EP0268058B1 - Procédé de décapage électrochimique de l'aluminium ou ses alliages pour supports pour plaques d'impression - Google Patents

Procédé de décapage électrochimique de l'aluminium ou ses alliages pour supports pour plaques d'impression Download PDF

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Publication number
EP0268058B1
EP0268058B1 EP87114630A EP87114630A EP0268058B1 EP 0268058 B1 EP0268058 B1 EP 0268058B1 EP 87114630 A EP87114630 A EP 87114630A EP 87114630 A EP87114630 A EP 87114630A EP 0268058 B1 EP0268058 B1 EP 0268058B1
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EP
European Patent Office
Prior art keywords
nitrate
graining
carried out
aluminum
electrochemical
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 - Lifetime
Application number
EP87114630A
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German (de)
English (en)
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EP0268058A3 (en
EP0268058A2 (fr
Inventor
Engelbert Pliefke
Dieter Mohr
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
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Publication of EP0268058A2 publication Critical patent/EP0268058A2/fr
Publication of EP0268058A3 publication Critical patent/EP0268058A3/de
Application granted granted Critical
Publication of EP0268058B1 publication Critical patent/EP0268058B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C3/00—Reproduction or duplicating of printing formes
    • B41C3/08—Electrotyping; Application of backing layers thereon
    • 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 process for the production of plate, foil or strip-shaped aluminum or its alloys as a carrier material for printing plates, in which firstly mechanically and subsequently electrochemically in a nitrate-containing electrolyte is roughened with direct current.
  • Printing plates with this term are meant offset printing plates in the context of the present invention, generally consist of a support and at least one radiation (light)-sensitive reproduction layer arranged on it, this layer either from the consumer (in the case of non-precoated plates) or from industrial 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 relevant literature), a chemical one or electrochemical oxidation and / or treatment with hydrophilizing agents.
  • the roughening is carried out, for example, in aqueous acids such as aqueous HCl or HNO3 solutions or in aqueous salt solutions such as aqueous NaCl or Al (NO3) 3 solutions using alternating current.
  • aqueous acids such as aqueous HCl or HNO3 solutions
  • aqueous salt solutions such as aqueous NaCl or Al (NO3) 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 (as of October 1970).
  • the roughness depth R z is then the arithmetic mean of the individual roughness depths of five adjacent individual measurement 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 reproductive layers working electrophotographically
  • the image points which carry color during later printing and the non-image points which carry water generally the exposed carrier surface
  • Very different parameters have an influence on the later topography of the roughened aluminum surface.
  • the following references provide information:
  • 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 / dm2 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 HCl there is only a local attack on the surface and at the high values an irregular dissolution of aluminum takes place.
  • hydrochloric acid or nitric acid as an electrolyte for roughening aluminum substrates can therefore be assumed to be known.
  • a uniform grain size can be obtained which is suitable for lithographic plates and is within a useful roughness range.
  • pure nitric acid electrolytes the setting of a flat and uniform surface topography is difficult, and it is necessary to maintain the operating conditions within very narrow limits.
  • JP application 91 334/78 describes AC roughening in a combination of hydrochloric acid and an alkali halide to produce a lithographic base material.
  • DE-C 120 061 describes a treatment for producing a water-attracting layer by using electricity, which can also take place in hydrofluoric acid.
  • US-A-2,344,510 describes the use of a direct current roughening in an electrolyte containing hydrochloric acid, which follows a mechanical roughening as the second roughening.
  • the object of the present invention is to provide a method for the electrochemical roughening of aluminum for printing plate supports with direct current, which provides a uniform, scar-free and area-wide roughening structure without having to maintain a large outlay on equipment and / or particularly narrow parameter limits and in terms of energy is saved.
  • the finished printing plates should have a high print run and low wiping water consumption.
  • This object is achieved in that solutions of alkali metal, alkaline earth metal, ammonium or aluminum nitrate and / or mixtures thereof and / or mixtures with nitric acid are used as the nitrate-containing electrolyte and that the concentration of the nitrate compound is from 1.0 g / l to is set to the saturation limit.
  • the concentration of the nitrate compound is adjusted from greater than 100 g / l to the saturation limit.
  • Electrochemical roughening is carried out for a time of 1 to 300 s, in particular 2 to 60 s.
  • an alkaline cleaning step and anodization are carried out in such a way that the cleaning is carried out by acids or alkalis or by hydroxyl ions generated in the electrolytic bath during electrochemical roughening.
  • Electrochemical roughening with direct current takes place at a temperature of 20 to 80 ° C.
  • the mechanical roughening is carried out with a wet abrasive as a wet brush, but other mechanical methods, such as dry brushing, sandblasting, spherical grain, embossing and similar methods can also be used for the mechanical pre-structuring.
  • the sheet is preferably cleaned by an etching step with metal removal.
  • This etching step pickling
  • a nitrate electrolyte is used, the concentration of the nitrate compound being between 1.0 g / l and the saturation limit, particularly preferably between 5.0 g / l and 100.0 g / l.
  • Aluminum nitrate and / or nitric acid and / or sodium nitrate is used as the preferred compound containing nitrate ions. Combinations of other compounds containing nitrate ions are of course also within the scope of the invention.
  • the current density used is less critical than the total amount of charge.
  • the process according to the invention is carried out either discontinuously or preferably continuously with strips made of aluminum or its alloys.
  • the process parameters in continuous processes during electrochemical roughening lie in the following ranges: the temperature of the electrolyte between 20 and 80 ° C, the current density between 1 and 300 A / dm2, the residence time of a material point to be roughened in the electrolyte between 1 and 300 s, preferably between 2 and 60 s, and the electrolyte flow rate at the surface of the material to be roughened between 5 and 1000 cm / s.
  • the required current densities tend to be in the lower part and the dwell times are in the upper part of the ranges specified, the flow of the electrolyte can also be dispensed with.
  • pulsed, corrugated and differently shaped direct currents can also be used as long as the plate does not change polarity during the entire roughening process.
  • the method according to the invention can also be applied to other aluminum alloys.
  • Direct current is preferably used for the anodic oxidation, but alternating current or a combination of these types of current (eg direct current with superimposed alternating current) can also be used.
  • the layer weights of aluminum oxide range from 1 to 10 g / m2, corresponding to a layer thickness of approximately 0.3 to 3.0 ⁇ m.
  • a modification can also be applied which causes surface abrasion from the roughened surface, as described, for example, in DE-A 30 09 103.
  • Such a modifying intermediate treatment can u. a. allow the build-up of abrasion-resistant oxide layers and a lower tendency to tone when printing later.
  • the stage of anodic oxidation of the aluminum printing plate support material can also be one or multiple post-treatment levels can be recreated.
  • 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.
  • 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.
  • the light-sensitive reproduction layers include such as z. B. in "Light-Sensitive Systems” by Jaromir Kosar, John Wiley & Sons Verlag, New York 1965, are described: The layers containing unsaturated compounds, in which these compounds are isomerized, rearranged, cyclized or crosslinked during exposure (Kosar, Chapter 4); the layers containing photopolymerizable compounds, in which monomers or prepolymers optionally polymerize during exposure by means of an initiator (Kosar, Chapter 5); and the layers containing o-diazo-quinones such as naphthoquinonediazides, p-diazo-quinones or diazonium salt condensates (Kosar, Chapter 7).
  • the suitable layers also include the electrophotographic layers, ie those which contain an inorganic or organic photoconductor.
  • these layers can of course also contain other constituents, such as, for example, resins, dyes, pigments, wetting agents, sensitizers, adhesion promoters, indicators, plasticizers or other customary auxiliaries.
  • the following light-sensitive compositions or compounds can be used in the coating of the carrier materials: positive-working, o-quinonediazide, preferably o-naphthoquinonediazide compounds, which are described, for example, in DE-C 854 890, 865 109, 879 203, 894 959, 938 233, 1 109 521, 1 144 705, 1 118 606, 1 120 273 and 1 124 817; negative working condensation products from aromatic diazonium salts and compounds with active carbonyl groups, preferably condensation products from diphenylamine diazonium salts and formaldehyde, which are described, for example, in DE-C 596 731, 1 138 399, 1 138 400, 1 138 401, 1 142 871, 1 154 123, US Pat.
  • Negative working, mixed condensation products of aromatic diazonium compounds for example according to DE-A 20 24 244, which each have at least one unit of the general types A (-D) n and B connected by a double-bonded intermediate member derived from a condensable carbonyl compound.
  • A is the remainder of a compound containing at least two aromatic carbocyclic and / or heterocyclic nuclei, which is capable of condensing with an active carbonyl compound in an acidic medium at at least one position.
  • D is a diazonium salt group attached to an aromatic carbon atom of A; n is an integer from 1 to 10 and B is the remainder of a diazonium group-free compound capable of condensing with an active carbonyl compound in an acidic medium at at least one position on the molecule; positive-working layers according to DE-A 26 10 842, which contain a compound which cleaves off on irradiation, a compound which has at least one COC group which can be cleaved off by acid (for example an orthocarboxylic acid ester group or a carboxylic acid amide acetal group) and optionally a binder; Negative working layers of photopolymerizable monomers, photoinitiators, binders and optionally other additives.
  • the monomers used here are, for example, acrylic and methacrylic acid esters or reaction products of diisocyanates with partial esters of polyhydric alcohols, as described, for example, in US Pat. Nos. 2,760,863 and 3,060,023 and DE-A 20 64 079 and 23 61 041.
  • Suitable photoinitiators include benzoin, benzoin ethers, multinuclear quinones, acridine derivatives, phenazine derivatives, quinoxaline derivatives, quinazoline derivatives or synergistic mixtures of various ketones.
  • a variety of soluble organic polymers can be used as binders, e.g. B.
  • Negative working layers according to DE-A 30 36 077 which contain a diazonium salt polycondensation product or an organic azido compound as the photosensitive compound and a high molecular weight polymer with pendant alkenylsulfonyl or cycloalkenylsulfonylurethane groups as the binder.
  • photo-semiconducting layers such as are described, for example, in DE-C 11 17 391, 15 22 497, 15 72 312, 23 22 046 and 23 22 047, to the support materials, thereby producing highly light-sensitive, electrophotographic layers.
  • the materials for printing plate supports roughened by the process according to the invention have a very uniform topography, which has a positive influence on the support stability and the water flow during printing of printing forms made from these supports.
  • "scars" compared to the roughening of the surroundings: distinctive depressions
  • the method according to the invention is particularly successful in producing flat, scar-free supports.
  • Comparative examples V1 to V5, in direct comparison with examples 1 to 4, show the effect of direct current in electrolytes containing nitrate ions as a means of achieving uniform surfaces which have significant advantages in printing in terms of reducing the wiping water requirement and increasing the circulation . These surface properties can be realized without any great expenditure on equipment.
  • the water consumption is 25 divisions.
  • Example 2 A prepared and coated as in Example 1, but in 10% aluminum nitrate solution at 20 A / dm2 for 5 s anodically roughened plate, which was cleaned in 2.5% NaOH at 60 ° C for 60 s, prints 150,000 copies under the same conditions with a water consumption of 30 scale divisions.
  • a plate produced and coated analogously to Example 1, but anodically roughened with an alternating current of 20 A / dm 2 for 20 s has a circulation of 120,000 and a water consumption of 40 scale parts.
  • a plate manufactured and coated as in Comparative Example V4, but anodically roughened in 12 g / l HCl and 50 g AlCl3 ⁇ 6 H2O has a circulation of 115,000 and a water consumption of 39 scale parts.
  • the printing was carried out under the same conditions using the same printing press (Roland Favorit).
  • the application quantity of the wiping water is determined by a display device in a dampening unit from Dahlgren. These are relative comparative measurements. The lower the scale divisions, the lower the water consumption.

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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)
  • Manufacturing & Machinery (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Claims (10)

  1. Procédé de fabrication de plaques, feuilles ou bandes d'aluminium ou de ses alliages, comme matériaux supports pour plaques d'impression, dans lequel on opère un grainage, d'abord mécanique puis électrochimique, avec un courant continu, dans un électrolyte contenant un nitrate, caractérisé en ce qu'on utilise, comme électrolyte nitraté, des solutions de nitrate alcalin, alcalino-terreux, d'ammonium ou d'aluminium et/ou de leurs mélanges et/ou de leurs mélanges avec l'acide nitrique, et en ce que la concentration du nitrate est ajustée à une valeur comprise entre 1,0 g/l et la limite de saturation.
  2. Procédé selon la revendication 1, caractérisé en ce que la concentration du nitrate est ajustée à une valeur supérieure à 100 g/l et allant jusqu'à la limite de saturation.
  3. Procédé selon les revendications 1 et 2, caractérisé en ce que le grainage est effectué avec un courant continu de 1 à 300 A/dm² et une quantité de charge de 1 à 400 C/dm².
  4. Procédé selon la revendication 3, caractérisé en ce que le grainage est effectué avec un courant continu de 10 à 100 A/dm² et une quantité de charge de 10 à 200 C/dm².
  5. Procédé selon une ou plusieurs des revendications 1 à 4, caractérisé en ce qu'on réalise un grainage électrochimique qui dure de 1 à 300 s.
  6. Procédé selon la revendication 5, caractérisé en ce qu'on réalise un grainage électrochimique qui dure de 2 à 60 s.
  7. Procédé selon une ou plusieurs des revendications 1 à 6, dans lequel on adjoint au grainage mécanique et/ou électrochimique une étape supplémentaire de nettoyage alcalin ainsi qu'une oxydation anodique, caractérisé en ce que le nettoyage s'effectue par des acides ou par des lessives alcalines ou par les ions hydroxyle formés dans le bain électrolytique lors du grainage électrochimique.
  8. Procédé selon la revendication 7, caractérisé en ce qu'on réalise un grainage électrochimique à une température comprise entre 20 et 80 °C.
  9. Procédé selon la revendication 7, caractérisé en ce que le grainage mécanique est réalisé sous forme de brossage humide.
  10. Procédé selon une ou plusieurs des revendications 1 à 8, caractérisé en ce que le grainage électrochimique est réalisé dans un électrolyte en mouvement avec une vitesse de courant comprise entre 5 et 1000 cm/s.
EP87114630A 1986-10-17 1987-10-07 Procédé de décapage électrochimique de l'aluminium ou ses alliages pour supports pour plaques d'impression Expired - Lifetime EP0268058B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3635304 1986-10-17
DE19863635304 DE3635304A1 (de) 1986-10-17 1986-10-17 Verfahren zur elektrochemischen aufrauhung von aluminium fuer druckplattentraeger

Publications (3)

Publication Number Publication Date
EP0268058A2 EP0268058A2 (fr) 1988-05-25
EP0268058A3 EP0268058A3 (en) 1989-07-19
EP0268058B1 true EP0268058B1 (fr) 1993-06-23

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EP87114630A Expired - Lifetime EP0268058B1 (fr) 1986-10-17 1987-10-07 Procédé de décapage électrochimique de l'aluminium ou ses alliages pour supports pour plaques d'impression

Country Status (5)

Country Link
US (1) US4824535A (fr)
EP (1) EP0268058B1 (fr)
JP (1) JPS63104890A (fr)
KR (1) KR890000246A (fr)
DE (2) DE3635304A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2707339B2 (ja) * 1989-10-18 1998-01-28 富士写真フイルム株式会社 平版印刷版用支持体の製造方法
JP3217194B2 (ja) * 1993-08-31 2001-10-09 富士写真フイルム株式会社 平版印刷版用支持体の製造方法
JP4159058B2 (ja) * 1997-06-13 2008-10-01 コニカミノルタホールディングス株式会社 画像形成材料及び画像形成方法
DE69818204T2 (de) 1997-12-16 2004-07-01 Fuji Photo Film Co., Ltd., Minami-Ashigara Verfahren zur Herstellung eines Aluminiumträgers für eine Flachdruckplatte

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DE1621115C3 (de) * 1967-10-17 1981-06-25 Metalloxyd GmbH, 5000 Köln Verfahren zur Herstellung eines Trägers aus Aluminium für lithographische Druckplatten
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Also Published As

Publication number Publication date
DE3635304A1 (de) 1988-04-28
US4824535A (en) 1989-04-25
EP0268058A3 (en) 1989-07-19
KR890000246A (ko) 1989-03-13
DE3786327D1 (de) 1993-07-29
JPS63104890A (ja) 1988-05-10
EP0268058A2 (fr) 1988-05-25

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