EP0082452B1 - Procédé de grenage électrochimique d'aluminium avec un courant alternatif triphasé et son utilisation dans la fabrication des plaques à imprimer - Google Patents

Procédé de grenage électrochimique d'aluminium avec un courant alternatif triphasé et son utilisation dans la fabrication des plaques à imprimer Download PDF

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Publication number
EP0082452B1
EP0082452B1 EP82111543A EP82111543A EP0082452B1 EP 0082452 B1 EP0082452 B1 EP 0082452B1 EP 82111543 A EP82111543 A EP 82111543A EP 82111543 A EP82111543 A EP 82111543A EP 0082452 B1 EP0082452 B1 EP 0082452B1
Authority
EP
European Patent Office
Prior art keywords
aluminum
roughening
alternating current
electrodes
roughened
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
EP82111543A
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German (de)
English (en)
Other versions
EP0082452A1 (fr
Inventor
John E. Walls
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.)
CNA Holdings LLC
Original Assignee
American Hoechst Corp
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 American Hoechst Corp filed Critical American Hoechst Corp
Publication of EP0082452A1 publication Critical patent/EP0082452A1/fr
Application granted granted Critical
Publication of EP0082452B1 publication Critical patent/EP0082452B1/fr
Expired legal-status Critical Current

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Classifications

    • 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
    • Y10S205/00—Electrolysis: processes, compositions used therein, and methods of preparing the compositions
    • Y10S205/921—Electrolytic coating of printing member, other than selected area coating

Definitions

  • the invention relates to a process for the bilateral electrochemical roughening of plate, foil or tape-shaped material made of aluminum with three-phase alternating current and the use of the material in the production of printing plates.
  • Printing plates generally consist of a support and at least one radiation-sensitive reproduction layer arranged thereon, this layer either from the consumer (in the case of non-precoated plates) or from the industrial one Manufacturer (for pre-coated boards) is applied to the substrate.
  • Aluminum or one of its alloys has established itself as a layer material in the printing plate field.
  • these substrates can also be used without a modifying pretreatment, but they are generally modified in or on the surface, for example by mechanical, chemical and / or electrochemical roughening (sometimes called grain or etching in the literature), chemical or electrochemical oxidation and / or treatment with hydrophilizing agents.
  • a combination of the above-mentioned types of modification is often used, in particular a combination of electrochemical roughening and anodic oxidation, optionally with a subsequent hydrophilization step.
  • the roughening is carried out, for example, in aqueous acids such as aqueous HCl or HNO 1 solutions or in aqueous salt solutions such as aqueous NaCl or Al (N0 3 ) 3 solutions using alternating current.
  • the roughness depths that can be achieved in this way are in the range from about 1 to 15 ⁇ m, in particular in the range from 2 to 8 ⁇ 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.
  • a process for the electrochemical roughening of aluminum in which an aluminum foil strip is guided as a central conductor through an aqueous electrolyte containing HCI and treated with alternating current, the n phases ( preferably has 3 phases R, S and T). At least as many electrodes are alternately arranged in succession in the electrolyte as the alternating current has phases, i. H. usually 3, 6, etc. electrodes. When roughening on one side, the electrodes all face the same hinge side, alternately on both sides of the hinge on both sides.
  • the object of the present invention is therefore to propose a method for the electrochemical roughening of aluminum materials on both sides, which can be used in particular as a carrier material for printing plates and in which the energy of the current to be used can be used as far as possible for the roughening.
  • the invention is based on the known method for bilateral electrochemical roughening of plate, foil or strip material made of aluminum or its alloys in an aqueous electrolyte solution and three-phase alternating current.
  • the method according to the invention is then characterized in that two of the three phases are conductively connected with electrodes arranged on both sides of the material and the rest of the phase with the material to be roughened.
  • a three-phase alternating current is to be understood as a current which has three phases (R, S and T) with the same amplitude, but with a phase shift of 120 ° each; if these three phases are equally loaded, a neutral conductor would not carry any current (see, for example, Dorn, Physik - Oberissue - Issue A, Hermann Schroedel Verlag - Hanover, 1966, 10th edition, pp. 256 to 258).
  • consumers are connected to the power grid of the power plant either in a star connection or in a delta connection.
  • the materials to be roughened are, for example, those with an aluminum content of a99.5, 99.2, a 98.5 or 98.3, which are added as Fe, Si, Cu and optionally Zn, Ti, Mn and / or contain Mg; these are traded with the names »pure aluminum «, »1100 «, »3003 « or »A-19 «.
  • the thickness of these materials is generally in the range of about 0.1 to 0.65 mm.
  • one pole of a three-phase alternating current source is connected to one of two electrodes which are located in front of and behind the aluminum material in the preferred vertical material guide or are arranged above and below the aluminum material with a horizontal material guide, while the third pole is Three phase AC power source is connected to the aluminum material itself, the aluminum material and the electrodes being in an aqueous electrolyte solution.
  • This arrangement allows both sides of the aluminum material to be roughened simultaneously, both a discontinuous procedure with aluminum sections and preferably a continuous procedure with aluminum strips being possible. It has been shown that the total energy requirement of the current for a material to be roughened on both sides at the same time is substantially less than if each side were roughened individually.
  • the roughening results in a very uniform roughening pattern when the method according to the invention is used, since the degree of roughening in the regions of the material near the edges is substantially equal to that in the middle of the material. This is not the case with roughened surfaces in two separate steps.
  • the surface obtained according to the invention also has a uniform hole structure and has little pitting.
  • Typical aqueous electrolyte solutions which can be used are those known from the prior art which, in addition to water, generally contain one or more electrolytes, such as acids or salts; These include, for example, hydrochloric acid, nitric acid, aluminum salts of mineral acids and compounds containing chloride or phosphate ions; in addition, these aqueous electrolyte solutions can also contain modifiers such as gluconic acid, tartaric acid, boric acid or hydrogen peroxide in a known manner.
  • the exact parameters The conditions under which the electrochemical roughening can take place are variable and depend, inter alia, on the results desired in the individual case and on the composition of the aqueous electrolyte solution.
  • the concentration of the aqueous electrolyte solution can in principle be in a range of about 1 g / l until the solution is saturated on the electrolyte or electrolytes.
  • the concentration of the electrolyte is preferably between 3 and 20 g / l, in particular between 8 to 20 g / l, and particularly preferably between 10 and 15 g / l.
  • the aluminum material to be roughened is usually connected to the S-pole of a three-phase variable transformer in the practical implementation of the method according to the invention, the R-pole and the T-pole are conductively connected, for example, to two graphite plates serving as electrodes. The graphite plates are then set up on both sides of the support, the preferred distance being 1.5 cm.
  • the material to be roughened can be conductively connected to the S pole in a known manner, for example via a contact roller or contact cell.
  • the electrolyte solution While the aluminum material and electrodes are immersed in the aqueous electrolyte solution, it is very advantageous to move the electrolyte solution so that it flows between the material and the electrodes, and the preferred speed of movement can be, for example, 0.3 m / sec or more. As a result of this flowing movement, the gas generated during the roughening process is flushed away, so that a constant surface resistance is ensured. In addition, fresh electrolyte solution is constantly passed by, which ensures that the roughening conditions are as constant as possible.
  • the electrodes are preferably made of graphite, but other conductive materials such as lead or stainless steel can also be used.
  • the distance between the electrodes and the aluminum material is in particular less than 10 cm, preferably less than 5 cm and particularly preferably less than 3 cm.
  • the three-phase alternating current used coming from the network can be, for example, 60 A and 480 V, but these values are not mandatory. This current can then be converted into a current of 1320 A and about 20 to 25 V via a variable transformer. These values are not critical and can be tailored to the respective requirements by a person skilled in the art, on the other hand the current density is of greater importance.
  • the current flow from the electrodes to the material to be roughened should be such that on each side of the aluminum material a current density of about 30 to 120 A / dm 2 , preferably 40 to 100 A / dm 2 , and in particular 60 to 75 A / dm 2 is reached.
  • an anodic oxidation of the aluminum can then follow in a further process step to be used, for example to improve the abrasion and adhesion properties of the surface of the material.
  • the usual electrolytes such as H 2 S0 4 , H 3 P0 4 , H 2 C 2 0 4 , amidosulfonic acid, sulfosuccinic acid, sulfosalicylic acid or mixtures thereof can be used for anodic oxidation.
  • the layer weights of aluminum oxide range from 1 to 10 g / m 2 , corresponding to a layer thickness of approximately 0.3 to 3.0 ⁇ m.
  • a modification which removes the surface from the roughened surface can also be used, as described, for example, in DE-OS 3 009 103.
  • Such a modifying intermediate treatment can, among other things, enable the build-up of abrasion-resistant oxide layers and a lower tendency to tone during later printing.
  • the step of anodic oxidation of the aluminum material can also be followed by one or more post-treatment steps.
  • all layers are suitable as light-sensitive reproduction layers which, after exposure, optionally with subsequent development and / or fixation, provide an image-like area from which printing can take place and / or which represent a relief image of an original. They are applied either by the manufacturer of presensitized printing plates or by so-called dry resists or directly by the consumer to one of the usual carrier materials. To the photosensitive Chen reproduction layers count such as z. B.
  • the suitable layers also include the electrophotographic layers, ie those which contain an inorganic or organic photoconductor. In addition to the light-sensitive substances, these layers can of course also other components such.
  • An aluminum plate with a content of more than 99.5% aluminum is immersed together with a graphite electrode arranged at a distance of 1.5 cm in an aqueous electrolyte solution which contains 13 parts by weight of HN0 3 and 65 parts by weight in 1000 parts by volume. Contains parts of aluminum nitrate.
  • One side of the plate is roughened by the action of a single-phase alternating current of 300 A for 60 seconds, so that the power consumption is 6.6 kW.
  • the plate is then turned over and the other side roughened in the same way, so that the total power consumption is 13.2 kW. This means that the power required to achieve a roughening, which can already meet printing requirements, is 91.1 kW / m 2 , but the roughening does not have the uniformity of roughening according to the method according to the invention.
  • a further aluminum plate of the same quality is immersed in the same electrolyte together with 2 graphite electrodes, which are located on both sides of the plate at a distance of 1.5 cm each. Both sides are roughened by the action of 300 A each from two phases (R and T) of the three-phase alternating current, the remaining phase (S) lies on the aluminum plate; only 52.8 seconds are required for the roughening process.
  • the total power consumption to achieve a substantially uniform roughening of both plate surfaces suitable for printing purposes is thus 11.6 kW. This corresponds to a power consumption of 80 kW / m 2 aluminum surface or a saving of 12% compared to the conventional processes.
  • An aluminum plate containing 99.2% aluminum is degreased in a conventional aqueous alkaline solution and rinsed well with water.
  • the plate treated in this way is placed wet in an aqueous electrolyte solution which contains 13 parts by weight of HNO 3 and 65 parts by weight of aluminum nitrate in 1000 parts by volume.
  • the aluminum plate is firmly connected to a pole of an AC power source, being held in place by a non-conductive bracket.
  • a graphite electrode is placed opposite the aluminum plate at a distance of 1.5 cm, which is connected to the second pole of the single-phase AC power source. With constant stirring of the electrolyte solution between the graphite electrode and the aluminum plate, a voltage of 22 V (60 Hz) with a current flow of 600 A is applied for 60 seconds.
  • the plate After the treatment, the plate is rinsed well and dried. A microscopic examination shows that due to the extensive effect of the current, all four edges of the opposite side are roughened about 1 cm wide. The treated side has an even, weak roughening in the middle, the roughening is coarser near the edge, and a slight aluminum dissolution is found on the edge. In order to be able to use a printing plate carrier produced in this way, one would have to use an oversized plate format and cut off the edges after the treatment. A microscopic evaluation using a scanning electron microscope (SEM) in 1000, 2000 and 5000 times magnification confirms the visual impression. The middle part looks even but undertreated, which means the roughening is too flat.
  • SEM scanning electron microscope
  • a roughened plate is produced according to the information in comparative example V2.
  • the plate is removed from the bath, turned over and immersed again in the bath, so that its untreated side is now facing the electrode, this side is handled in the same way as with the first screen te.
  • both the visual inspection and the examination with the scanning electron microscope confirm that the plate obtained has a rather undertreated central zone and an excessively roughened edge area.
  • the page treated first shows no changes, ie a plate roughened on both sides is obtained which cannot be accepted for the practice in the printing plate area.
  • a plate is degreased as described in comparative example V2 and immersed in a solution of the composition given there. It is connected to a pole (S) of a three-phase variable transformer.
  • the existing graphite electrode is connected to a second pole (R), in addition a graphite electrode of the same type is attached to the opposite side of the plate and connected in the same way to the third remaining pole (T).
  • the two electrodes are 1.5 cm apart from the aluminum plate attached between them.
  • a voltage of 22 V (60 Hz) and 530 A is applied for 60 seconds and the plate is thus electrochemically roughened. After the treatment, the plate is removed from the bath, rinsed and wiped dry.
  • the plate has a very uniform appearance on both sides, i. that is, both sides look exactly the same, they show no signs of insufficient roughening in the middle, rougher roughening in the edge area or etched away aluminum edges.

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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 (6)

1. Procédé pour la cratérisation électrochimique des deux côtés d'un matériau d'aluminium ou d'un alliage d'aluminium en forme de plaques, de feuilles ou de rubans, dans une solution électrolytique aqueuse avec un courant alternatif triphasé, caractérisé par le fait que deux des trois phases sont connectées à des électrodes disposées sur les deux côtés du matériau et la phase restante au matériau à cratériser lui- même.
2. Procédé selon la revendication 1, caractérisé par le fait que la première et la troisième des trois phases sont reliées aux électrodes et la deuxième phase au matériau.
3. Procédé selon l'une des revendications 1 ou 2, caractérisé par le fait que les électrodes et le matériau sont disposés verticalement.
4. Procédé selon l'une des revendications 1 à 3, caractérisé par le fait que la solution aqueuse contient en tant qu'électrolyte de l'acide chlorhydrique et/ou de l'acide nitrique et/ou un sel.
5. Procédé selon l'une des revendications 1 à 4, caractérisé par le fait que l'on procède après la cratérisation électrochimique à une oxydation anodique dans une solution électrolytique aqueuse qui contient H2SO4 et/ou H3PO4.
6. Utilisation du matériau cratérisé selon les revendications 1 à 5 dans la fabrication de clichés portant une couche de reproduction sensible aux radiations.
EP82111543A 1981-12-21 1982-12-13 Procédé de grenage électrochimique d'aluminium avec un courant alternatif triphasé et son utilisation dans la fabrication des plaques à imprimer Expired EP0082452B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US332392 1981-12-21
US06/332,392 US4396468A (en) 1981-12-21 1981-12-21 Three phase graining of aluminum substrates

Publications (2)

Publication Number Publication Date
EP0082452A1 EP0082452A1 (fr) 1983-06-29
EP0082452B1 true EP0082452B1 (fr) 1985-09-11

Family

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EP82111543A Expired EP0082452B1 (fr) 1981-12-21 1982-12-13 Procédé de grenage électrochimique d'aluminium avec un courant alternatif triphasé et son utilisation dans la fabrication des plaques à imprimer

Country Status (4)

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US (1) US4396468A (fr)
EP (1) EP0082452B1 (fr)
JP (1) JPS58157997A (fr)
DE (1) DE3266243D1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3217499A1 (de) * 1982-05-10 1983-11-10 Hoechst Ag, 6230 Frankfurt Verfahren zur elektrochemischen aufrauhung von aluminium fuer druckplattentraeger
JPS5938389A (ja) * 1982-08-26 1984-03-02 Okuno Seiyaku Kogyo Kk アルミニウム合金鋳物又はアルミニウム合金ダイカストの表面処理法
CH655135A5 (de) * 1983-07-14 1986-03-27 Alusuisse Vorbehandlung eines bandes oder einer folie aus aluminium durch elektrochemische oxidation.
US4502925A (en) * 1984-06-11 1985-03-05 American Hoechst Corporation Process for aluminum surface preparation
US4548683A (en) * 1984-09-28 1985-10-22 Polychrome Corp. Method of electrolytically graining a lithographic plate
DE3910213A1 (de) * 1989-03-30 1990-10-11 Hoechst Ag Verfahren und vorrichtung zum aufrauhen eines traegers fuer lichtempfindliche schichten
IT1235332B (it) * 1989-06-05 1992-06-26 Diaprint S P A Granitura elettrochimica di superfici in alluminio o in lega di alluminio
JP3117322B2 (ja) * 1993-04-05 2000-12-11 富士写真フイルム株式会社 感光性平版印刷版およびその支持体の製造方法
EP0689096B1 (fr) 1994-06-16 1999-09-22 Kodak Polychrome Graphics LLC Plaques d'impression lithographiques utilisant une couche oléophile à formation d'image
US5728503A (en) * 1995-12-04 1998-03-17 Bayer Corporation Lithographic printing plates having specific grained and anodized aluminum substrate
BRPI0802427A2 (pt) * 2008-08-05 2010-03-23 Ibf Ind Brasileira De Filmes L processo para o tratamento das superfÍcies de chapas de alumÍnio para uso em impressço de imagens digitalizadas, processo para a produÇço de chapas de alumÍnio prÉ-sensibilizada e chapa

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2598043A (en) * 1947-02-20 1952-05-27 Reynolds Metals Co Process of preparing planographic printing plates
CH562334A5 (fr) * 1972-02-04 1975-05-30 Alusuisse
GB1498179A (en) * 1974-08-07 1978-01-18 Kodak Ltd Electrolytic graining of aluminium
US3929591A (en) * 1974-08-26 1975-12-30 Polychrome Corp Novel lithographic plate and method
US3935080A (en) * 1974-10-02 1976-01-27 Polychrome Corporation Method of producing an aluminum base sheet for a printing plate
US3963594A (en) * 1975-06-03 1976-06-15 Aluminum Company Of America Electrochemical treatment of aluminum surfaces with an aqueous solution of hydrochloric acid and gluconic acid
US4021836A (en) * 1976-04-12 1977-05-03 The United States Of America As Represented By The Secretary Of The Air Force Inverted heterojunction photodiode
US4052275A (en) * 1976-12-02 1977-10-04 Polychrome Corporation Process for electrolytic graining of aluminum sheet
US4214961A (en) * 1979-03-01 1980-07-29 Swiss Aluminium Ltd. Method and apparatus for continuous electrochemical treatment of a metal web

Also Published As

Publication number Publication date
EP0082452A1 (fr) 1983-06-29
DE3266243D1 (en) 1985-10-17
JPH0525960B2 (fr) 1993-04-14
US4396468A (en) 1983-08-02
JPS58157997A (ja) 1983-09-20

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