EP0423555B1 - Procédé et dispositif pour le grainage électrochimique d'une surface métallique - Google Patents

Procédé et dispositif pour le grainage électrochimique d'une surface métallique Download PDF

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Publication number
EP0423555B1
EP0423555B1 EP90119115A EP90119115A EP0423555B1 EP 0423555 B1 EP0423555 B1 EP 0423555B1 EP 90119115 A EP90119115 A EP 90119115A EP 90119115 A EP90119115 A EP 90119115A EP 0423555 B1 EP0423555 B1 EP 0423555B1
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zone
electrolyte
equal
range
chamber
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EP90119115A
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German (de)
English (en)
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EP0423555A1 (fr
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Kurt Hausmann
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching
    • C25F3/04—Etching of light metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N3/00—Preparing for use and conserving printing surfaces
    • B41N3/03—Chemical or electrical pretreatment
    • B41N3/034—Chemical or electrical pretreatment characterised by the electrochemical treatment of the aluminum support, e.g. anodisation, electro-graining; Sealing of the anodised layer; Treatment of the anodic layer with inorganic compounds; Colouring of the anodic layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S204/00—Chemistry: electrical and wave energy
    • Y10S204/09—Wave forms

Definitions

  • the invention relates to a method for the electrochemical roughening of the surface of preferably band-shaped carrier metal, in particular for printing plates, preferably offset printing plates, in which the carrier metal is preferably introduced after degreasing into an electrolyte bath containing several zones and in the region of each zone of action exposed to alternating current introduced into the electrolyte bath, and according to a further inventive concept goes to a preferred device for carrying out this method.
  • a method and an apparatus of the type mentioned above are known from US Pat. No. 3,755,116.
  • two zones are provided, each of which is assigned a chamber of a trough divided into two chambers by an intermediate wall.
  • the intermediate wall is provided with a passage recess for the band-shaped carrier metal, so that the two chambers communicate with one another and act as a single space.
  • the selection of special roughening parameters such as the selection of a special temperature for each zone and / or the selection of a special electrolyte for each zone, is not possible here.
  • the current density and current frequency inevitably match in both zones.
  • An electrode is assigned to each chamber. However, the electrodes provided are connected to the same current source, so that the same current density and frequency result everywhere. In another case, disruptions would also be feared.
  • Another object of the present invention is to improve a method of the type mentioned at the beginning with simple and inexpensive means in such a way that not only can a uniformly roughened, streak-free and smudge-free surface be produced, but also high economic efficiency is achieved.
  • Another object of the present invention is to provide a device which is suitable and particularly expedient for carrying out the method.
  • the solution relating to the method is that the current frequency is higher in the first zone and the current density is at least not less than in the second zone, in which a longer dwell time is maintained than in the first zone, and that a third zone is provided in which the current frequency is greatest.
  • the comparatively high frequency in the area of the first stage leads to a comparatively large number of points of attack in the area of surface to be roughened, ie small depressions begin to form at comparatively many places on this surface.
  • the particularly high frequency that is subsequently used in the area of the third stage primarily eliminates the smut that has meanwhile settled in the area of the depressions.
  • the current density in the region of the first zone can also advantageously be greater than in the region of the second zone. Due to the correspondingly high current density in the area of the first zone, the attack on the surface to be roughened, which occurs here in many places, is particularly intense.
  • a further advantageous measure can consist in the fact that the current density in the region of the third zone lies in the region between the current densities of the first and the second zone. This ensures that there is no significant change in the roughness in the area of the third zone and that there is primarily removal of smut. Accordingly, a comparatively short dwell time is sufficient in the area of the third zone.
  • the residence time in the region of the third zone can expediently lie in the region between the residence times in the region of the first and the second zone. This is sufficient to remove smut.
  • a further expedient measure can consist in the fact that the highest electrolyte temperature is present at least in the area of the first zone. This can also intensify the attack on the surface to be roughened, which occurs in many places. Accordingly, the electrolyte temperature in the region of the first zone can advantageously be higher than in the other two zones, the electrolyte temperature in the region of the third zone expediently in the region between the electrolyte temperatures the first and second zones.
  • electrolytes can be used in the area of the three zones. This enables individual adaptation to the needs of the individual case. Nevertheless, at least one identical component can be contained in the electrolyte of each stage to achieve good economy, preferably in the form of HCl, preferably in the concentration of 5 g / l.
  • the device-related solution to the problem can be based on a device with at least one roughening station, which contains a plurality of chambers, each of which can be charged with heatable, electrolytic liquid, into which at least one electrode can be connected to a power source, and with transport devices, preferably formed by transport rollers, for Transport of the preferably strip-shaped carrier metal past the electrodes consists, according to the invention, in that the chambers of a roughening station do not communicate with one another and that each chamber is assigned its own electrolyte source and its own, preferably adjustable heating device, as well as a power supply device with individually predeterminable current density and current frequency.
  • the path of this band-shaped carrier metal through the chambers can advantageously be of different lengths in accordance with the difference in the desired throughput times.
  • the chambers can simply have a different, clear length. In this way, the desired throughput times can be achieved in a simple manner despite the constant belt speed.
  • a strip-shaped carrier metal for example made of Al 1050 or Al 3003, is assumed, the surface of which is first roughened, then coated with an oxide layer and then treated with a so-called interlayer before a photosensitive one Layer applied becomes.
  • the device on which the drawing is based contains a roughening station designated as a whole by 1. This has a trough-shaped container 2, which is divided into two chambers 4, 5, 6 by two partitions 3. In and outside the chambers 4, 5, 6 guide elements formed by deflection rollers 7 are provided, via which the band 9 unwound from a roller 8 is guided and which are arranged such that the band 9 in the form of U-shaped loops through each chamber 4 , 5, 6 is passed. Some of the deflection rollers 7 can be driven to accomplish a belt transport. In many cases, however, the tension exerted on the tape in the region of a winding station (not shown here) is sufficient.
  • the belt 9 Before the belt 9 enters the roughening station 1, it is degreased and then rinsed.
  • the unwinding station receiving the roll 8 is followed by a degreasing basin 10 to which sodium hydroxide solution or the like can be applied, through which the belt 9 is passed in the form of a U-shaped loop.
  • pre-etching takes place at the same time.
  • the belt 9 passes through a rinsing station 12 which is provided with spray nozzles 11 on both sides of the transport plane and can be acted upon by rinsing water.
  • the belt pretreated in this way runs into the roughening station 1, in which roughening is accomplished electrochemically.
  • the roughening station 1 and accordingly also the processing taking place here are in three zones I, corresponding to the number of successive chambers 4, 5, 6, II, III divided, each of which a chamber 4, 5, 6 is assigned.
  • the chambers 4, 5, 6 each contain a filling of an electrolytic liquid. This consists essentially of water, to which certain agents have been added.
  • the agents added can consist of one or more components.
  • HCl is to be found in all three zones and everywhere in the concentration of 5 g / l.
  • Zone I there are no other agents apart from HCl.
  • zone II there is also H3BO3 in addition to HCl in the concentration of 10g / l.
  • zone III there is also H3BO3 in addition to HCl, here in the concentration of 1g / l.
  • H3BO3 in addition to HCl, here in the concentration of 1g / l.
  • other reagents could also be used.
  • hydrochloric acid instead of hydrochloric acid, nitric acid could also be used and the like. The same applies to further electrolyte compositions which can be found in the prior art.
  • each chamber 4, 5, 6 should be acted upon by an electrolyte of a special composition, each chamber 4, 5, 6 is assigned its own electrolyte storage container 14, 15, 16, one of which leads to the assigned chamber 4, 5, 6, with a pump 17 provided supply line 18 goes out.
  • the chambers 4, 5, 6 are acted upon by the associated electrolyte during continuous operation. Accordingly, from each chamber 4, 5, 6 a return line 19 connected to an overflow leads back to the associated storage container 14, 15, 16.
  • each chamber has its own heating device 20 assigned, which can be controlled by means of an associated control device 21.
  • the heating device can be a flow heater arranged in the supply line 18.
  • the heating device 20 is designed in the form of a heating coil arranged in the respectively assigned chamber 4, 5, 6. In the exemplary embodiment shown, this should be electrically heatable and is accordingly connected to the electrical network 22.
  • the controller of the control device 21 is adjustable, as indicated by the scale 23.
  • control devices 21 are to be set so that the electrolyte temperature in the chamber 4 belonging to zone I is 36 ° C., in the chamber 5 belonging to zone II 28 ° C. and in the chamber 6 belonging to zone III 6 31 ° C. .
  • the electrolyte temperature of zone I can be between 30 ° C and 40 ° C, zone II between 20 ° C and 40 ° C and zone III between 25 ° C and 35 ° C. Within these ranges, the temperatures are in any case chosen so that the highest electrolyte temperature is present in zone I and the lowest electrolyte temperature in zone II and the electrolyte temperature of zone III is in between.
  • each chamber 4, 5, 6. can be blocks made of graphite and spaced next to one another, on the underside of which the strip 9 is guided. In such a case, only the upper side of the tape facing the electrodes 24 is roughened, which is desirable in the production of printing plates is. If both sides of the strip are to be roughened, opposing electrodes can be provided, between which the strip is passed, or electrodes provided with corresponding drive-through windows can be used.
  • the electrodes 24 are supplied with alternating current via the power network 22.
  • each electrode set 24 is assigned its own frequency setting device 25 constructed in the manner of a frequency amplifier and its own current or voltage setting device 26 constructed in the manner of a current or voltage amplifier, which are adjustable, as indicated by the scale 27 or 28 .
  • the frequency setting devices 25 should be set so that a current frequency of 210 Hz is present in zone I, 45 Hz in zone II and 315 Hz in zone III.
  • the frequency in Zone I can be between 120Hz to 240Hz, in Zone II between 20Hz to 80Hz and in Zone III between 250Hz to 360Hz. Within these ranges, the frequency is always chosen so that the frequency in zone I is much higher than in zone II, but remains lower than in zone III, in which the greatest frequency is used.
  • the current or voltage setting devices 26 are set here so that there is a current density of 50A / dm2 in the area of Zone I, 20A / dm2 in Zone II and 30A / dm2 in Zone III.
  • the current density in zone I can be between 40A / dm2 to 80A / dm2, in zone II between 10A / dm2 to 30A / dm2 and in zone III between 15A / dm2 to 50A / dm2. Within these areas the current density is always chosen so that the greatest current density is present in the region of the first zone I and the lowest current density is present in the region of the second zone II, and that the current density lies in the region of zone III in between.
  • the belt 9 should move at a constant speed here.
  • the passage paths of the belt 9 through the zones I, II, III are accordingly chosen so that the desired dwell times result. Different residence times are desirable in the present case.
  • the chambers 4, 5, 6 assigned to the zones I, II, III accordingly have different clear widths depending on the desired dwell time in the running direction of the belt.
  • the longest dwell time is desired in zone II. Accordingly, the chamber 5 assigned to zone II has the greatest length.
  • the shortest dwell time is desired in zone I. Accordingly, the chamber 4 assigned to zone I has the smallest length.
  • the length of the chamber 6 is between the lengths of the chambers 4 and 5.
  • the chamber lengths are dimensioned so that there is a dwell time of 3 seconds in the chamber 4 belonging to zone I and a dwell time of 10 seconds in zone 5 belonging to zone II . and in the chamber 6 belonging to zone III a dwell time of 4 seconds. results.
  • the dwell time can be varied by changing the belt speed.
  • the usable range for chamber 4 belonging to zone I is 2 seconds. to 5sec., for chamber 5 belonging to Zone II between 6sec. up to 15sec. and for the chamber 6 belonging to zone III between 2sec. up to 6s ..
  • the current density in zone I was 50A / dm2, the current frequency was 210Hz and the dwell time was 3 seconds. and the temperature 36 ° C.
  • the liquid contained the component HCl in a concentration of 5 g / l.
  • the current density was also 50A / dm2, the frequency 45Hz, the dwell time 10sec. and the electrolyte temperature is 28 ° C.
  • the liquid contained the component HCl in a concentration of 5 g / l and the component H 3 BO 3 in a concentration of 10 g / l.
  • the current density was again in zone III 50A / dm2, the current frequency 315Hz, the dwell time 4sec.
  • the electrolyte temperature is 31 ° C.
  • the liquid contained the components HCl in a concentration of 5g / l and H3BO3 in a concentration of 1g / l.
  • the tape processed in this way had a very uniform, practically white, streak- and smut-free surface.
  • the belt 9 After leaving the roughening station 1, the belt 9 passes through a rinsing station 29 which is arranged downstream of the roughening station 1 and which is provided with spray nozzles 30 which are arranged on both sides of the transport plane and can be acted upon by water.
  • the tape 9 prepared in this way can then be fed to an anodizing device, which is no longer shown here, in which the roughened surface is coated with an oxide layer.
  • the tape can then pass through an application station for applying a so-called interlayer.
  • the roughened tape which is provided with an oxide layer and an interlayer layer, forms the base material for the production of printing plates. For this purpose, the tape is cut into pieces and coated with a photosensitive layer before or after.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Printing Plates And Materials Therefor (AREA)

Claims (15)

  1. Procédé pour le grainage électrochimique de la surface d'un métal de support, avantageusement en forme de bande, notamment pour des plaques d'impression, avantageusement des plaques d'impression Offset, selon lequel le métal de support, avantageusement après un graissage, est introduit dans un bain d'électrolyte contenant plusieurs zones et est exposé, dans le domaine de chaque zone, à l'action d'un courant alternatif acheminé dans le bain d'électrolyte, procédé caractérisé en ce que la fréquence du courant dans la première zone est plus grande, et la densité du courant n'est au moins pas plus petite que dans la seconde zone, dans laquelle on maintient une plus longue durée de séjour que dans la première zone, et en ce qu'il est prévu une troisième zone dans laquelle la fréquence du courant est la plus grande.
  2. Procédé selon la revendication 1, caractérisé en ce que la densité de courant est plus grande dans la première zone que dans la seconde zone et en ce que, avantageusement, la densité de courant se situe dans la troisième zone entre les densités de courant de la première zone et de la seconde zone.
  3. Procédé selon l'une des revendications précédentes, caractérisé en ce que le temps de séjour dans la troisième zone correspond au moins au temps de séjour dans la première zone et au maximum au temps de séjour dans la seconde zone et se situe avantageusement entre les temps de séjour dans les première et seconde zones.
  4. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'au moins dans la première zone, la température de l'électrolyte est la plus élevée et en ce que, avantageusement, la température de l'électrolyte dans la première zone est plus grande que celle régnant dans les deux autres zones, et en ce que la température de l'électrolyte dans la troisième zone se situe entre les températures de l'électrolyte dans les première et seconde zones.
  5. Procédé selon l'une des revendications précédentes, caractérisé en ce que, dans les trois zones, servent des électrolytes différents, l'électrolyte de chaque zone contenant avantageusement au moins un même constituant, avantageusement sous forme de HCl, avantageusmeent encore en la concentration de 5 g/l.
  6. Procédé selon la revendication 5, caractérisé en ce que l'électrolyte de la première zone ne contient, en plus de l'additif commun à toutes les zones, pas d'autre additif; en ce que l'électrolyte de la seconde zone contient, en plus de l'additif commun à toutes les zones, un autre additif, avantageusement sous forme de H₃BO₃, avantageusement à nouveau en une concentration de 10 g/l, et l'électrolyte de la troisième zone contient, en plus de l'additif commun à toutes les zones, un autre additif, avantageusement sous forme de H₃BO₃, en une plus faible concentration que la seconde étape, avantageusement en la concentration d'1 g/l.
  7. Procédé selon l'une des revendications précédentes, caractérisé en ce que la fréquence du courant se situe, dans la première zone, entre 120 HZ et 240 HZ, et elle est avantageusement de 210 HZ; en ce que la fréquence du courant dans la seconde zone se situe entre 20 Hz et 80 Hz, et elle est avantageusement de 45 Hz; et en ce que la fréquence du courant dans la troisième zone se situe entre 250 Hz et 360 Hz, et elle est avantageusement de 315 Hz.
  8. Procédé selon l'une des revendications précédentes, caractérisé en ce que la densité du courant se situe dans la première zone entre 40 A/dm² et 80 A/dm² , avantageusement à 50 A/dm²; en ce que la densité de courant dans la seconde zone se situe entre 10 A/dm² et 30 A/dm², avantageusment à 20 A/dm², et en ce que la densité de courant se situe dans la troisième zone entre 15 A/dm² et 50 A/dm², avantageusement à 30 A/dm².
  9. Procédé selon l'une des revendications précédentes, caractérisé en ce que la température de l'électrolyte se situe, dans la première zone, entre 30°C et 40°C, avantageusement à 36°C; en ce que la température de l'électrolyte dans la seconde zone se situe entre 20°C et 40°C, avantageusement à 28°C, et en ce que la température de l'électrolyte se situe dans la troisième zone entre 20°C et 35°C, avantageusement à 31°C.
  10. Procédé selon l'une des revendications précédentes, caractérisé en ce que le temps de séjour dans la première zone se situe entre 2 secondes et 5 secondes, avantageusement à 3 secondes; en ce que la durée de séjour dans la seconde zone se situe entre 6 secondes et 15 secondes, avantageusement à 10 secondes; et en ce que la durée de séjour dans la troisième zone se situe entre 2 secondes et 6 secondes, avantageusement à 4 secondes.
  11. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'en cas d'utilisation de Al 1050 comme métal de support, la densité du courant est dans l'ensemble des trois zones de 50 A/dm² et en ce que, pour la fréquence, le temps de séjour, la température de l'électrolyte et la nature de l'électrolyte, on a affaire aux valeurs préférées.
  12. Procédé selon l'une des revendications 1 à 10 ci-dessus, caractérisé en ce qu'en cas d'utilisation de AL 3003 comme métal de support, la densité de courant est de 50 A/dm² dans la première zone et dans la troisième zone et elle est de 20A/dm² dans la seconde zone; et en ce que, pour la fréquence, le temps de séjour, la température de l'électrolyte et la nature de l'électrolyte, on a à faire aux valeurs préférées.
  13. Dispositif pour la conduite du procédé, comportant au moins un poste (1) de grainage, qui contient plusieurs chambres (4,5,6), pouvant chacune être alimentée en liquide électrolytique chauffable, dans chacune desquelles plonge au moins une électrode (24), pouvant être connectée à une source de courant, avantageusement un groupe de deux électrodes (24), et comportant des agencements de transport, avantageusement formés par des rouleaux de transport (7) pour le transport devant les électrodes (24) du métal de support (9), avantageusement en forme de bande, dispositif caractérisé en ce que les chambres (4,5,6) d'un poste de grainage (1) ne communiquent pas l'une avec l'autre et en ce que chaque chambre (4,5,6) est associée à une source (14,15,16) propre d'électrolyte et à un dispositif (20) propre de chauffage, avantageusement réglable, ainsi qu'à une installation (25,26) d'alimentation en courant, dont la densité de courant et la fréquence du courant sont individuellement pré-réglables.
  14. Dispositif selon la revendication 13, caractérisé en ce que le trajet du métal de support (g) en forme de bande a une longueur différente lors de la traversée des chambres (4,5,6) selon la différence entre les temps de séjour voulus, et, avantageusement, la chambre (5) médiane, associée à la zone II, est plus longue que la première chambre (4) associée à la zone I;la longueur de la troisième chambre (6) associée à la zone III, correspondant au moins à la longueur de la première chambre (4) et au maximum à la longueur de la seconde chambre (5) en se situant avantageusement entre la longueur de la première chambre (4) et celle de la seconde chambre (5).
  15. Dispositif selon l'une des revendications 13 ou 14 précédentes, caractérisé en ce qu'à chaque chambre (4,5,6) sont associés à chaque fois un amplificateur de fréquence (25) et un amplificateur de courant ou de tension (26), avantageusement réglables.
EP90119115A 1989-10-18 1990-10-05 Procédé et dispositif pour le grainage électrochimique d'une surface métallique Expired - Lifetime EP0423555B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3934683A DE3934683A1 (de) 1989-10-18 1989-10-18 Verfahren und vorrichtung zur elektrochemischen aufrauhung einer metalloberflaeche
DE3934683 1989-10-18

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EP0423555A1 EP0423555A1 (fr) 1991-04-24
EP0423555B1 true EP0423555B1 (fr) 1993-09-29

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US (1) US5041198A (fr)
EP (1) EP0423555B1 (fr)
JP (1) JPH03134200A (fr)
DE (2) DE3934683A1 (fr)

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US5171416A (en) * 1990-10-10 1992-12-15 Space Systems/Loral, Inc. Method for making a battery cell electrode
JPH06509754A (ja) * 1991-07-22 1994-11-02 コダック　ポリクロウム　グラフィクス　リミティド　ライアビリティ　カンパニー 二段電解砂目立て方法、それにより製造したアルミニウムシート材料及びそのアルミニウムシート材料からなる平版印刷版
US5186795A (en) * 1991-07-22 1993-02-16 Eastman Kodak Company Two-stage process for electrolytic graining of aluminum
US5122243A (en) * 1991-07-22 1992-06-16 Eastman Kodak Company Lithographic printing plates comprising an aluminum support grained in a two stage-electrolytic process
DE4129909A1 (de) * 1991-09-09 1993-03-11 Hoechst Ag Verfahren zum aufrauhen von aluminium bzw. von aluminiumlegierungen als traegermaterial fuer druckplatten und eine druckplatte
JP3567402B2 (ja) * 1996-06-12 2004-09-22 コニカミノルタホールディングス株式会社 平版印刷版用支持体の製造方法、その製造方法で得られる平版印刷版用支持体及びその支持体を用いた感光性平版印刷版
US20030032879A1 (en) * 1997-07-07 2003-02-13 Steven Quay Microbubble formation using ultrasound
DE60021140T2 (de) 1999-04-22 2006-05-04 Fuji Photo Film Co., Ltd., Minami-Ashigara Verfahren zur Herstellung eines Aluminiumträgers für lithographische Druckplatten
US20030047464A1 (en) * 2001-07-27 2003-03-13 Applied Materials, Inc. Electrochemically roughened aluminum semiconductor processing apparatus surfaces
JP4038041B2 (ja) * 2001-12-05 2008-01-23 富士フイルム株式会社 電解処理装置

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DE3217552A1 (de) * 1982-05-10 1983-11-10 Hoechst Ag, 6230 Frankfurt Verfahren zur elektrochemischen aufrauhung von aluminium fuer druckplattentraeger
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EP0423555A1 (fr) 1991-04-24
US5041198A (en) 1991-08-20
DE3934683A1 (de) 1991-04-25
JPH03134200A (ja) 1991-06-07
DE59002917D1 (de) 1993-11-04

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