EP0089508B1 - Procédé de grainage électrolytique de l'aluminium et son application comme support pour plaques lithographiques - Google Patents

Procédé de grainage électrolytique de l'aluminium et son application comme support pour plaques lithographiques Download PDF

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Publication number
EP0089508B1
EP0089508B1 EP83101811A EP83101811A EP0089508B1 EP 0089508 B1 EP0089508 B1 EP 0089508B1 EP 83101811 A EP83101811 A EP 83101811A EP 83101811 A EP83101811 A EP 83101811A EP 0089508 B1 EP0089508 B1 EP 0089508B1
Authority
EP
European Patent Office
Prior art keywords
aluminum
acid
electrolyte
roughened
roughening
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
EP83101811A
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German (de)
English (en)
Other versions
EP0089508A1 (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 EP0089508A1 publication Critical patent/EP0089508A1/fr
Application granted granted Critical
Publication of EP0089508B1 publication Critical patent/EP0089508B1/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

Definitions

  • the present invention relates to a method for the electrochemical roughening of plate, foil or tape-shaped material made of aluminum and its use as a carrier material for offset printing plates.
  • a long-known method for producing offset printing plates from printing plates consists in coating an aluminum plate serving as a carrier material with a radiation-sensitive mixture suitable for later printing purposes, then exposing this layer to a template and finally developing it.
  • the oleophilic image areas remaining after development take on ink and transfer them during the printing process, whereas the surface exposed during development forms the hydrophilic non-image areas, which take on water or aqueous solutions during printing and thus repel the bold printing inks.
  • the electrochemical roughening of aluminum has numerous advantages over the mechanical roughening. For certain applications, a very fine and uniform roughening is desirable, especially if the aluminum is to be used as a carrier material for offset printing plates. A fine and uniform roughening can be achieved in an electrolyte consisting of an aqueous hydrochloric acid solution, although the current density must be kept very low if no scarring of the aluminum surface is to be caused, and due to the low current density, the roughening process takes a relatively long time.
  • the electrochemical roughening of aluminum plates with hydrochloric acid or nitric acid is known from the prior art, for example from US Pat. Nos.
  • the electrolytes are either aqueous hydrochloric acid solutions, optionally with an inhibiting or stabilizing additive, or aqueous nitric acid solutions with additives such as nitrates, amines, diamines, aldehydes, complexing agents such as ethylenediaminetetraacetate or acids such as phosphoric acid, chromic acid and sulfosalicylic acid.
  • the surface of the aluminum support is also said to be When printing, allow it to be wetted sufficiently with aqueous solutions so that bold printing inks cannot adhere to it.
  • this method should be suitable for the use of aluminum alloys with a content of less than 99.5% of Al.
  • the invention is based on the known method for the electrochemical roughening of plate, sheet or strip material made of aluminum or its alloys in an aqueous electrolyte containing nitric acid and oxalic acid.
  • the process according to the invention is then characterized in that the electrolyte is free from hydrochloric acid and contains 3 to 20 g / l nitric acid and 1 to 80 g / l oxalic acid.
  • the process according to the invention accordingly comprises an electrochemical treatment of aluminum in an aqueous electrolyte solution which contains nitric acid and oxalic acid in sufficient quantities to produce a fine, uniform and essentially scar-free roughening.
  • the respective optimal concentration of nitric acid and oxalic acid is dependent on various factors, such as. B. the current density, the temperature of the electrolyte and the properties of the aluminum product to be roughened, and can be easily determined by a few simple experiments.
  • the aqueous electrolyte can optionally also contain boric acid, aluminum nitrate and / or H 2 0 2 .
  • the concentration of the aqueous hydrochloric acid-free electrolyte in nitric acid is 3 to 20 g / l, in particular 8 to 20 g / l and preferably 10 to 15 g / l. With quantities above 20 g / l there is no significant difference in the roughening until the roughening effect then begins to decrease at around 500 g / l.
  • the oxalic acid is present in the electrolyte in a concentration of 1 to 80 g / l, in particular 5 to 45 g / l, preferably 8 to 20 g / l.
  • boric acid 1 g / l is generally added to this acid up to the saturation point of the electrolyte, but in particular 5 to 15 g / l, preferably 8 to 12 g / l. If it is added, the proportion of hydrogen peroxide is generally at a concentration of 1 to 60 g / l, in particular 10 to 30 g / l and preferably 15 to 20 g / l. If aluminum nitrate is also added, its concentration can correspond approximately to the saturation point of the solution on this salt, it is in particular 65 to 70 g / l, preferably approximately 65 g / l.
  • the current density in the process according to the invention which can be carried out batchwise or continuously, is generally 30 to 120 A / dm 2 , in particular 45 to 80 A / dm 2 and preferably 45 to 60 A / dm 2 .
  • the roughening time is between 20 and 180 s, in particular between 20 and 90 s and preferably between 20 and 60 s.
  • the aluminum surface and the inert electrode which generally consists of graphite, chromium or lead, are preferably arranged at a distance of up to 1.5 cm, in particular between 1 and 1.5 cm, from one another. Alternating current is particularly suitable for the roughening process, a frequency above about 55 Hz giving the best roughening effect. The frequency is best between 60 and about 300 Hz.
  • the materials to be roughened can, for example, be those with an aluminum content of 99 99.5, 99.2, 98 98.5 or 98.3%, which are added as Fe, Si, Cu and optionally Zn, Contain Ti, Mn and / or Mg; these are, for example, with the designation «pure aluminum», «1100». "3003 or" A-19 traded.
  • the thickness of these materials is generally in the range of about 0.1 to 0.65 mm.
  • the method is preferred for such alloys with a content of less than 99.5% of Al, in particular of less than 99.0% of Al, such as the “ 3003 ” type, in which a uniformly roughened surface has essentially no pitting (Scars) can be achieved, which was not yet known with the previous electrolytes or electrolyte additives.
  • This aluminum alloy in particular has previously caused greater difficulties - presumably because of its Mn content - because a roughened film is formed during the roughening - presumably from a manganese oxide hydrate; this no longer occurs in the method according to the invention.
  • a plate made of bright-rolled aluminum alloy in offset quality (for example the types “3003 or” 1100 from Alcoa or the type “A-19” from Conalco), in particular "3003”, is electrolytically roughened under the above conditions only in aqueous nitric acid the surface after the treatment, for example, has a surface area increased by about 40%.
  • the surface is relatively flat and so soft that the plate must be hardened by anodizing before it can be used for printing.
  • a roughened plate the aqueous roughening electrolyte of which contains, for example, 13 g / l of nitric acid, 20 g / l of oxalic acid and 65 g / l of aluminum nitrate, has a surface area which is approximately 250% larger than that of the bright-rolled plate.
  • the plate can optionally be anodized, but this is not necessary.
  • a plate is roughened in an aqueous electrolyte containing 13 g / l nitric acid, 20 g / l oxalic acid and 10 g / l boric acid, the surface area of its surface also increases by about 625% compared to that of bright rolled aluminum .
  • the surface shows an extremely fine pore structure, whereby the pore walls are relatively thick. Anodic oxidation is no longer absolutely necessary.
  • aluminum nitrate is advantageously added to the aqueous electrolyte from the outset.
  • Aluminum nitrate is best contained in the electrolyte up to the point of saturation of the solution in this salt, so that additional aluminum nitrate formed during the process is only deposited on the bottom of the electrolyte vessel, while the concentration of the solution in this salt remains relatively constant.
  • the plate can optionally also be anodically oxidized, for example in an aqueous electrolyte which contains sulfuric and / or phosphoric acid.
  • the roughened or the roughened and anodized plate it is advantageous to subject the roughened or the roughened and anodized plate to a hydrophilizing intermediate treatment before the photosensitive coating is applied.
  • Such intermediate treatments have u. a. the purpose of bringing about better surface adhesion of the coating and making the aluminum surface increasingly hydrophilic, for example polyvinylphosphonic acid, sodium silicate or alkali zirconium fluoride are used.
  • Radiation-sensitive compounds suitable for offset printing for the radiation-sensitive coatings are, for example, the known aromatic diazonium salts, quinonediazides and photopolymerizable compounds. These are usually mixed with resins to increase the print run of the plate. These resins include, for example, polyurethanes and phenol formaldehyde resins, as well as many other known resins.
  • a plate made of aluminum alloy «1100 is treated with a conventional alkaline degreasing solution and then immersed in a 1.5% aqueous nitrate solution.
  • a system in which the aluminum forms one electrode and a lead plate forms the other electrode carries alternating current at a frequency of 60 Hz.
  • the electrodes are spaced 1.0 cm apart and a current density of 45 A / dm 2 is used for a period of 60 s.
  • the resulting roughened surface is examined with a scanning electron microscope at 1000, 2000 and 5000 times magnification. It shows that it has been roughened completely, but very unevenly. There are areas with extensive, undesirable scarring, bordered by more uniform areas, but which have scars of different diameters.
  • the surface area of this surface is 40% larger than that of untreated aluminum. Such a surface is unsuitable for quality printing.
  • a plate made of the aluminum alloy "3003 is treated according to the information in comparative example V1. The results are similar, i. H. Extensive scarring can be seen under the scanning electron microscope.
  • a plate made of the aluminum alloy "A-19” is treated as described in Comparative Example V1. Similar results are obtained, but here the scarring is more extensive and more noticeable.
  • a "1100 aluminum alloy plate is treated with a conventional alkaline degreasing solution and then immersed in an aqueous solution containing 1.5% nitric acid and 6.5% aluminum nitrate.
  • AC is conducted through a system in which the aluminum forms one electrode and a lead plate forms the other electrode.
  • the electrodes are spaced 1.0 cm apart and a current density of 45 Aldm 2 is used for a period of 60 s.
  • the sample proves to be somewhat uniformly roughened.
  • the surface is flat and has holes of different sizes with rather thin walls. There are signs of scarring, compared to untreated aluminum a surface area increased by 45% is measured. Because of the brittleness of the holes, this surface must be anodized if one wants to achieve an acceptable pressure behavior.
  • a plate made of the aluminum alloy "3003" is treated according to the information in comparative example V4.
  • the results are similar, i. H. There are holes of different sizes and scarring.
  • a plate made of the aluminum alloy "A-19" is treated according to the information given in Comparative Example V4.
  • the surface is extremely poor, 5 since it has an uneven hole size and, in addition, has some non-roughened areas and severe scarring.
  • a plate made of aluminum alloy «1100» is treated with a conventional alkaline degreasing solution and then immersed in an aqueous solution containing 1.5% nitric acid, 6.5% aluminum nitrate and 3.0% oxalic acid.
  • AC is conducted through a system in which the aluminum sample forms one electrode and a lead plate forms the other electrode.
  • the electrodes are spaced 1.0 cm apart and a current density of 45 A / dm 2 is used for a period of 60 s.
  • a plate made of the aluminum alloy "3003" is treated according to the instructions in Example 1. The results are similar, i. H. the surface is roughened very evenly.
  • a plate made of aluminum alloy "A-19” is treated as described in Example 1. The results are similar, ie the surface is also roughened very uniformly.
  • a plate made of the aluminum alloy "1100" is treated as described in Example 1, but in an aqueous solution containing 1.5% nitric acid, 6.5% aluminum nitrate, 3.0% oxalic acid and 1.0 % boric acid.
  • the roughened plate shows a surface which corresponds to that of Example 1 in terms of its uniformity and overall appearance.
  • the holes are smaller and more numerous here.
  • a modification of the surface not yet observed in the above examples is shown, because smaller holes occur within the larger holes.
  • the increase in the surface area compared to the untreated aluminum is determined at 625%.
  • a plate made of the aluminum alloy "300 3 is treated according to the instructions in Example 4. The results are similar, ie the surface is roughened very evenly.
  • a plate made of the aluminum alloy "A-19 is treated according to the instructions in Example 4. The results are similar, i. H. the surface is roughened very evenly.

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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)
  • Electroplating And Plating Baths Therefor (AREA)

Claims (6)

1. Procédé pour le grainage électrochimique de supports sous forme de plaques, de feuilles ou de bandes, en aluminium ou ses alliages dans un électrolyte aqueux contenant de l'acide nitrique et de l'acide oxalique, caractérisé en ce que l'électrolyte est dépourvu d'acide chlorhydrique et contient de 3 à 20 g/I d'acide nitrique et de 1 à 80 g/I d'acide oxalique.
2. Procédé selon la revendication 1, caractérisé en ce que l'électrolyte contient en outre de l'acide borique, du nitrate d'aluminium et/ou de l'eau oxygénée.
3. Procédé selon la revendication 2, caractérisé en ce que l'électrolyte contient de l'acide borique à raison de 1 g/1 jusqu'à la saturation de l'électrolyte.
4. Procédé selon la revendication 2, caractérisé en ce que l'électrolyte contient de 1 à 60 g/I d'eau oxygénée.
5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le support est oxydé anodiquement après grainage et est recou- vert ensuite d'une couche sensible aux radiations.
6. Utilisation d'un matériau grainé selon l'une quelconque des revendications 1 à 5, éventuellement après oxydation anodique de la surface grainée, comme support pour une plaque d'impression offset portant une couche sensible aux radiations.
EP83101811A 1982-03-18 1983-02-24 Procédé de grainage électrolytique de l'aluminium et son application comme support pour plaques lithographiques Expired EP0089508B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US359338 1982-03-18
US06/359,338 US4374710A (en) 1982-03-18 1982-03-18 Electrolytic graining of aluminum with nitric and oxalic acids

Publications (2)

Publication Number Publication Date
EP0089508A1 EP0089508A1 (fr) 1983-09-28
EP0089508B1 true EP0089508B1 (fr) 1987-04-15

Family

ID=23413396

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83101811A Expired EP0089508B1 (fr) 1982-03-18 1983-02-24 Procédé de grainage électrolytique de l'aluminium et son application comme support pour plaques lithographiques

Country Status (6)

Country Link
US (1) US4374710A (fr)
EP (1) EP0089508B1 (fr)
JP (1) JPS58171590A (fr)
BR (1) BR8301335A (fr)
CA (1) CA1224181A (fr)
DE (1) DE3370975D1 (fr)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4437955A (en) 1983-07-05 1984-03-20 U.S. Philips Corporation Combined AC and DC etching of aluminum foil
DE3339410C1 (de) * 1983-10-29 1991-08-29 Dürener Maschinenfabrik und Eisengießerei H. Depiereux GmbH & Co, 5160 Düren Verfahren zum elektrochemischen Aufrauhen von Aluminiumoberflaechen bei der Herstellung von Offsetdruckplatten
DE3400250A1 (de) * 1984-01-05 1985-07-18 Hoechst Ag, 6230 Frankfurt Verfahren zur elektrochemischen aufrauhung von aluminium fuer druckplattentraeger in einem waessrigen mischelektrolyten
US4502925A (en) * 1984-06-11 1985-03-05 American Hoechst Corporation Process for aluminum surface preparation
US4678551A (en) * 1984-10-11 1987-07-07 Fuji Photo Film Co., Ltd. Process for producing an aluminum support for a lithographic printing plate
US5728503A (en) * 1995-12-04 1998-03-17 Bayer Corporation Lithographic printing plates having specific grained and anodized aluminum substrate
US20120091495A1 (en) 2009-06-26 2012-04-19 Fujifilm Corporation Light reflecting substrate and process for manufacture thereof
JP2012033853A (ja) 2010-04-28 2012-02-16 Fujifilm Corp 絶縁性光反射基板
US9573404B2 (en) 2011-10-28 2017-02-21 Fujifilm Corporation Manufacturing method and manufacturing apparatus of support for planographic printing plate
CN105934540B (zh) 2014-01-31 2018-03-13 富士胶片株式会社 铝板的制造方法、铝板、蓄电装置用集电体及蓄电装置
WO2017150099A1 (fr) 2016-02-29 2017-09-08 富士フイルム株式会社 Corps composite
EP3434814A1 (fr) 2016-03-25 2019-01-30 Fujifilm Corporation Procédé de fabrication de feuille d'aluminium et appareil de fabrication de feuille d'aluminium
JPWO2018168786A1 (ja) 2017-03-13 2020-01-16 富士フイルム株式会社 電磁波シールド部材
WO2018181139A1 (fr) 2017-03-27 2018-10-04 富士フイルム株式会社 Structure d'insonorisation, panneau d'absorption acoustique et panneau de réglage
JPWO2018235659A1 (ja) 2017-06-21 2020-04-16 富士フイルム株式会社 アルミニウム複合材料
EP3643497A4 (fr) 2017-06-21 2020-04-29 Fujifilm Corporation Corps composite
EP3675119A4 (fr) 2017-08-22 2020-08-26 FUJIFILM Corporation Structure d'insonorisation et panneau d'absorption sonore
WO2019044589A1 (fr) 2017-08-28 2019-03-07 富士フイルム株式会社 Structure et corps insonorisés
EP3689595A1 (fr) 2017-09-29 2020-08-05 FUJIFILM Corporation Stratifié

Citations (2)

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Publication number Priority date Publication date Assignee Title
DE2535142A1 (de) * 1974-08-07 1976-02-19 Eastman Kodak Co Verfahren zum elektrolytischen aufrauhen von aluminium und aluminiumlegierungen
DE2149899B2 (de) * 1970-10-06 1977-12-08 Schweizerische Aluminium Ag, Chippis (Schweiz) Verfahren zum gleichmaessigen und feinen elektrolytischen aufrauhen von aluminiumoberflaechen mittels wechselstrom

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JPS5926480B2 (ja) * 1978-03-27 1984-06-27 富士写真フイルム株式会社 平版印刷版用支持体
US4242417A (en) * 1979-08-24 1980-12-30 Polychrome Corporation Lithographic substrates
US4336113A (en) * 1981-06-26 1982-06-22 American Hoechst Corporation Electrolytic graining of aluminum with hydrogen peroxide and nitric or hydrochloric acid

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
DE2149899B2 (de) * 1970-10-06 1977-12-08 Schweizerische Aluminium Ag, Chippis (Schweiz) Verfahren zum gleichmaessigen und feinen elektrolytischen aufrauhen von aluminiumoberflaechen mittels wechselstrom
DE2535142A1 (de) * 1974-08-07 1976-02-19 Eastman Kodak Co Verfahren zum elektrolytischen aufrauhen von aluminium und aluminiumlegierungen

Also Published As

Publication number Publication date
CA1224181A (fr) 1987-07-14
EP0089508A1 (fr) 1983-09-28
BR8301335A (pt) 1983-11-29
US4374710A (en) 1983-02-22
JPS58171590A (ja) 1983-10-08
DE3370975D1 (en) 1987-05-21

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