EP0178297B1 - Verfahren und vorrichtung zur kontinuierlichen einseitigen anodischen oxidation von aluminiumbändern und deren verwendung bei der herstellung von offsetdruckplatten - Google Patents

Verfahren und vorrichtung zur kontinuierlichen einseitigen anodischen oxidation von aluminiumbändern und deren verwendung bei der herstellung von offsetdruckplatten Download PDF

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Publication number
EP0178297B1
EP0178297B1 EP83901816A EP83901816A EP0178297B1 EP 0178297 B1 EP0178297 B1 EP 0178297B1 EP 83901816 A EP83901816 A EP 83901816A EP 83901816 A EP83901816 A EP 83901816A EP 0178297 B1 EP0178297 B1 EP 0178297B1
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EP
European Patent Office
Prior art keywords
anode
cathode
electrolyte
strip
anodic oxidation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP83901816A
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German (de)
English (en)
French (fr)
Other versions
EP0178297A1 (de
Inventor
Joachim Stroszynski
Gerhard Sprintschnik
Walter 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
Original Assignee
Hoechst AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Priority to AT83901816T priority Critical patent/ATE38063T1/de
Publication of EP0178297A1 publication Critical patent/EP0178297A1/de
Application granted granted Critical
Publication of EP0178297B1 publication Critical patent/EP0178297B1/de
Expired legal-status Critical Current

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    • 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 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 directly by the consumer or by the manufacturer of precoated printing plates or 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 which is roughened on the surface by known methods by dry brushing, wet brushing, sandblasting, chemical and / or electrochemical treatment, is used particularly frequently as the base material for such layer supports.
  • 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 4 , H 2 C 2 0 4 , H 3 B0 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 strip is separated from the contact roller, arc discharges can take place, which irreversibly destroy the surface of the aluminum strip and form defects in the subsequent anodic oxidation or can even render 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 being at least partially also electrolytes.
  • 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 device for the continuous one-sided anodic oxidation of aluminum strips, which makes 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 device for the continuous one-sided anodic oxidation of strips made of aluminum or one of its alloys using direct current, comprising a) at least one treatment bath which is filled with an aqueous electrolyte, b) at least one anode, each below and c) at least one cathode each, above the strip to be treated in the elec- trolytes are arranged, the characteristic feature of which is that the width of the anode (s) is smaller and the width of the cathode (s) is greater than the width of the strip.
  • 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.
  • Essentially horizontal is to be understood to mean that angular deviations of up to 30 ° from the horizontal should also be included.
  • a device is provided, the length of the anode (s) being greater than the length of the cathode (s).
  • the 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); However, 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.
  • “length” is to be understood as the extent of the respective electrode surface in the tape transport direction and “width” is the expansion of the electrode surface perpendicular to the tape transport direction.
  • the tape to be treated does not touch the electrode surface during transport, 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 P0 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.
  • aqueous electrolyte is moved parallel to the surface of the strip to be treated, for example at a speed of 5 to 100 cm / sec, in particular the direction of movement of the electrolyte is opposite to the strip 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 for example have a content of. have 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 HCl) -, 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 HCl
  • 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 / l (even higher for salts) , the current density between 15 and 250 Aldm 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; AC is mostly used as the type of current, but modified types of current such as alternating current with different amplitudes of the current strength for the anode and cathode currents are also 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 z 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 Serve removal of electrolyte 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 tapes produced with the device 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 on one or both sides either by the manufacturer of presensitized printing plates or directly by the consumer material applied.
  • a radiation-sensitive coating is applied to the carrier on one or both sides either by the manufacturer of presensitized printing plates or directly by the consumer material applied.
  • all layers are suitable as radiation (light) sensitive layers which, after irradiation (exposure), optionally with subsequent development and / or fixation, provide an image-like area from which printing can take place.
  • coated offset printing plates produced with the tapes treated according to the invention 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 HA04 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 a grid; 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.
  • the advantages of the device according to the invention are not only that the disadvantages of the anode arranged outside the aqueous electrolyte do not work, but in particular that a large space and investment cost requirement for the second electrolyte bath or baths is saved. It is particularly surprising that this latter advantage does not come at the expense of surface quality.
  • 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 6,000 mm x 500 mm x 0.5 mm (length x width x height) serves as an anode on the underside of the strip, which protects against contact by the moving strip with gauze with a mesh width of 0.2 mm is enveloped.
  • the distance between the strip and the anode is 5 mm.
  • Several smaller lead cathodes with the total dimensions of 3,000 mm x 1,000 mm x 100 mm are arranged at a distance of 50 mm above the strip.
  • a 20% aqueous H 2 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 layer weight is about 2 g / m 2 .
  • Test pieces are used to manufacture the printing form 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 Aldm 2 (voltage 14 V) and a temperature of 50 ° C, anodizing is carried out for 60 seconds.
  • the oxide layer weight is 3.6 g / m2.
  • Example 2 The procedure of Example 2 is followed, but a titanium lattice coated with activated noble metal oxide (RuO 2 ) is used as the anode. The results correspond to those of Example 2.
  • RuO 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 of Example 2 is followed, 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)
EP83901816A 1983-06-13 1983-06-13 Verfahren und vorrichtung zur kontinuierlichen einseitigen anodischen oxidation von aluminiumbändern und deren verwendung bei der herstellung von offsetdruckplatten Expired EP0178297B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83901816T ATE38063T1 (de) 1983-06-13 1983-06-13 Verfahren und vorrichtung zur kontinuierlichen einseitigen anodischen oxidation von aluminiumbaendern und deren verwendung bei der herstellung von offsetdruckplatten.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP1983/000152 WO1984004934A1 (en) 1983-06-13 1983-06-13 Method and plants for the continuous unilateral anodic oxidation of aluminium bands and utilization thereof to make offset printing plates

Publications (2)

Publication Number Publication Date
EP0178297A1 EP0178297A1 (de) 1986-04-23
EP0178297B1 true EP0178297B1 (de) 1988-10-19

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Application Number Title Priority Date Filing Date
EP83901816A Expired EP0178297B1 (de) 1983-06-13 1983-06-13 Verfahren und vorrichtung zur kontinuierlichen einseitigen anodischen oxidation von aluminiumbändern und deren verwendung bei der herstellung von offsetdruckplatten
EP84106318A Expired EP0132549B1 (de) 1983-06-13 1984-06-02 Verfahren und Vorrichtung zur kontinuierlichen einseitigen anodischen Oxidation von Aluminiumbändern und deren Verwendung bei der Herstellung von Offsetdruckplatten

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EP84106318A Expired EP0132549B1 (de) 1983-06-13 1984-06-02 Verfahren und Vorrichtung zur kontinuierlichen einseitigen anodischen Oxidation von Aluminiumbändern und deren Verwendung bei der Herstellung von Offsetdruckplatten

Country Status (11)

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US (1) US4605480A (xx)
EP (2) EP0178297B1 (xx)
JP (1) JPS60501564A (xx)
AU (1) AU568081B2 (xx)
BR (1) BR8307765A (xx)
CA (1) CA1244793A (xx)
DE (1) DE3378270D1 (xx)
ES (1) ES533256A0 (xx)
FI (1) FI80728C (xx)
WO (1) WO1984004934A1 (xx)
ZA (1) ZA844446B (xx)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

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DE4006363C1 (xx) * 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
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

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
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

Also Published As

Publication number Publication date
AU568081B2 (en) 1987-12-17
EP0178297A1 (de) 1986-04-23
ES8603594A1 (es) 1985-12-16
AU1606983A (en) 1985-01-04
WO1984004934A1 (en) 1984-12-20
JPH0514031B2 (xx) 1993-02-24
US4605480A (en) 1986-08-12
JPS60501564A (ja) 1985-09-19
ES533256A0 (es) 1985-12-16
FI852728L (fi) 1985-07-10
FI80728C (fi) 1990-07-10
CA1244793A (en) 1988-11-15
EP0132549B1 (de) 1988-10-19
EP0132549A1 (de) 1985-02-13
ZA844446B (en) 1985-01-30
FI80728B (fi) 1990-03-30
FI852728A0 (fi) 1985-07-10
BR8307765A (pt) 1986-04-15
DE3378270D1 (en) 1988-11-24

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