EP0150464A2 - Procédé pour rendre rugueux électrolytiquement des plaques d'impression en aluminium dans un électrolyte composite aqueux - Google Patents

Procédé pour rendre rugueux électrolytiquement des plaques d'impression en aluminium dans un électrolyte composite aqueux Download PDF

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Publication number
EP0150464A2
EP0150464A2 EP84116020A EP84116020A EP0150464A2 EP 0150464 A2 EP0150464 A2 EP 0150464A2 EP 84116020 A EP84116020 A EP 84116020A EP 84116020 A EP84116020 A EP 84116020A EP 0150464 A2 EP0150464 A2 EP 0150464A2
Authority
EP
European Patent Office
Prior art keywords
aluminum
aqueous
und
acid
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.)
Granted
Application number
EP84116020A
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German (de)
English (en)
Other versions
EP0150464B1 (fr
EP0150464A3 (en
Inventor
E. Dr. Dipl-Chemiker Pliefke
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
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Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0150464A2 publication Critical patent/EP0150464A2/fr
Publication of EP0150464A3 publication Critical patent/EP0150464A3/de
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Publication of EP0150464B1 publication Critical patent/EP0150464B1/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 invention relates to a method for the electrochemical roughening of aluminum for printing plate supports, which is carried out with alternating current in an aqueous mixed electrolyte.
  • 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 also called grain or etching in literature), chemical or electrochemical oxidation and / or treatment with hydrophilizing agents.
  • a combination of the above-mentioned Mo Types of dification applied, 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 HN0 3 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 is then the arithmetic mean of the individual roughness depths of five adjacent individual measuring sections.
  • the roughening is carried out, inter alia, in order to improve the adhesion of the reproduction layer on the substrate and the water flow of the printing plate resulting from the printing plate by irradiation (exposure) and development.
  • irradiation and development or decoating in the case of reproduction layers working electrophotographically
  • the image points which carry color during later printing and the water-bearing non-image points are produced on the printing plate, whereby the actual printing form is created.
  • Various parameters have an influence on the later topography of the aluminum surface to be roughened, which may be exemplified by the following explanations of the prior art:
  • the essay "The Alternating Current Etching of Aluminum Lithography Sheet" by AJ Dowell in Transactions of the Institute of Metal Finishing, 1979, Vol. 57, pp. 138 to 144 contains basic explanations made to roughen aluminum in aqueous hydrochloric acid solutions, the following process parameters varied and the corresponding effects were examined.
  • the electrolyte composition is changed with repeated use of the electrolyte, for example with regard to the H + (H 3 O + ) ion concentration (measurable via the pH value) and the Al 3+ ion concentration, effects on the surface topography being observed.
  • the temperature variation between 16 ° C and 90 ° C shows a changing influence only from about 50 ° C, which is expressed, for example, by the sharp decline in the formation of layers on the surface.
  • the roughening time change between 2 and 25 min also leads to an increasing metal dissolution with increasing exposure time.
  • the variation of the current density between 2 and 8 A / dm 2 results in higher roughness values with increasing current density. If the acid concentration is in the range 0.17 to 3.3% of HCl, then only insignificant changes in the hole structure occur between 0.5 and 2% of HCl, below 0.5% of HC1 there is only a local attack on the Surface and at the high values an irregular dissolution of Al instead.
  • the addition of SO 4 2- ions or Cl - ions in salt form [e.g. B. by adding Al 2 (SO 4 ) 3 or NaCl] can also influence the topography of the roughened Aluminum. The rectification of the alternating current shows that both types of half-wave are obviously required for a uniform roughening.
  • aqueous HCl solutions as an electrolyte solution for the electrochemical roughening of support materials made of aluminum must therefore be assumed to be known. It can be obtained - as many examples of commercial printing plates show - a uniform grain size, which is particularly suitable for the field of application of lithography and is within a roughness range that is generally useful in practice. For certain areas of application of printing plates (e.g.
  • the known organic additives to aqueous acid electrolytes such as HCl or HN0 3 solutions have the aftermath partly that they become electrochemically unstable at high current loads (voltage) in modern continuously operating conveyor systems and at least partially decompose.
  • the known inorganic additives such as phosphoric, chromic or boric acid have the disadvantage that the intended protective effect frequently breaks down locally and individual, particularly pronounced scars then develop there.
  • the object of the present invention is therefore to propose a method for the electrochemical roughening of aluminum for printing plate supports which makes it possible light, to achieve a uniformly roughened surface topography with a wide range in the mean roughness values.
  • the invention is based on the known method for the electrochemical roughening of aluminum or its alloys for printing plate supports in an aqueous mixed electrolyte solution containing HC1 and a further inorganic acid under the action of alternating current.
  • the process according to the invention is then characterized in that hydrofluoric acid (HF) is used as the inorganic acid.
  • HF hydrofluoric acid
  • the aqueous electrolyte solution contains 0.5 to 10% by weight, in particular 0.8 to 3% by weight, of HCl and 0.05 to 5% by weight, in particular 0.1 to 1.0 % By weight of HF.
  • Suitable base materials for the material to be roughened 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 carrier materials can also be roughened mechanically (for example by brushing and / or with abrasive treatments) before the electrochemical stage, if appropriate after pre-cleaning. All process steps can be carried out discontinuously with plates or foils, but they are preferably carried out continuously with tapes.
  • the process parameters are in the following ranges: the temperature of the electrolyte between 20 and 60 ° C, the current density between 3 and 200 A / dm 2 , the residence time of a material point to be roughened in the electrolyte between 3 and 100 sec and the electrolyte flow rate at the surface of the material to be roughened between 5 and 100 cm / sec; in the batchwise process, the required current densities tend to be in the lower part and the dwell times are in the upper part of the ranges specified, and the flow of the electrolyte can also be dispensed with.
  • alternating current of a frequency of 50 to 60 Hz is usually 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 current, lower frequencies, current interruptions or overlapping of two currents of different frequency and waveform are also possible.
  • the average roughness depth R z of the roughened surface is in the range from 1 to 15 ⁇ m, in particular from 1.5 to 8.0 ⁇ m.
  • aluminum ions in the form of aluminum salts in particular A1C1 3 or A1F 3 , can also be added to the aqueous electrolyte.
  • 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 essentially 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.
  • an anodic oxidation of the aluminum can then preferably follow in a further process step to be used, for example in order to improve the abrasion and adhesion properties of the surface of the carrier material.
  • the usual electrolytes such as H 2 SO 4 , H 3 PO 4 , H 2 C 2 O 4 , amidosulfonic acid, sulfosuccinic acid, sulfosalicylic acid or mixtures thereof can be used for anodic oxidation; in particular, H 2 S0 4 and H 3 P0 4 are used alone, in a mixture and / or in a multi-stage anodizing process.
  • the stage of anodic oxidation of the aluminum support material 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 often sufficient, while at least the other known properties of this layer are retained.
  • the materials produced according to the invention are used as supports for offset printing plates, i. H. a radiation-sensitive coating is applied to one or both sides of the carrier material either by the manufacturer of presensitized printing plates or directly by the consumer.
  • a radiation-sensitive coating is applied to one or both sides of the carrier material either by the manufacturer of presensitized printing plates or directly by the consumer.
  • all layers are suitable as radiation (light) sensitive layers which, after irradiation (exposure), optionally with subsequent development and / or fixation, provide an imagewise surface from which printing can take place.
  • photo-semiconducting layers such as e.g. in DE-C 11 17 391, 15 22 497, 15 72 312, 23 22 046 and 23 22 047 are described, are applied to the carrier materials produced according to the invention, thereby producing highly light-sensitive, electrophotographic printing plates.
  • 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, for example an aqueous alkaline developer solution.
  • a developer for example an aqueous alkaline developer solution.
  • % data always mean% by weight, unless stated otherwise. Parts by weight relate to parts by volume in the ratio of g to cm 3 .
  • EXAMPLES 1 TO 28 AND COMPARATIVE EXAMPLES VI TO V29 An aluminum sheet is first pickled for 60 seconds in an aqueous solution of 20 g NaOH per liter at room temperature and then freed from any alkali residues that may be present by briefly immersing it in a solution corresponding to the roughening electrolyte. The roughening takes place in the electrolyte systems shown in the following tables and under the conditions listed there. After roughening, an anodic oxidation is carried out in an aqueous electrolyte containing H 2 S0 4 and A1 3 + ions up to a layer weight of 3.0 g / m 2 .
  • Examples 1 to 28 and comparative examples V1 to V22 are carried out with symmetrical alternating current at a frequency of 50 Hz, one electrode being the aluminum sheet and the other a graphite plate. In the comparative examples V23 to V26, direct current is used and the aluminum sheet is switched as the cathode; in the comparative examples V27 to V29, the aluminum is switched as the anode; the graphite plate is then the counter electrode.
  • Example 29 An analogous to Example 29 in an aqueous electrolyte with an HCl content of 20 g / l without the addition of HF, anodized, coated and copied plate has a print run of 90,000 prints.

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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)
EP84116020A 1984-01-05 1984-12-21 Procédé pour rendre rugueux électrolytiquement des plaques d'impression en aluminium dans un électrolyte composite aqueux Expired EP0150464B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3400249 1984-01-05
DE19843400249 DE3400249A1 (de) 1984-01-05 1984-01-05 Verfahren zur elektrochemischen aufrauhung von aluminium fuer druckplattentraeger in einem waessrigen mischelektrolyten

Publications (3)

Publication Number Publication Date
EP0150464A2 true EP0150464A2 (fr) 1985-08-07
EP0150464A3 EP0150464A3 (en) 1985-09-11
EP0150464B1 EP0150464B1 (fr) 1987-04-29

Family

ID=6224399

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84116020A Expired EP0150464B1 (fr) 1984-01-05 1984-12-21 Procédé pour rendre rugueux électrolytiquement des plaques d'impression en aluminium dans un électrolyte composite aqueux

Country Status (5)

Country Link
US (1) US4566958A (fr)
EP (1) EP0150464B1 (fr)
JP (1) JPS60159092A (fr)
CA (1) CA1256058A (fr)
DE (2) DE3400249A1 (fr)

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* Cited by examiner, † Cited by third party
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JP2011205051A (ja) 2009-06-26 2011-10-13 Fujifilm Corp 光反射基板およびその製造方法
JP2012033853A (ja) 2010-04-28 2012-02-16 Fujifilm Corp 絶縁性光反射基板
CN103085523B (zh) 2011-10-28 2016-12-21 富士胶片株式会社 用于平版印刷版的载体的制备方法和制备装置
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
CN108698360B (zh) 2016-02-29 2021-03-23 富士胶片株式会社 复合体
CN108779571A (zh) 2016-03-25 2018-11-09 富士胶片株式会社 铝板的制造方法及铝板的制造装置
CN110431926A (zh) 2017-03-13 2019-11-08 富士胶片株式会社 电磁波屏蔽部件
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
WO2018235488A1 (fr) 2017-06-21 2018-12-27 富士フイルム株式会社 Corps composite
CN110678257A (zh) 2017-06-21 2020-01-10 富士胶片株式会社 铝复合材料
JPWO2019039469A1 (ja) 2017-08-22 2020-10-15 富士フイルム株式会社 防音構造体および吸音パネル
JPWO2019044589A1 (ja) 2017-08-28 2020-08-06 富士フイルム株式会社 防音構造、及び防音構造体
KR20200044057A (ko) 2017-09-29 2020-04-28 후지필름 가부시키가이샤 적층체

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE120061C (fr) * 1900-02-05
GB294237A (en) * 1927-07-22 1929-09-12 Electrolux Ltd A process for treating aluminium or other light metals
DE695182C (de) * 1939-01-25 1940-08-19 Mahle Kg Verfahren zur Erzeugung von Poren auf Laufflaechentmaschinen
US2775553A (en) * 1952-12-31 1956-12-25 Sprague Electric Co Electrolytic etching process for electrolytic capacitors
US3330745A (en) * 1964-08-11 1967-07-11 Grace W R & Co Electrolytic process for graft polymerization
DE1496825A1 (de) * 1965-04-13 1969-04-10 Fischer Dr Wilhelm Anton Verfahren zur elektrochemischen Behandlung von als Anode geschalteten Werkstuecken
US3445355A (en) * 1966-07-15 1969-05-20 Ibm Method and composition for the electrolytic etching of beryllium-copper alloys
DE1621115C3 (de) * 1967-10-17 1981-06-25 Metalloxyd GmbH, 5000 Köln Verfahren zur Herstellung eines Trägers aus Aluminium für lithographische Druckplatten
JPS517081B1 (fr) * 1971-04-17 1976-03-04
DE2250275A1 (de) * 1972-10-13 1974-04-25 Oce Van Der Grinten Nv Verfahren zur elektrochemischen behandlung von aluminium zur herstellung lithographischer druckplatten
FR2241633B1 (fr) * 1973-07-13 1976-06-18 Ugine Kuhlmann
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
JPS5317580A (en) * 1976-08-02 1978-02-17 Yuuroku Dev Ab Method of increasing filtration and sedimentation of suspension of macromolecular biological substances
US4072589A (en) * 1977-04-13 1978-02-07 Polychrome Corporation Process for electrolytic graining of aluminum sheet

Also Published As

Publication number Publication date
EP0150464B1 (fr) 1987-04-29
CA1256058A (fr) 1989-06-20
EP0150464A3 (en) 1985-09-11
US4566958A (en) 1986-01-28
DE3400249A1 (de) 1985-07-18
DE3463400D1 (en) 1987-06-04
JPS60159092A (ja) 1985-08-20

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