanical, personnel and time expenditure. In particular, it is very difficult and only with great experience possible, the molette on the outer circumference of the Unroll mother matrix base body that over the Outer circumference of the mother matrix base body Helix in the longitudinal and circumferential direction of the mother matrix base body seen no offset in the raster image having. In addition, the production of molettes very complex because of the extensive mechanical processing steps required are. Every grid change also makes a modified Molette necessary. Another disadvantage is that the Material of the mother matrix base body relatively soft must be so that the desired ones through the Molette Wells can be pressed or rolled in. For this reason, practically only copper can be used up to now can be used for the mother matrix base body, the is superficially provided with a thin chrome plating. To increase stability due to the rolling of the Molette with high contact pressure is required, the Mother matrix base body also has a stable steel core have what the mother matrix is very much difficult and therefore difficult to handle and transport makes.
Die durch das Molettieren erzeugbaren Vertiefungen können nur pyramidenstumpf- oder kegelstumpfförmig mit relativ flach geneigten Flanken sein. Dies führt zu dem Nachteil, daß die in den Vertiefungen liegende elektrisch nichtleitende Füllmasse an den Rändern der Vertiefungen sehr dünn wird und dort leicht ausbricht. Beim späteren galvanischen Auftragen von Metall auf die Muttermatrize zur Bildung der Siebdruckschablone kommt es dann beim Abziehen der fertig galvanisierten Schablone zu einem Beschädigen der Oberfläche der Muttermatrize durch von der Schablone nach innen vorragende Metallnasen, die sich in den Ausbruchstellen der Füllmasse bilden konnten. Da zudem die Muttermatrize aus relativ weichem Kupfer besteht, gegenüber welchem beispielsweise Nickel als bevorzugtes Siebdruckschablonenmaterial relativ hart ist, bilden sich trotz der Verchromung, die aber nur sehr dünn sein kann, leicht Riefen in Längsrichtung der Muttermatrize, die deren Verwendbarkeit auf relativ wenige Produktionsdurchgänge für die Erzeugung von Siebdruckschablonen begrenzen.The depressions that can be produced by the mettling can only truncated pyramid or truncated cone with relative be flat inclined flanks. This leads to the disadvantage that the lying in the wells electrically non-conductive filling compound at the edges of the depressions becomes very thin and breaks out easily there. Later galvanic application of metal to the mother matrix The screen printing stencil is then formed when peeling off the finished galvanized template to damage through the surface of the mother matrix Stencil protruding metal noses, which are in could form the breakouts of the filling compound. Since also the mother matrix is made of relatively soft copper, over which, for example, nickel is preferred Screen printing stencil material is relatively hard to form themselves despite the chrome plating, which is only very thin can be slight striations in the longitudinal direction of the mother matrix, their usability on relatively few production runs for the production of screen printing stencils limit.
Außer dem zuvor beschriebenen mechanischen Molettieren sind aus EP 0 030 774 A1 weitere Verfahren der eingangs genannten Art bekannt. Als erstes bekanntes Verfahren zur Herstellung einer Muttermatrize ist dort beschrieben, daß die Vertiefungen, die mit nicht leitendem Material gefüllt werden sollen, durch Ätzung hergestellt werden. Wie diese Ätzung vorgenommen werden soll, ist in der Schrift nicht beschrieben, jedoch ist es für den Fachmann selbstverständlich, daß hierzu eine Ätzmaske verwendet werden muß. Zur Herstellung, Art und Behandlung der Ätzmaske gibt die Schrift aber ebenfalls keinerlei Hinweise. Als zweites Herstellungsverfahren zur Herstellung einer Muttermatrize ist der Schrift zu entnehmen, mit einem gesteuerten Energiestrahl durch thermische Einwirkung direkt näpfchenartige Bereiche des Muttermatrizen-Grundkörpers in einen nichtleitenden Zustand zu versetzen. Beispielsweise wird bei einem aus elektrisch leitendem Aluminium bestehenden Muttermatrizen-Grundkörper durch den Energiestrahl Aluminium oberflächlich in Aluminiumoxyd umgewandelt, das nicht elektrisch leitend ist. Except for the mechanical mettling described above are further methods from the beginning of EP 0 030 774 A1 known type known. First known method for the production of a mother matrix is described there, that the wells covered with non-conductive material to be filled, produced by etching become. How this etching is to be carried out is shown in the writing is not described, however it is for the Of course, those skilled in the art will need an etching mask must be used. For production, type and treatment the etching mask does not give the writing either Hints. As a second manufacturing process for manufacturing a mother matrix can be found in the script, with a controlled energy beam through thermal Exposure to directly cup-like areas of the mother matrix base body in a non-conductive state to move. For example, one becomes electrical conductive aluminum mother matrix base body superficial due to the energy beam aluminum converted into aluminum oxide, which is not electrical is leading.
Als nachteilig wird bei dem aus EP 0 030 774 Al bekannten Stand der Technik angesehen, daß die erreichbare Genauigkeit der Konturen der nichtleitenden Bereiche auf der Oberfläche der Muttermatrize begrenzt ist und daß dadurch die Qualität der auf dieser Muttermatrize erzeugten Siebdruckschablonen nicht optimal ist.A disadvantage of the known from EP 0 030 774 Al State of the art viewed that the achievable accuracy the contours of the non-conductive areas the surface of the mother matrix is limited and that the quality of those produced on this mother matrix Screen printing stencils is not optimal.
Es stellt sich daher die Aufgabe, ein Verfahren der eingangs genannten Art anzugeben, welches die Herstellung einer Muttermatrize für die galvanische Erzeugung von nahtlosen Rotations-Siebdruckschablonen, insbesondere aus Nickel, mit einem geringen maschinellen, personellen und zeitlichen Aufwand erlaubt und mittels welchem Muttermatrizen mit hoher Qualität und langer Standzeit herstellbar sind.It is therefore the task of a process of the beginning Specify the type mentioned, which is the manufacture a mother matrix for the galvanic generation of seamless rotary screen printing stencils, in particular made of nickel, with a small mechanical, personal and time expenditure allowed and by means of which mother matrices producible with high quality and long service life are.
Die Lösung dieser Aufgabe gelingt erfindungsgemäß durch
ein Verfahren der eingangs genannten Art, welches gekennzeichnet
ist durch folgende Verfahrensschritte:
Eine alternative Ausgestaltung des erfindungsgemäßen Verfahrens
schlägt gemäß Anspruch 2 vor, daß der Verfahrensschritt
b) wie folgt ausgeführt wird:
Die Erfindung bietet den Vorteil, daß alle Molettierwerkzeuge und die hierfür benötigten Vorrichtungen nicht mehr erforderlich sind. Dadurch wird eine große Einsparung hinsichtlich des technischen, personellen und zeitlichen Aufwandes erreicht. Da die Umrißform der Vertiefungen und das Raster, in dem diese Vertiefungen angeordnet sind, nun elektronisch gespeichert sind, können die Umrißform der Vertiefungen und deren Verteilung innerhalb des Rasters sehr genau hergestellt und mit geringem Aufwand verändert und an die jeweiligen Bedürfnisse angepaßt werden, ohne daß, wie dies zuvor erforderlich war, neue Molettierwerkzeuge herzustellen wären.The invention has the advantage that all the mettling tools and not the devices required for this are more needed. This will save a lot in terms of technical, personnel and time Effort reached. Because the outline of the depressions and the grid in which these depressions are arranged are now electronically stored, the Outline shape of the wells and their distribution within of the grid made very precisely and with little Effort changed and adapted to the respective needs without, as was previously required, would be to produce new filleting tools.
Durch das Ätzen oder den elektrolytischen Metallabtrag erhalten die Vertiefungen eine Kontur, die einen verbesserten Halt der elektrisch nichtleitenden Füllmasse bietet. Dies beruht darauf, daß die Vertiefungen nun nicht mehr mit flachen Flanken ausgebildete Kegelstümpfe oder Pyramidenstümpfe sind, sondern im Querschnitt betrachtet eher die Form von ovalen Näpfen erhalten. Hierdurch behält die Füllmasse innerhalb der Vertiefungen auch in deren Randbereichen eine vergleichsweise große Dicke, so daß Ausbrüche der Füllmasse vermieden werden. Hierdurch können sich auch keine vorspringenden Metallnasen bei der späteren Aufgalvanisierung der Siebdruckschablone bilden, was eine bessere Qualität der Siebdruckschablonen ergibt und Beschädigungen der Muttermatrize beim axialen Abziehen der Schablone vermeidet. Hierdurch erhält die Muttermatrize eine höhere Standzeit, die in der Praxis zwei- bis dreimal so lang sein kann, wie dies bei bisher verwendeten Muttermatrizen erreichbar war.Through the etching or the electrolytic metal removal the depressions get a contour that improves Hold the electrically non-conductive filling compound offers. This is because the wells are not now more truncated cones or with flanks Are truncated pyramids, but viewed in cross section rather get the shape of oval bowls. This keeps the filling mass within the wells also in whose edge areas have a comparatively large thickness, so that breakouts of the filling compound are avoided. Hereby can also no protruding metal lugs the later electroplating of the screen printing stencil form what better quality stencils results and damage to the mother matrix when axially pulling off the template avoids. This gives the mother matrix has a longer service life, which in the Practice can be two to three times as long as this previously used mother matrices was accessible.
Bevorzugt ist weiter vorgesehen, daß als Strahl ein Ultraviolett-Laserstrahl oder ein thermisch wirkender Laserstrahl oder ein Elektronenstrahl verwendet wird. Die genannten Strahlen lassen sich vergleichsweise einfach erzeugen und fokussieren, so daß, im Zusammenwirken mit einer entsprechend ausgewählten Beschichtung mit passender Sensitivität, Vertiefungen und Raster mit einer hohen Auflösung und Genauigkeit sowie großen MESH-Zahlen erzeugen lassen.It is also preferably provided that an ultraviolet laser beam is used as the beam or a thermal laser beam or an electron beam is used. The mentioned rays can be comparatively easily generate and focus so that, in cooperation with a correspondingly selected coating with a suitable Sensitivity, deepening and grid with a high Resolution and accuracy as well as large MESH numbers let generate.
Da bei dem erfindungsgemäßen Verfahren kein mechanisches Eindrücken der Vertiefungen in den Muttermatrizen-Grundkörper mehr erfolgt, muß dieser nicht mehr aus dem relativ weichen Kupfer bestehen, sondern kann auch aus einem härteren Metall bestehen, wobei dieses bevorzugt Nickel ist. Das Metall Nickel bietet den Vorteil einer hohen Härte, einer hohen Festigkeit und einer hohen Gefügedichte. Weiterhin weist es eine gute elektrische Leitfähigkeit auf und ist gut galvanisierbar. Hierdurch kann eine Verchromung der Oberfläche der Muttermatrize entfallen, was das Recyceln von nicht mehr einsetzbaren Muttermatrizen erleichtert. Ein weiterer durch die Verwendung von Nickel als Material für die Muttermatrize erreichbarer Vorteil besteht darin, daß sich die Nickeloberfläche der Muttermatrize selbsttätig durch die Bildung einer Nickeloxydschicht schützt, die aber elektrisch leitend bleibt. Zugleich sorgt diese Nickeloxydschicht aber dafür, daß sich die auf die Muttermatrize aufgalvanisierte Siebdruckschablone leicht von der Muttermatrize abziehen läßt, da die Nickeloxydschicht auf der Muttermatrize als Trennmittel wirkt.Since no mechanical Press the depressions into the mother matrix base body more takes place, this no longer has to be relative soft copper, but can also consist of one harder metal exist, this preferably nickel is. The metal nickel offers the advantage of a high Hardness, high strength and a high structural density. It also has good electrical conductivity and is easy to galvanize. As a result, a Chromium plating of the surface of the mother matrix is eliminated, what is the recycling of mother matrices that can no longer be used facilitated. Another by using Nickel more accessible as a material for the mother matrix The advantage is that the nickel surface of the Mother die automatically through the formation of a nickel oxide layer protects, but remains electrically conductive. At the same time, this nickel oxide layer ensures that the screen printing stencil galvanized onto the mother die slightly pull off the mother matrix leaves, because the nickel oxide layer on the mother matrix as Release agent works.
Um Material und insbesondere Gewicht einzusparen, kann als Muttermatrizen-Grundkörper auch eine hohlzylindrische Nickelhülse eingesetzt werden. Dies ist ohne weiteres möglich, weil wegen des Wegfalls der mechanischen Andruckkräfte zwischen Molette und Muttermatrizen-Grundkörper letzterer keine besonders hohe mechanische Stabilität mehr aufweisen muß. Zudem erlaubt die Verwendung einer hohlzylindrischen Nickelhülse eine leichtere Handhabung und einen erleichterten und kostengünstigeren Transport oder Versand zwischen dem Hersteller der Muttermatrize und dem im allgemeinen damit nicht identischen Hersteller von Siebdruckschablonen.To save material and especially weight, can as a mother matrix base body also a hollow cylindrical one Nickel sleeve are used. This is straightforward possible because of the elimination of mechanical Pressure forces between the Molette and the base matrix body the latter does not have a particularly high mechanical stability must have more. The use also allows a hollow cylindrical nickel sleeve easier handling and a lighter and cheaper one Transport or shipping between the manufacturer of the mother matrix and generally not the same Manufacturer of screen printing stencils.
Als elektrisch nichtleitende Füllmasse wird bevorzugt ein aushärtbares Kunstharz oder eine aushärtbare keramische Masse eingesetzt. Diese Materialien bieten den Vorteil, daß sie einerseits zunächst als noch viskose Masse in die Vertiefungen einbringbar sind und daß sie andererseit nach dem Aushärten sehr fest in den Vertiefungen haften und eine hohe Festigkeit und Oberflächengüte aufweisen. Insbesondere sind diese Materialien nach dem Aushärten auch durch mechanische Verfahren, z.B. Drehen oder Schleifen, bearbeitbar, ohne daß sie sich aus den Vertiefungen lösen oder am Rand der Vertiefungen ausbrechen.Preferred is the electrically non-conductive filling compound a curable synthetic resin or a curable ceramic Mass used. These materials offer the advantage that on the one hand it was initially still a viscous mass can be introduced into the recesses and that they are on the other side after hardening very firm in the wells adhere and have high strength and surface quality. In particular, these materials are after curing also by mechanical methods, e.g. Rotate or loops, editable without them coming out of the Loosen depressions or break out at the edge of the depressions.
Die Vertiefungen werden vorzugsweise mit einem regelmäßigen sechseckigen Umriß erzeugt; weiterhin werden die Vertiefungen bevorzugt wabenförmig in einem Hexagonalraster verteilt angeordnet. Dies bietet den Vorteil, daß die auf dieser Muttermatrize erzeugten Siebdruckschablonen eine hohe Festigkeit und Stabilität bei geringem Gewicht sowie ein gutes Steg-Durchlaß-Verhältnis aufweisen. Aufgrund der elektronischen Speicherbarkeit der Umrißform der Vertiefungen und deren Verteilung im Raster ist aber selbstverständlich jede Freiheit bei der Gestaltung dieser Parameter gegeben.The wells are preferably made with a regular generated hexagonal outline; the deepening continues preferably honeycomb in a hexagonal grid distributed. This has the advantage that the screen printing stencils produced on this mother die high strength and stability with low weight and have a good web-to-passage ratio. Because of the electronic storability of the outline form the wells and their distribution in the grid is of course, every freedom in the design of this Given parameters.
Im folgenden wird anhand einer Zeichnung ein Ablaufbeispiel des erfindungsgemäßen Verfahrens beschrieben. Die Figuren 1 bis 5 der Zeichnung zeigen einen Ausschnitt aus dem Umfangsbereich eines Muttermatrizen-Grundkörpers während verschiedener Verfahrensschritte; die Figur 6 der Zeichnung zeigt einen Ausschnitt aus dem Umfangsbereich einer fertigen Muttermatrize.The following is a flow example using a drawing described the inventive method. The Figures 1 to 5 of the drawing show a section from the peripheral area of a mother matrix base body during various process steps; the figure 6 the drawing shows a section of the peripheral area a finished mother matrix.
Gemäß Figur 1 der Zeichnung besteht der Muttermatrizen-Grundkörper
1 aus Metall und weist eine zylindrische Mantelfläche
10 auf. Der Grundkörper 1 kann als Zylinder
oder hohlzylindrische Hülse ausgeführt sein.According to Figure 1 of the drawing, the mother
Auf die Mantelfläche 10 des Grundkörpers 1 ist eine sensitive
Beschichtung 2 in Form einer vergleichsweise dünnen
Schicht aufgetragen, die in der Zeichnung übertrieben
dick dargestellt ist. Bei dieser Beschichtung 2 kann
es sich um ein photo-, thermo- oder elektrosensitives Material
handeln, wie dies an sich bekannt ist. Auch Auftragverfahren
für derartige Beschichtungen zur Erzielung
einer gleichmäßigen Schichtdicke sind bekannt und brauchen
hier nicht näher erläutert zu werden.A sensitive is on the
Figur 2 der Zeichnung zeigt den Muttermatrizen-Grundkörper
1 während eines Verfahrensschrittes, in welchem mittels
eines Lasers 30, der einen Laserstrahl 3 gesteuert
aussendet, eine Belichtung der sensitiven Beschichtung
2, hier mit dem Negativ-Bild der gewünschten Vertiefungen
erfolgt. Dabei werden der Muttermatrizen-Grundkörper
1 und der Laser 30 relativ zueinander in zwei Richtungen,
vorzugsweise die Axialrichtung und die Umfangsrichtung
bewegt, so daß nach und nach die gesamte Umfangsfläche
des Muttermatrizen-Grundkörpers 1 überstrichen wird.
Während dieser relativen Bewegung zueinander wird der
Strahl 3 nach Maßgabe elektronisch gespeicherter Daten
ein- und ausgeschaltet, um das Positiv- oder Negativbild
eines gewünschten Rasters auf die Beschichtung 2 aufzubelichten,
je nachdem, ob diese photopositiv oder photonegativ
reagiert. Im vorliegenden Fall, der in der Zeichnung
dargestellt ist, wird die Beschichtung 2 durch die
Belichtung in den Bereichen 20 so verändert, daß sie für
einen nachfolgenden chemischen und/oder physikalischen
Abtragprozeß unlöslich wird. Zwischen den belichteten Bereichen
20 verbleiben unbelichtete Bereiche 21, die den
Bereichen entsprechen, in denen später Vertiefungen in
dem Grundkörper 1 erzeugt werden sollen.Figure 2 of the drawing shows the mother
Figur 3 der Zeichnung zeigt den Muttermatrizen-Grundkörper
1 nach Durchlaufen des Abtragprozesses, in welchem
die unbelichteten Bereiche 21 der Beschichtung 2 abgetragen
worden sind. Nunmehr verbleiben von der Beschichtung
2 auf der Mantelfläche 10 lediglich noch die belichteten
Bereiche 20, die ein netzförmiges Raster von nach
außen vorragenden Stegen bilden, die jeweils regelmäßige
Sechsecke einschließen.Figure 3 of the drawing shows the mother
In der Figur 4 der Zeichnung ist der Muttermatrizen-Grundkörper
nach Durchlaufen eines Ätzbades oder eines
elektrolytischen Abtragvorganges gezeigt. Durch dieses
Ätzen oder elektrolytische Abtragen wird Metall des Muttermatrizen-Grundkörpers
1 dort abgetragen, wo die ätzende
Säure oder die Elektrolytflüssigkeit Zugang zur Mantelfläche
10 hat. Unterhalb der Bereiche 20 der Beschichtung
2 hat die Säure oder die Elektrolytflüssigkeit keinen
Zugang zur Mantelfläche 10 des Grundkörpers 1, so
daß hier ein Metallabtrag nicht erfolgen kann. In the figure 4 of the drawing is the mother matrix base body
after passing through an etching bath or one
electrolytic removal process shown. Because of this
Etching or electrolytic removal becomes metal of the mother
In einem weiteren Verfahrensschritt wird durch ein geeignetes
Abtragverfahren der verbleibende Teil 20 der Beschichtung
2 ebenfalls abgetragen, wonach der Muttermatrizen-Grundkörper
die in Figur 5 gezeigte Oberflächenform
aufweist. Diese ist charakterisiert durch ein Raster
von im Umriß sechseckigen Vertiefungen 11, zwischen
denen netzförmig verteilt Stege 12 liegen. Die äußere
Oberfläche der Stege 12 entspricht dabei der Mantelfläche
10 des Grundkörpers 1.In a further process step, a suitable
Removal process of the remaining
Figur 6 der Zeichnung schließlich zeigt die fertige Muttermatrize
1', bei welcher nun die Vertiefungen 11 vollständig
mit einer Füllmasse 4 bis in Höhe der Oberkante
der Stege 12 und damit bis zur ursprünglichen Mantelfläche
10 des Muttermatrizen-Grundkörpers 1 ausgefüllt
sind. Hierdurch werden auf der Mantelfläche 10 der Muttermatrize
1' in der gewünschten Verteilung Bereiche mit
unterschiedlichen elektrischen Eigenschaften gebildet,
nämlich im Bereich der Oberfläche der Füllmasse 4 elektrisch
nichtleitende Bereiche und im Bereich der Oberfläche
der Stege 12 elektrisch leitfähige Bereiche.Figure 6 of the drawing finally shows the finished mother matrix
1 ', in which the
Die fertige Muttermatrize 1' kann dann in bekannter Weise
mehrmals zur galvanischen Erzeugung von nahtlosen Rotations-Siebdruckschablonen
verwendet werden, wobei sich
dann im Bereich der elektrisch leitfähigen Stege 12 an
der Mantelfläche 10 der Muttermatrize 1' Metall galvanisch
ablagert, bis eine gewünschte Schichtdicke erreicht
ist. Diese so gebildete Siebdruckhülse kann dann
in Axialrichtung der Muttermatrize 1', d.h. parallel zur
Mantelfläche 10, von der Muttermatrize 1' abgezogen
werden.The finished mother die 1 'can then in a known manner
several times for the galvanic generation of seamless rotary screen printing stencils
be used, where
then in the area of the electrically conductive webs 12
the
Claims (8)
- Process for producing a base mould (1') for electrolytically producing seamless rotary screen printing stencils, in particular of nickel, wherein a metallic base mould body (1) with a cylindrical surface area (10) at the outer circumference thereof is provided with indentations (11) distributed in a regular grid with the indentations comprising a round or polygonal contour, and between which indentations grid webs (12) remain forming a regular net, and wherein the indentations (11) subsequently are filled with an electrically non-conducting filler (4) flush with the level of the grid webs (12), whereupon repeatedly by electrolytically applying metal and axially removing the generated sleeve screen printing stencils are to be produced,
characterized by
the following process steps:a) the surface area (10) of the base mould body (1) is covered with a photo- or thermo-sensitive or electrically sensitive layer (2),b) the layer (2) is exposed to a beam (3) controlled by means of electronically stored data with the positive or negative image of the required indentation grid wherein in the data the shape of the contours of the indentations (11) and their distribution in the grid is stored ad lib, and the layer (2) is removed directly or after a developing process in the areas (21) where the indentations (11) are to be provided by means of a chemical and/or physical removing process,c) in the areas of the surface area (10) of the base mould body (1) where the layer (2) has been removed the indentations (11) are generated by etching or electrolytical metal removing,d) the remaining parts (20) of the layer (2) are completely removed, ande) the indentations (11) are filled with an electrically non-conductive filler (4). - Process according to claim 1, characterized in that the process step b) is accomplished as follows:b) the layer (2) is directly removed in the areas (21) where indentations (11) are provided by a beam (3) controlled by means of electronically stored data wherein in the data the shape of the contour of the indentations (11) and their distribution in the grid are stored ad lib.
- Process according to claim 1 or 2, characterized in that an ultra-violet laser beam or a thermically acting laser beam or an electronic beam are used as the beam (3).
- Process according to one of the claims 1 to 3, characterized in that a nickel cylinder is used as the base mould body (1).
- Process according to one of the claims 1 to 3, characterized in that a hollow-cylindrical nickel sleeve is used as the base mould body (1).
- Process according to one of the preceeding claims, characterized in that a curable synthetic resin or a curable ceramic material is used as the electrically non-conductive filler (4).
- Process according to one of the preceeding claims, characterized in that the indentations (11) are generated with a regular hexagonal contour.
- Process according to claim 7, characterized in that the indentations (11) are arranged in a honeycombed distribution in a hexagonal grid.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4404560 | 1994-02-12 | ||
DE4404560A DE4404560C1 (en) | 1994-02-12 | 1994-02-12 | Process for producing a mother die for the galvanic production of seamless rotary screen printing stencils, in particular made of nickel |
PCT/EP1995/000458 WO1995021951A1 (en) | 1994-02-12 | 1995-02-09 | Process for producing a base mould for electrolycally producing seamless rotary screen printing stencils, in particular of nickel |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0694088A1 EP0694088A1 (en) | 1996-01-31 |
EP0694088B1 true EP0694088B1 (en) | 1999-05-19 |
Family
ID=6510148
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95908917A Expired - Lifetime EP0694088B1 (en) | 1994-02-12 | 1995-02-09 | Process for producing a base mould for electrolycally producing seamless rotary screen printing stencils, in particular of nickel |
Country Status (9)
Country | Link |
---|---|
US (1) | US5972194A (en) |
EP (1) | EP0694088B1 (en) |
CN (1) | CN1095881C (en) |
AT (1) | ATE180291T1 (en) |
AU (1) | AU1706195A (en) |
DE (2) | DE4404560C1 (en) |
ES (1) | ES2133736T3 (en) |
GR (1) | GR3031024T3 (en) |
WO (1) | WO1995021951A1 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1851060B (en) * | 2006-04-10 | 2011-05-04 | 南京航空航天大学 | Hollow part electroforming furrow filling method |
CN101271275B (en) * | 2008-04-28 | 2011-08-10 | 彩虹集团电子股份有限公司 | Horn net manufacturing technique by etching method |
CN101373334B (en) * | 2008-10-13 | 2011-02-16 | 彩虹集团电子股份有限公司 | Method for manually shivering materials of grating net semi-etching connection point |
KR100903962B1 (en) * | 2008-11-21 | 2009-06-25 | 주식회사 센트랄 | Ball seat manufacturing method |
DE102009017686A1 (en) | 2009-04-16 | 2010-10-28 | Steinemann Technology Ag | Rotatable screen printing unit for use in screen printing machine, has gripper that protrudes into outer contour of circular screen during running through column and partially imprints lateral surface of circular screen |
DE102011015456A1 (en) | 2011-03-30 | 2012-10-04 | Thomas Walther | Screen printing method for sheet-fed printing machine, involves filling openings of circumferential screen printing frame with coating agent by scraper adjoined to inner surface of screen printing frame |
CN111051575B (en) * | 2017-09-04 | 2022-03-15 | 富士胶片株式会社 | Master plate for electroforming and method for manufacturing electroforming mold using same |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2166366A (en) * | 1935-11-30 | 1939-07-18 | Edward O Norris Inc | Means and method of producing metallic screens |
BE788470A (en) * | 1971-11-12 | 1973-01-02 | Buckbee Mears Co | IMPROVED PROCESS FOR INCREASING THE RIGIDITY OF IMPRESSIO SCREENS |
AT311294B (en) * | 1972-05-23 | 1973-11-12 | Zimmer Johannes | Stencil sleeve |
US3960675A (en) * | 1975-04-17 | 1976-06-01 | Motter Printing Press Co. | Method for deplating and replating rotogravure cylinders |
DE2544603A1 (en) * | 1975-10-04 | 1977-04-14 | Kabel Metallwerke Ghh | Matrix cylinder for electrolytic mfr. of templates - for rotary screen printing, including mfr. of printed circuit boards |
IN155834B (en) * | 1976-10-05 | 1985-03-16 | Iten K Ag | |
JPS54156880A (en) * | 1978-05-04 | 1979-12-11 | Kenseido Kagaku Kogyo Kk | Production of sleeve for rotary screen printing |
US4384945A (en) * | 1978-09-26 | 1983-05-24 | Sword Wallace W | Production of rotary screen printing cylinders and other fine-apertured sheet materials |
NL7909089A (en) * | 1979-12-17 | 1981-07-16 | Stork Screens Bv | METHOD FOR MANUFACTURING A DIE |
DE3011192A1 (en) * | 1980-03-22 | 1981-10-01 | Hoechst Ag, 6000 Frankfurt | METHOD FOR THE PRODUCTION OF SCREEN PRINTING STENCILS ON A GALVANIC WAY |
JPH0793255B2 (en) * | 1987-07-23 | 1995-10-09 | 松下電器産業株式会社 | Fine pattern forming method |
JPH01254944A (en) * | 1988-04-04 | 1989-10-11 | Fuji Photo Film Co Ltd | Silver halide photographic sensitive material |
NL8802928A (en) * | 1988-11-28 | 1990-06-18 | Stork Screens Bv | A METHOD AND APPARATUS FOR FORMING A RESISTANT PATTERN ON A CYLINDRICAL ART AND A METAL CYLINDER CREATED BY THE USE OF SUCH A RESISTANCE PATTERN. |
BE1002787A7 (en) * | 1989-01-31 | 1991-06-11 | Centre Rech Metallurgique | DEVICE FOR THE MANUFACTURE, BY ELECTRODEPOSITION, OF A PERFORATED METAL SHEET OF LOW THICKNESS, AS WELL AS METHODS OF MAKING AND USING SUCH A DEVICE. |
JP2727445B2 (en) * | 1991-05-25 | 1998-03-11 | 株式会社 シンク・ラボラトリー | Rotary screen manufacturing method |
US5328537A (en) * | 1991-12-11 | 1994-07-12 | Think Laboratory Co., Ltd. | Method for manufacturing screen printing plate |
US5334815A (en) * | 1992-01-15 | 1994-08-02 | Wear Guard Corp. | Apparatus and method for producing a printing screen |
US5573815A (en) * | 1994-03-07 | 1996-11-12 | E. I. Du Pont De Nemours And Company | Process for making improved metal stencil screens for screen printing |
-
1994
- 1994-02-12 DE DE4404560A patent/DE4404560C1/en not_active Revoked
-
1995
- 1995-02-09 AU AU17061/95A patent/AU1706195A/en not_active Abandoned
- 1995-02-09 WO PCT/EP1995/000458 patent/WO1995021951A1/en active IP Right Grant
- 1995-02-09 ES ES95908917T patent/ES2133736T3/en not_active Expired - Lifetime
- 1995-02-09 AT AT95908917T patent/ATE180291T1/en not_active IP Right Cessation
- 1995-02-09 CN CN95190085A patent/CN1095881C/en not_active Expired - Lifetime
- 1995-02-09 US US08/535,131 patent/US5972194A/en not_active Expired - Lifetime
- 1995-02-09 DE DE59505958T patent/DE59505958D1/en not_active Expired - Lifetime
- 1995-02-09 EP EP95908917A patent/EP0694088B1/en not_active Expired - Lifetime
-
1999
- 1999-08-18 GR GR990402102T patent/GR3031024T3/en unknown
Also Published As
Publication number | Publication date |
---|---|
ATE180291T1 (en) | 1999-06-15 |
EP0694088A1 (en) | 1996-01-31 |
AU1706195A (en) | 1995-08-29 |
ES2133736T3 (en) | 1999-09-16 |
US5972194A (en) | 1999-10-26 |
CN1123039A (en) | 1996-05-22 |
DE59505958D1 (en) | 1999-06-24 |
DE4404560C1 (en) | 1995-08-24 |
GR3031024T3 (en) | 1999-12-31 |
WO1995021951A1 (en) | 1995-08-17 |
CN1095881C (en) | 2002-12-11 |
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