EP0149833B1 - Verfahren zur elektrochemischen Aufrauhung von Aluminium für Druckplattenträger in einem wässrigen Mischelektrolyten - Google Patents

Verfahren zur elektrochemischen Aufrauhung von Aluminium für Druckplattenträger in einem wässrigen Mischelektrolyten Download PDF

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Publication number
EP0149833B1
EP0149833B1 EP84116022A EP84116022A EP0149833B1 EP 0149833 B1 EP0149833 B1 EP 0149833B1 EP 84116022 A EP84116022 A EP 84116022A EP 84116022 A EP84116022 A EP 84116022A EP 0149833 B1 EP0149833 B1 EP 0149833B1
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EP
European Patent Office
Prior art keywords
weight
aluminum
aqueous
und
electrolyte
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
EP84116022A
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German (de)
English (en)
French (fr)
Other versions
EP0149833A2 (de
EP0149833A3 (en
Inventor
Dieter Dr. Dipl-Chem. Mohr
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Hoechst AG
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Hoechst AG
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Publication of EP0149833A3 publication Critical patent/EP0149833A3/de
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Publication of EP0149833B1 publication Critical patent/EP0149833B1/de
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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 layer support.
  • 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 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 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 z is then the arithmetic mean of the individual roughness depths of five adjacent individual measuring sections.
  • the known organic additives to aqueous acid electrolytes such as HCl or HN0 3 solutions have the Disadvantage 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 use of H 2 0 2 or oxalic acid to form a nitric acid electrolyte which has only recently been described, does not lead to a significant improvement in the surface topography, because the scarring is still too strong for good lithography quality.
  • the previously known complexing additives generally accelerate the "trapping" of released Al 3 + ions to dissolve the aluminum and thereby increase the roughening attack; However, this often leads to the fact that no additional hole nuclei are created, but that already formed nuclei and holes continue to grow, ie there is then increased scar formation.
  • the previously known inhibitory additives generally have the effect that the hole growth of individual holes is stopped relatively soon and new hole nuclei can arise; However, they have the decisive disadvantage that this protective effect due to defects, alloy components and the like. ⁇ . can collapse; this then leads to deep holes in an otherwise flat and evenly roughened surface. Backing materials with such imperfections are unsuitable for lithographic purposes.
  • 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 to achieve a uniformly roughened surface topography with a wide range in the mean roughness depth values and to achieve long bath service lives and with the aid of which aluminum alloys with less than 99.5% of AI can be roughened evenly.
  • the invention is based on the known method for electrochemical roughening of aluminum or its alloys for printing plate supports in an aqueous mixed electrolyte solution containing HN0 3 and at least one other inorganic electrolyte under the action of alternating current.
  • the process according to the invention is then characterized in that the further inorganic electrolyte is an inorganic fluorine compound which is present as an acid or alkali metal salt and whose anion contains fluorine and optionally at least one further element.
  • the aqueous electrolyte solution contains 0.3 to 4% by weight, in particular 0.8 to 3% by weight, and preferably 1.0 to 2% by weight of HNO 3 and 0.05 to 5% by weight .-%, in particular 0.1 to 1.5 wt .-%, of the fluorine compound.
  • the suitable inorganic fluorine compounds include in particular complex fluorine compounds or compounds comparable to them.
  • Preferred examples of such fluorine compounds are acids or alkali salts (including the ammonium salts) with the anions: SiF 6 2- , TiF 6 2-, ZrF 6 2- . BF 4- , PF 6 -, HfF 6 2-, S0 3 F- and PO 3 F 2- ;
  • compounds with the following anions can also be used: NbF 6 -, TaF 6 -, FeF 63 AsF 6 - and SbF 6 -.
  • the compounds are preferably used individually, but can also be used as a mixture of several.
  • Suitable base materials for the material to be roughened according to the invention include those made of aluminum or one of its alloys, which, for example, contain more than 98.0% by weight, in particular less than 99.5% by weight, of Al and proportions Si, Fe, Ti, Cu, Zn, Mn and / or Mg.
  • These aluminum carrier materials can also, if necessary after pre-cleaning, mechanically (e.g. by brushing and / or with abrasive treatments) before the electrochemical stage. to be roughened. 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, low frequencies, current interruptions or superimpositions of two currents of different frequency and waveform are also possible.
  • the mean surface roughness R z of the roughened surface lies in the range of 1 to 15 .mu.m, in particular from 1.5 to 8.0 1 1m.
  • aluminum ions in the form of aluminum salts in particular 2% by weight to saturation and preferably 4 to 8% by weight of Al (NO 3 ) 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 additional application treatment can additionally be carried out, in particular a maximum of 2 g / m 2 being applied (between the stages up to 5 g / m 2 are generally used as ablative solutions aqueous alkali hydroxide solutions or aqueous solutions of alkaline salts or aqueous acid solutions based on HN0 3 , H 2 S0 4 or H 3 P0 4.
  • non-electrochemical treatments which essentially only have a rinsing and / or cleaning action and are used, for example, to remove deposits ("Schmant") formed during roughening or simply to remove electrolyte residues; for this purpose, for example, dilute aqueous alkali metal hydroxide solutions or water are used.
  • 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 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; 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 image-like area 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.
  • coated offset printing plates obtained from the carrier materials produced by the process 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, for example an aqueous alkaline developer solution.
  • a developer for example an aqueous alkaline developer solution.
  • 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 of 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 from the
  • the following tables show the respective electrolyte systems and under the conditions listed there.
  • an anodic oxidation is carried out in an aqueous electrolyte containing H 2 S0 4 and Al 3 + - ions up to a layer weight of 3.0 g / m 2 .
  • the classification into the quality classes takes place by visual assessment under the microscope, whereby the quality level "1" (best value) is assigned to a homogeneously roughened and scar-free surface.
  • Quality level "10" (worst value) is assigned to a surface with thick scars of a size of more than 100 ⁇ m or an extremely unevenly roughened or almost rolled surface.
  • Intermediate qualities are rated “2" to "9". All examples and the comparative examples 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.
  • the layer is negatively charged to about 400 V in the dark by means of a corona.
  • the charged plate is exposed imagewise in a repro camera and then with an electrophotographic suspension developer, which by dispersing 3.0 parts by weight of magnesium sulfate in a solution of 7.5 parts by weight of pentaerythritol resin ester in 1200 parts by volume of an isoparaffin mixture with a Boiling range of 185 to 210 ° C was obtained.
  • the developer is fixed and the plate in a solution of 35 parts by weight of sodium metasilicate for 60 seconds.
  • 9 H 2 0, 140 parts by weight of glycerol, 550 parts by weight of ethylene glycol and 140 parts by weight of ethanol immersed.
  • the plate is then rinsed off with a powerful jet of water, removing the areas of the photoconductor layer not covered with toner.
  • the printing form is then ready for printing.

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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)
EP84116022A 1984-01-05 1984-12-21 Verfahren zur elektrochemischen Aufrauhung von Aluminium für Druckplattenträger in einem wässrigen Mischelektrolyten Expired EP0149833B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843400250 DE3400250A1 (de) 1984-01-05 1984-01-05 Verfahren zur elektrochemischen aufrauhung von aluminium fuer druckplattentraeger in einem waessrigen mischelektrolyten
DE3400250 1984-01-05

Publications (3)

Publication Number Publication Date
EP0149833A2 EP0149833A2 (de) 1985-07-31
EP0149833A3 EP0149833A3 (en) 1985-09-11
EP0149833B1 true EP0149833B1 (de) 1987-04-29

Family

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Family Applications (1)

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EP84116022A Expired EP0149833B1 (de) 1984-01-05 1984-12-21 Verfahren zur elektrochemischen Aufrauhung von Aluminium für Druckplattenträger in einem wässrigen Mischelektrolyten

Country Status (5)

Country Link
US (1) US4566960A (enrdf_load_stackoverflow)
EP (1) EP0149833B1 (enrdf_load_stackoverflow)
JP (1) JPS60159094A (enrdf_load_stackoverflow)
CA (1) CA1270791A (enrdf_load_stackoverflow)
DE (2) DE3400250A1 (enrdf_load_stackoverflow)

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GB9113214D0 (en) * 1991-06-19 1991-08-07 Alcan Int Ltd Treating al sheet
US5432046A (en) * 1993-09-29 1995-07-11 Hoechst Celanese Corporation Process for preparing improved lithographic printing plates by brushgraining with alumina/quartz slurry
US5658651A (en) 1995-09-29 1997-08-19 Creative Products Resource, Inc. Fabric treatment and softener system for in-dryer use
GB9711382D0 (en) * 1997-06-03 1997-07-30 Du Pont Uk Heat sensitive printing plate precursors
JP3491811B2 (ja) * 1997-10-31 2004-01-26 スズキ株式会社 摺動部材及びピストン
CN100549231C (zh) * 1997-10-31 2009-10-14 铃木株式会社 滑动部件
US6569537B1 (en) 1999-04-28 2003-05-27 Suzuki Motor Corporation Surface treatment method sliding member and piston
US6716569B2 (en) * 2000-07-07 2004-04-06 Fuji Photo Film Co., Ltd. Preparation method for lithographic printing plate
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
EP2586621B1 (en) 2011-10-28 2014-08-20 Fujifilm Corporation Manufacturing method and manufacturing apparatus of support for planographic printing plate
EP3101159B1 (en) 2014-01-31 2019-05-15 FUJIFILM Corporation Method for manufacturing aluminum plate, aluminum plate, current collector for electric storage device, and electric storage device
JP6563583B2 (ja) 2016-02-29 2019-08-21 富士フイルム株式会社 金属調装飾体成型用複合体
EP3434814A4 (en) 2016-03-25 2019-01-30 Fujifilm Corporation ALUMINUM LEAD MANUFACTURING METHOD AND ALUMINUM LEVER MANUFACTURER
EP3598863A4 (en) 2017-03-13 2020-03-18 FUJIFILM Corporation ELECTROMAGNETIC SHAFT SHIELDING ELEMENT
CN110476204B (zh) 2017-03-27 2020-10-23 富士胶片株式会社 隔音结构体、以及吸音面板及调音面板
EP3643402A4 (en) 2017-06-21 2020-06-24 FUJIFILM Corporation ALUMINUM COMPOSITE MATERIAL
WO2018235488A1 (ja) 2017-06-21 2018-12-27 富士フイルム株式会社 複合体
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
EP3678127A4 (en) 2017-08-28 2020-09-09 FUJIFILM Corporation SOUND INSULATION STRUCTURE AND SOUND INSULATION SYSTEM
KR20200044057A (ko) 2017-09-29 2020-04-28 후지필름 가부시키가이샤 적층체

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Also Published As

Publication number Publication date
DE3400250A1 (de) 1985-07-18
JPH0522597B2 (enrdf_load_stackoverflow) 1993-03-30
EP0149833A2 (de) 1985-07-31
DE3463399D1 (en) 1987-06-04
CA1270791A (en) 1990-06-26
EP0149833A3 (en) 1985-09-11
US4566960A (en) 1986-01-28
JPS60159094A (ja) 1985-08-20

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