EP0132549A1 - Procédé et dispositif pour l'anodisation en continu sur une seule face des bandes d'aluminium et son utilisation dans la fabrication des plaques d'impression - Google Patents

Procédé et dispositif pour l'anodisation en continu sur une seule face des bandes d'aluminium et son utilisation dans la fabrication des plaques d'impression Download PDF

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Publication number
EP0132549A1
EP0132549A1 EP84106318A EP84106318A EP0132549A1 EP 0132549 A1 EP0132549 A1 EP 0132549A1 EP 84106318 A EP84106318 A EP 84106318A EP 84106318 A EP84106318 A EP 84106318A EP 0132549 A1 EP0132549 A1 EP 0132549A1
Authority
EP
European Patent Office
Prior art keywords
anode
cathode
electrolyte
aluminum
continuous
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
EP84106318A
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German (de)
English (en)
Other versions
EP0132549B1 (fr
Inventor
Joachim Dipl.-Ing. Stroszynski
Gerhard Dr. Dipl.-Chem. Sprintschnik
Walter Dr. Dipl.-Phys. Niederstätter
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
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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 EP0132549A1 publication Critical patent/EP0132549A1/fr
Application granted granted Critical
Publication of EP0132549B1 publication Critical patent/EP0132549B1/fr
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/005—Apparatus specially adapted for electrolytic conversion coating

Definitions

  • the invention relates to a method and a device for the continuous one-sided anodic oxidation of aluminum or one of its alloys in strip form, which can be used in particular as a carrier material for offset printing plates.
  • Ribbon-shaped, roughened and anodized aluminum is required, for example, for the production of electrolytic capacitors, in construction, for packaging materials or in the production of carrier materials for offset printing plates.
  • the band-shaped material is generally divided into smaller formats.
  • Carrier materials for offset printing plates are provided either by the consumer directly or by the manufacturer of pre-coated printing plates on one or both sides with a radiation (light) sensitive layer (reproduction layer), with the help of which a printing image of a template is generated by photomechanical means.
  • the support carries the image areas which will guide the color during later printing and at the same time forms the hydrophilic image background for the lithographic printing process at the areas which are free of image (non-image areas) during later printing.
  • Aluminum is used particularly frequently as the base material for such layer supports, which by known methods by dry brushing, wet brushing, sandblasting, chemical and / or electrochemical treatment is roughened superficially.
  • electrochemically roughened substrates in particular are subjected to an anodization step to build up a thin oxide layer.
  • These anodic oxidation processes are usually carried out in aqueous electrolytes containing H 2 S0 4 , H 3 P0 41 H 2 C 2 O 4 , H 3 BO 3 , amidosulfonic acid, sulfosuccinic acid, sulfosalicylic acid or mixtures thereof.
  • aqueous electrolytes or electrolyte mixtures differ in structure, layer thickness and resistance to chemicals. As already mentioned, such roughened and anodized materials also play a certain role in other technical fields.
  • aqueous H 2 S0 4 and / or H 3 P0 4 solutions are used.
  • Variant 1 has the following disadvantages: the aluminum strip - despite previous treatment steps in solutions as a rule - must hit the contact roller as dry as possible, which means additional construction and energy costs for intermediate drying. In addition, when the tape is separated from the contact roller, arc discharges can take place which cover the surface of the Destroy the aluminum strip irreversibly and form defects in the subsequent anodic oxidation or even make the strip completely unusable. These disadvantages can have a particularly negative effect at the high working speeds of 300 m / min and more required in conjunction with the high current densities required for this.
  • the aluminum strip is in each case guided vertically over deflection rollers and between separating devices within an electrolyte, these separating devices at least partially also being electrodes.
  • all separating devices can also be connected as electrodes; two adjacent separating devices are then always anodes or cathodes and thus effect a bilateral treatment of the aluminum surface.
  • this method cannot be used for one-sided treatment and is also not transferable to an essentially horizontal tape guide.
  • the object of the present invention is to find a method and a device for the continuous one-sided anodic oxidation of aluminum strips, which make it possible to get by with reasonable lengths of the electrolyte bath or the electrolyte baths in the actual anodizing zone, even at high strip speeds, without negatively influencing the strip surface .
  • the invention is based on a process for the continuous one-sided anodic oxidation of strips made of aluminum or one of its alloys in an aqueous electrolyte using direct current, which comes into effect through at least one anode and cathode arranged in the electrolyte.
  • the method according to the invention is then characterized in that the anode (s) and the cathode (s) act from opposite sides and at the same time electrochemically on the strip moving past them.
  • the strip is guided essentially horizontally past the electrodes arranged essentially horizontally
  • the aqueous electrolyte contains sulfuric acid and / or phosphoric acid and mechanical, chemical and / or electrochemical roughening is carried out before the anodic oxidation.
  • substantially horizontal it is to be understood that angular deviations of up to 30 ° from the horizontal should also be included.
  • Another solution to the problem is one Device for the continuous one-sided anodic oxidation of strips of aluminum or one of its alloys using direct current containing a) at least one treatment bath which is filled with an aqueous electrolyte, b) at least one anode below and c) at least one cathode, which are arranged above the strip to be treated in the electrolyte.
  • a device according to the invention can consist of only one treatment bath, but it can also have several such baths in a row, but each bath contains at least one of the specified pairs of electrodes; The baths can then be the same, but different aqueous electrolytes can also be present.
  • the strip to be treated can be introduced and / or carried out in the bath or guided in the bath in a known manner via deflection rollers (rollers);
  • deflection rollers rollers
  • other transport variants are also possible, for example the insertion and / or removal of the band into the bath through sealed slots or one of the other variants mentioned in the prior art described at the beginning.
  • the width of an anode is smaller and the width of a cathode is greater than the width of the strip, and the length of an anode is greater than the length of a cathode.
  • “Length” is to be understood as the extent of the respective electrode surface in the tape transport direction and “width” is the extent of the electrode surface perpendicular to the tape transport direction.
  • the band to be treated does not touch the electrode surface during the process, it is preferably closer to the anode than to the cathode.
  • the terms "anode” or “cathode” or “electrode” are generally to be understood as an integral, electrically conductive body; However, arrangements are also possible in which the electrically conductive body consists of several partial bodies, so that several partial anodes connected to the same pole of a current source are then opposed, for example, in a treatment bath of a one-piece cathode.
  • the relative dimensions in the above explanations then relate not only to one-piece electrodes, but also to an electrode consisting of several partial bodies.
  • the aqueous electrolytes to be used are those known from the prior art (see also introduction to the description), ie in particular aqueous H 2 SO 4 or H 3 PO 4 solutions, but also oxalic acid, chromic acid etc., mixtures thereof or two or more baths with different electrolytes.
  • concentrations of acid are generally between 2 and 60% by weight, the temperature of the electrolyte between 5 and 60 ° C, the current densities of the direct current to be used or modifications thereof between 0.5 and 150 A / dm 2 and the anodizing times between 5 and 240 sec.
  • the layer weights of aluminum oxide range from 0.5 to 10 g / m 2 , corresponding to a layer thickness of approximately 0.15 to 3.0 ⁇ m.
  • the process according to the invention is preferably carried out so that the aqueous electrolyte is parallel to the surface of the treating tape is moved, for example at a speed of 5 to 100 cm / sec, in particular the direction of movement of the electrolyte is opposite to the tape transport direction.
  • Suitable base materials for the material to be oxidized according to the invention include those made of aluminum or one of its alloys, which have, for example, a content of more than 98.5% by weight of Al and proportions of Si, Fe, Ti, Cu and Zn. These aluminum strips are still, optionally after pre-cleaning, mechanical (e.g. by brushing and / or with abrasive treatments), chemical (e.g. by etching agents) and / or electrochemical (e.g. by AC treatment in aqueous HC1 -, HN0 3 - and / or in salt solutions) roughened.
  • mechanical e.g. by brushing and / or with abrasive treatments
  • chemical e.g. by etching agents
  • electrochemical e.g. by AC treatment in aqueous HC1 -, HN0 3 - and / or in salt solutions
  • the process parameters for continuous process control in an electrochemical roughening stage are in the following ranges: the temperature of the electrolyte between 20 and 60 ° C., the active substance (acid, salt) concentration between 2 and 100 g / 1 (even higher for salts) , the current density between 15 and 250 A / dm 2 , the residence time between 3 and 100 sec and the electrolyte flow rate on the surface of the workpiece to be treated between 5 and 100 cm / sec; change is usually the type of current Current used, but modified types of current such as alternating current with different amplitudes of the current strength for the anode and cathode current are possible.
  • the average roughness depth R z of the roughened surface is in the range from about 1 to 15 ⁇ m. The roughness depth is determined in accordance with DIN 4768 in the version from October 1970, the roughness depth R is then the arithmetic mean of the individual roughness depths of five adjacent individual measuring sections.
  • Pre-cleaning includes, for example, treatment with aqueous NaOH solution with or without degreasing agent and / or complexing agents, trichlorethylene, acetone, methanol or other commercially available aluminum stains.
  • the roughening or, in the case of several roughening stages, also between the individual stages, an abrasive treatment can additionally be carried out, in particular a maximum of 2 g / m 2 being removed (up to 5 g / m 2 between the stages);
  • aqueous solutions of alkali metal hydroxide or aqueous solutions of alkaline salts or aqueous acid solutions based on HN0 3 , H 2 SO 4 or H 3 PO 4 are used as abrasive solutions.
  • non-electrochemical treatments are also known which only have a rinsing and / or cleaning effect and, for example, for removing deposits formed during roughening ("Schmant") or simply for Removal of electrical serve lytic residues; For example, dilute aqueous alkali hydroxide solutions or water are used for these purposes.
  • the stage of anodic oxidation of the aluminum strip can also be followed by one or more post-treatment stages.
  • These post-treatment stages serve in particular to additionally increase the hydrophilicity of the aluminum oxide layer, which is already sufficient for many areas of application, the remaining known properties of this layer being at least retained.
  • the ribbons produced according to the invention are used in particular as carriers in the production of offset printing plates, ie a radiation-sensitive coating is applied to the carrier material on one or both sides either at the manufacturer of presensitized printing plates or directly from the consumer.
  • a radiation-sensitive coating is applied to the carrier material on one or both sides either at the manufacturer of presensitized printing plates or directly from the consumer.
  • all layers that are suitable for radiation (light) are suitable the irradiation (exposure), optionally with a subsequent development and / or fixation, provide an image-like area from which printing can take place.
  • Tested coated offset printing plates are converted into the desired printing form in a known manner by imagewise exposure or irradiation and washing out of the non-image areas with a developer, preferably an aqueous developer solution.
  • the already roughened aluminum strip 1 (FIGS. 1 and 2) is introduced via a roller 7 into the treatment bath 2, which is filled with the aqueous electrolyte 3 (for example an 'aqueous H 2 SO 4 solution). Further changes in direction of the belt 1 are brought about by further rollers 7 and 8.
  • the tape 1 is guided horizontally between the horizontally arranged electrodes 4, 5.
  • the electrodes 4, 5 have the shape of a plate or one Grid on; the cathode 4 consists for example of lead, the anode 5 of aluminum or a titanium modified with noble metal or noble metal oxide.
  • variant 1 of the prior art has the anode 6 outside the aqueous electrolyte and has the shape of a roller, rod or roller.
  • variant 2 of the prior art FIG. 4
  • the anode 5 ' is in a first treatment bath 2' and the cathode 4 'in a second treatment bath 2 ", which are filled with the same or different aqueous electrolytes 3', 3" are.
  • parts by weight relate to parts by volume such as kg to dm 3 , percentages relate to the weight.
  • An electrochemically roughened aluminum strip with a width of 650 mm is anodized as follows.
  • An aluminum plate with the dimensions 6000 mm x 500 mm x 0.5 mm (length x width x height) serves as the anode on the underside of the strip, which is coated with gauze with a mesh width of 0.2 mm to protect against contact by the moving strip is.
  • the distance between the strip and the anode is 5 mm.
  • Several smaller lead cathodes with the total dimensions of 3000 mm x 1000 mm x 100 mm are arranged above the belt at a distance of 50 mm.
  • a 20% aqueous H2 S0 4 solution containing 1% of aluminum sulfate is used as the electrolyte, the temperature is 40 ° C., the anodizing time is 20 seconds and the current density is 10 A / dm 2 (voltage 30 V).
  • the oxide layer weight is 1.5 g / m 2.
  • the belt After rinsing with water and drying, the belt is provided with the following positive-working light-sensitive layer:
  • the layer weight is about 2 g / m 2 .
  • test pieces are exposed in a known manner and developed with an aqueous alkaline solution. From such a printing form, approximately 150,000 to 200,000 prints can be produced in practical quality.
  • a grid anode 120 mm x 80 mm
  • a lead sheet cathode 100 mm x 100 mm
  • An aluminum sheet is dipped between the anode and cathode, which is 90 mm wide and is closer to the anode than to the cathode.
  • a current density of 15 A / dm 2 (voltage 14 V) and a temperature of 50 ° C, anodizing is carried out for 60 seconds.
  • the weight of the oxide layer is 3.6 g / m2 .
  • Example 2 The procedure of Example 2 is followed, but a titanium lattice coated with activated noble metal oxide (Ru0 2 ) is used as the anode. The results correspond to those of Example 2.
  • Ru0 2 activated noble metal oxide
  • Example 2 The procedure is as described in Example 2, but a solid aluminum sheet is used as the anode, the voltage increases from 14 to 26 V. The results correspond to those of Example 2.
  • Example 2 The procedure is as described in Example 2, but a 10% aqueous H 3 PO 4 solution is used as the electrolyte at 55 ° C., a current density of 10 A / dm 2 (voltage 30 V). The results correspond to those of Example 2.

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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)
EP84106318A 1983-06-13 1984-06-02 Procédé et dispositif pour l'anodisation en continu sur une seule face des bandes d'aluminium et son utilisation dans la fabrication des plaques d'impression Expired EP0132549B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
WOPCT/EP83/00152 1983-06-13
PCT/EP1983/000152 WO1984004934A1 (fr) 1983-06-13 1983-06-13 Procede et installation pour l'oxydation anodique unilaterale continue de bandes d'aluminium et leur utilisation lors de la fabrication de plaques d'impression offset

Publications (2)

Publication Number Publication Date
EP0132549A1 true EP0132549A1 (fr) 1985-02-13
EP0132549B1 EP0132549B1 (fr) 1988-10-19

Family

ID=8164890

Family Applications (2)

Application Number Title Priority Date Filing Date
EP83901816A Expired EP0178297B1 (fr) 1983-06-13 1983-06-13 Procede et installation pour l'oxydation anodique unilaterale continue de bandes d'aluminium et leur utilisation lors de la fabrication de plaques d'impression offset
EP84106318A Expired EP0132549B1 (fr) 1983-06-13 1984-06-02 Procédé et dispositif pour l'anodisation en continu sur une seule face des bandes d'aluminium et son utilisation dans la fabrication des plaques d'impression

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP83901816A Expired EP0178297B1 (fr) 1983-06-13 1983-06-13 Procede et installation pour l'oxydation anodique unilaterale continue de bandes d'aluminium et leur utilisation lors de la fabrication de plaques d'impression offset

Country Status (11)

Country Link
US (1) US4605480A (fr)
EP (2) EP0178297B1 (fr)
JP (1) JPS60501564A (fr)
AU (1) AU568081B2 (fr)
BR (1) BR8307765A (fr)
CA (1) CA1244793A (fr)
DE (1) DE3378270D1 (fr)
ES (1) ES8603594A1 (fr)
FI (1) FI80728C (fr)
WO (1) WO1984004934A1 (fr)
ZA (1) ZA844446B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111793816A (zh) * 2020-07-31 2020-10-20 常州费曼生物科技有限公司 单面阳极氧化多孔输液器滤膜连续阳极氧化设备及工艺

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4006363C1 (fr) * 1990-03-01 1991-01-17 Heidelberger Druckmaschinen Ag, 6900 Heidelberg, De
US7023162B2 (en) * 2003-02-18 2006-04-04 The Chamberlain Group, Inc. Automatic gate operator
DE102006052170A1 (de) * 2006-11-02 2008-05-08 Steinert Elektromagnetbau Gmbh Anodische Oxidschicht für elektrische Leiter, insbesondere Leiter aus Aluminium, Verfahren zur Erzeugung einer anodischen Oxidschicht und elektrischer Leiter mit anodischer Oxidschicht

Citations (1)

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Publication number Priority date Publication date Assignee Title
FR1014528A (fr) * 1946-02-26 1952-08-18 United Anodising Ltd Procédé d'anodisation de pièces métalliques

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US3296114A (en) * 1963-07-17 1967-01-03 Lloyd Metal Mfg Company Ltd Anodizing apparatus
NL131875C (fr) * 1964-02-04 1900-01-01 Aluminium Lab Ltd
US3359189A (en) * 1964-02-04 1967-12-19 Aluminium Lab Ltd Continuous anodizing process and apparatus
US3420760A (en) * 1965-04-30 1969-01-07 Gen Dynamics Corp Process for descaling steel strip in an aqueous organic chelating bath using alternating current
DE1621115C3 (de) * 1967-10-17 1981-06-25 Metalloxyd GmbH, 5000 Köln Verfahren zur Herstellung eines Trägers aus Aluminium für lithographische Druckplatten
ZA6807938B (fr) * 1967-12-04
DE1906538B2 (de) * 1968-04-10 1970-11-19 Matsushita Electric Industrial Co. Ltd., Osaka (Japan) Verfahren zur Herstellung anodischer Oxi-ischichten hoher Biegefestigkeit auf Aluiiinium und Aluminiumlegierungen
US3692640A (en) * 1969-09-18 1972-09-19 Matsushita Electric Industrial Co Ltd Continuous anodic oxidation method for aluminum and alloys thereof
US3718547A (en) * 1970-11-16 1973-02-27 Alcan Res & Dev Continuous electrolytic treatment for cleaning and conditioning aluminum surfaces
DE2234424C3 (de) * 1972-07-13 1980-10-09 Hoechst Ag, 6000 Frankfurt Verfahren und Vorrichtung zur einseitigen kontinuierlichen elektrolytischen Aufrauhung und/oder Oxidation von Aluminiumbändern
US3865700A (en) * 1973-05-18 1975-02-11 Fromson H A Process and apparatus for continuously anodizing aluminum
CH601502A5 (fr) * 1974-07-31 1978-07-14 Alusuisse
US3902976A (en) * 1974-10-01 1975-09-02 S O Litho Corp Corrosion and abrasion resistant aluminum and aluminum alloy plates particularly useful as support members for photolithographic plates and the like
DE2619821A1 (de) * 1976-05-05 1977-11-17 Hoechst Ag Verfahren und vorrichtung zur kontinuierlichen elektrolytischen behandlung eines metallbandes
US4226680A (en) * 1977-06-06 1980-10-07 Alcan Research And Development Limited Process for electrolytic coloration of anodized aluminium
JPS5481133A (en) * 1977-12-12 1979-06-28 Fuji Photo Film Co Ltd Anodic oxidation device
DE2811396A1 (de) * 1978-03-16 1979-09-27 Hoechst Ag Verfahren zur anodischen oxidation von aluminium und dessen verwendung als druckplatten-traegermaterial
JPS54123302A (en) * 1978-03-17 1979-09-25 Tokyo Ouka Kougiyou Kk Method of making photosensitive plate support for flat plate printing
EP0007233B1 (fr) * 1978-07-13 1982-04-28 BICC Public Limited Company Procédé de traitement de feuilles d'aluminium on de plaques lithographiques et produits obtenus de cette mainère
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FR1014528A (fr) * 1946-02-26 1952-08-18 United Anodising Ltd Procédé d'anodisation de pièces métalliques

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111793816A (zh) * 2020-07-31 2020-10-20 常州费曼生物科技有限公司 单面阳极氧化多孔输液器滤膜连续阳极氧化设备及工艺
CN111793816B (zh) * 2020-07-31 2022-03-25 常州费曼生物科技有限公司 单面阳极氧化多孔输液器滤膜连续阳极氧化设备及工艺

Also Published As

Publication number Publication date
JPS60501564A (ja) 1985-09-19
WO1984004934A1 (fr) 1984-12-20
ZA844446B (en) 1985-01-30
CA1244793A (fr) 1988-11-15
FI80728C (fi) 1990-07-10
US4605480A (en) 1986-08-12
FI80728B (fi) 1990-03-30
EP0132549B1 (fr) 1988-10-19
FI852728L (fi) 1985-07-10
ES533256A0 (es) 1985-12-16
EP0178297B1 (fr) 1988-10-19
DE3378270D1 (en) 1988-11-24
AU568081B2 (en) 1987-12-17
ES8603594A1 (es) 1985-12-16
FI852728A0 (fi) 1985-07-10
EP0178297A1 (fr) 1986-04-23
BR8307765A (pt) 1986-04-15
JPH0514031B2 (fr) 1993-02-24
AU1606983A (en) 1985-01-04

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