EP0008440A2 - Procédé d'oxydation anodique d'aluminium et son application comme support de plaque d'impression - Google Patents

Procédé d'oxydation anodique d'aluminium et son application comme support de plaque d'impression Download PDF

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Publication number
EP0008440A2
EP0008440A2 EP79102982A EP79102982A EP0008440A2 EP 0008440 A2 EP0008440 A2 EP 0008440A2 EP 79102982 A EP79102982 A EP 79102982A EP 79102982 A EP79102982 A EP 79102982A EP 0008440 A2 EP0008440 A2 EP 0008440A2
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EP
European Patent Office
Prior art keywords
aluminum
electrolyte
anodic oxidation
current density
acid
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Granted
Application number
EP79102982A
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German (de)
English (en)
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EP0008440B1 (fr
EP0008440A3 (en
Inventor
Gerhard Dr. Usbeck
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Hoechst AG
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Hoechst AG
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Publication of EP0008440A3 publication Critical patent/EP0008440A3/xx
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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids

Definitions

  • the invention relates to a method for the anodic oxidation of aluminum, the use of the material produced thereafter as a printing plate carrier material and a method for producing a printing plate carrier material.
  • foil or plate-shaped material made of aluminum or its alloys which is to be used as a carrier material for (planographic) printing plates, has proven to be Preliminary completion of the technical development, the combination of a mostly mechanical or electrochemical roughening stage with a subsequent treatment stage by anodic oxidation of the roughened aluminum surface.
  • anodic oxidations can also be carried out on aluminum materials that have not been subjected to a separate roughening treatment; they then only have to have a surface on which a sufficiently adhesive aluminum oxide layer can be produced by the anodic oxidation , which in turn should offer good adhesion for a photosensitive layer to be applied.
  • the substances causing the veil are also dissolved out of the depth of the oxide layer.
  • the corrected areas appear as bright areas on a tinted background. The .
  • alkali sensitivity and the correction spots mentioned lead to difficulties in printing, which can be caused by the tendency of the printing plates to toning in their non-image areas and by a reduced circulation of the printing plates.
  • Modified electrolytes based on phosphoric acid are therefore described in particular in the processes for the anodic oxidation of aluminum known from the prior art.
  • the process for the anodic treatment of objects made of aluminum according to DE-PS 821 898 is with an anodic gloss level in a bath of 70% H 2 S0 4 , 20% H 3 P0 4 and 10% water at a current density of 15 to 30 A. / dm 2 , a temperature between 70 and 90 ° C and carried out for 3 to 5 minutes and results in shiny and reflective surfaces.
  • DE-PS 957 616 describes a process for the galvanic production of uniformly granular, shiny surfaces on aluminum, in which the electrolyte 40 to 70 vol .-% H 2 S0 4 , 0 to 20 vol .-% H 3 PO 4 , 2 to 5 vol .-% HN0 3 , 0.5 to 2 vol .-% HF and a wetting agent.
  • the electrolyte temperature is approximately 60 to 100 ° C. over a period of 3 to 10 minutes, and the current density ranges from approximately 30 to 40 A / dm 2 at the beginning and 10 to 15 A / dm 2 towards the end of the treatment.
  • a 42, 50, 68 is at a temperature of at least 17 ° C. or 85% H 3 PO 4 brought into action.
  • the current densities used are 1.615, 2.153, 2.583 or 2.691 A / dm 2
  • the thickness of the aluminum oxide layer is at least 50. 10 -9 m and the cells of the aluminum oxide layer are 15 to 75.10 -9 m wide.
  • the process for producing offset printing plates made of aluminum according to DE-OS 19 56 795 has, inter alia, an anodizing stage in which the previously etched printing plate in a bath with 7.5% by volume H 2 SO 4 and 5 vol. -% H 3 PO 4 , is anodized at a temperature of 23.9 ° C for 10 min and with a current density of 1.08 A / dm 2 .
  • an aqueous solution containing 10 to 25% H 2 SO 4 and 20 to 50% N 3 PO 4 is used at temperatures above 80 ° C.
  • the pretreatment is completed in about 5 to 6 seconds at a current density of 100 A / dm 2 .
  • the bath is used to dissolve aluminum oxide at high current densities and within a short time.
  • the process for producing colored anodized aluminum according to DE-OS 25 48 177 has an anodizing stage in which the aluminum is anodized in an H 3 PO 4 and a small amount of another acid such as.
  • B. H 2 S0 4 containing bath is treated.
  • a bath of H 3 P0 4 (80 g / ltr.) And H2S04 (10 g / ltr.) Is listed, in which the aluminum is treated for 2 minutes.
  • the surface is already anodized in H 2 SO 4 ( 165 g / l ) for 30 min at 20 ° C. and a current density of 1.5 A / dm 2 .
  • DE-OS 27 29 391 describes a method for producing a support plate for lithography, in which a porous oxidized layer is produced in an electrolyte which contains a mixture of H 3 PO 3 (phosphorous acid) and H 2 S0 4 , the current density should be about 0.1 to 2 A / dm 2 .
  • the process for anodizing aluminum according to FR-PS 1 285 053 is used as a preliminary step before the application of a chrome or nickel layer and in an electrolyte containing 5 to 45% by volume of H 3 PO 4 , 1 to 30% by volume .-% H 2 SO 4 and 25 to 94 vol .-% water at a temperature of 27 ° C to 60 ° C, a duration of 1 to 30 min and a current density of 1.3 to 13 A / dm 2 performed.
  • the anodic oxidation according to US Pat. No. 2,703,781 which leads to bright, highly reflective surfaces on aluminum is made in an electrolyte from 15 to 40% by weight H 3 PO 4 , 2 to 10% by weight H 2 SO 4 and 50 up to 83% by weight of water in a Current density of about 0.5 to 3 A / dm 2 , a duration of 0.5 min to 50 min and a temperature of 15 ° C to 32 ° C.
  • a light-sensitive layer necessary surface structure cannot be achieved;
  • high temperatures of, for example, more than 65 ° C. to 70 ° C. are used during the anodizing process.
  • Low current densities of less than about 2 A / dm 2 or high current densities of more than about 30 A / dm 2 in conjunction with anodizing times of more than about 1.5 to 2 minutes also lead to layers that are either too slow for large-scale use or grow with too great porosity, or in which the layer build-up is too small or no, since the back-dissolving power of the electrolyte predominates.
  • the object of the invention is therefore to propose a method for producing anodically oxidized aluminum which uses the advantages of the electrolyte types H 2 SO 4 and H 3 P0 4 without taking on the disadvantages shown, ie with the abrasion-resistant, alkali-resistant, less porous Sufficient thickness of aluminum oxide layers can be produced on aluminum strips, foils or plates with economically justifiable energy costs.
  • the invention is based on the known process for the anodic oxidation of strip, sheet or plate-shaped material made of aluminum or its alloys in an aqueous electrolyte containing sulfuric acid and phosphoric acid, if necessary after prior mechanical, chemical or electrochemical roughening.
  • the process according to the invention is characterized in that the material in an electrolyte has a concentration of sulfuric acid of 25 to 150 g / l, of phosphoric acid of 10 to 50 g / l. and anodized on aluminum ions of 5 to 25 g / l, at a current density of 4 to 25 A / dm 2 and at a temperature of 25 ° to 65 ° C.
  • this method is used to produce a strip, film or plate-shaped printing plate carrier material.
  • printing plate is generally understood to mean a printing plate for planographic printing, which mainly consists of a flat support made of one or more materials and one or more likewise flat photosensitive layers attached to it.
  • the process is carried out in particular in an electrolyte with a concentration of sulfuric acid of 25 to 75 g / l, of phosphoric acid of 25 to 40 g / l. and performed on aluminum ions of 10, preferably 12 to 20 g / l, at a current density of 6 to 15 A / dm 2 and at a temperature of 35 ° C to 55 ° C.
  • the electrolyte is made of conc. H 2 SO 4 , conc. H 3 PO 4 , water and an added aluminum salt, in particular aluminum sulfate, prepared so that it to 1 liter. Based electrolyte 25 to 150 g H 2 SO 4, preferably 25 to 75 g H2S04, 10 to 50 g H 3 PO 4, preferably 25 to 40 g H 3 P0 4 and 5 to 25 g in solution located Al 3+ ions, preferably 10, in particular 12 to 20 g of A1 3+ ions. The concentration ranges of the electrolyte components are checked at regular intervals because they are crucial for an optimal process Have importance, and discontinuously or preferably continuously, the electrolyte is then regenerated.
  • This device has a treatment tub filled with the electrolyte, an inlet and an outlet for the band to be treated in the two end walls of the tub below the liquid level of the electrolyte, at least one electrode arranged above the metal band and devices for generating a rapid electrolyte flow between the transport path of the tape and the electrode surface.
  • the electrolyte flow is generated by a glockon-like chamber arranged along each end wall of the tub, which has an upper run for the electrolyte with a liquid drain into a reserve container located below the tub, a gas space sealed off from the outside air above of the liquid level and a gas line beginning in this gas space and connected to a suction pump.
  • this device also has a pump for conveying the electrolyte from the reserve container into the tub.
  • Treatment devices of a different design are also suitable for the method according to the invention, as long as they ensure the conditions listed below with regard to treatment duration, electrolyte movement, material and heat exchange.
  • the method according to the invention is expediently carried out in such a way that the duration of the treatment of the anodic oxidation - ie the stay of a surface point in the area of influence of the electrode (s) - ranges from 5 to 60 seconds, preferably from 10 to 35 seconds.
  • Layer weights of aluminum oxide in the range from 1 to 10 g / m 2 (corresponding to a layer thickness of approximately 0.3 to 3.0 ⁇ m), preferably approximately 2 to 4 g / m 2 can then be obtained.
  • Good electrolyte circulation is required in the practice of the invention. This can be generated either by stirring or by pumping around the electrolyte. In the case of a continuous process (see, for example, DE-AS 22 34 424), care must be taken that the electrolyte is guided as parallel as possible to the strip to be treated at high speed under turbulent flow while ensuring good material and heat exchange becomes. The flow rate of the electrolyte relative to the strip is then expediently more than 0.3 m / sec. 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 or the like) can also be used.
  • the process according to the invention for the anodic oxidation of aluminum can also be preceded by one or more pretreatment stages, in particular a roughening stage, in particular in the embodiment of the method according to the invention for producing a printing plate carrier material.
  • Pretreatment is understood to mean either a mechanical surface treatment by grinding, polishing, brushing or blasting, a chemical surface treatment for degreasing, pickling or matting or an electrochemical surface treatment by the action of the electric current (mostly from alternating current) in an acid such as HCl or HN0 3 .
  • the mechanical and electrochemical treatment of the surfaces of the aluminum in particular lead to roughened surfaces.
  • the average roughness depth R z is in the range from about 1 to 15 ⁇ m, in particular in the range from 4 to 8 pm.
  • 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 single roughness depth is defined as the distance between two parallels to the middle one Line that touches the roughness profile at the highest or lowest point within the individual measuring section.
  • the individual measuring section is the fifth part of the length of the part of the roughness profile which is used directly for evaluation and is projected perpendicularly onto the middle line.
  • the middle line is the line parallel to the general direction of the roughness profile of the shape of the geometrically ideal profile, which divides the roughness profile so that the sums of the material-filled areas above it and the material-free areas below it are equal.
  • the process according to the invention for the anodic oxidation of aluminum can also be simulated by one or more post-treatment steps, likewise in particular in the embodiment of the process according to the invention for producing a printing plate carrier material.
  • 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.
  • Suitable layers also include the electrophotographic layers, ie those which contain an inorganic or organic photoconductor.
  • the colloid layers containing chromates and dichromates Kosar, Chapter 2
  • 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
  • o-diazo-quinones such as naphthoquinonediazides, p-diazo-quinones or diazonium salt condensates containing layers
  • Suitable layers also include the electrophotographic layers, ie those which contain an inorganic or organic photoconductor.
  • 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-PS 596 731, 1 138 399, 1 138 400, 1 138 401, 1 142 871, 1 154 123 U.S. Patents 2,679,498 and 3,050,502 and GB Patent 712,606.
  • Negative mixed condensation products of aromatic diazonium compounds for example according to DE-OS 20 24 244, each having at least one unit of the general Types A (-D) n and B connected by a two-bonded intermediate member derived from a condensable carbonyl compound.
  • A is the residue of a compound containing at least two aromatic carbocyclic and / or heterocyclic nuclei which is capable of condensation with an active carbonyl compound in at least one position in an acid medium.
  • 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 compound free of diazonium groups and 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-OS 26 10 842 which contain a compound which cleaves off when irradiated, a compound which has at least one C-O-C group which can be cleaved off by acid (e.g. an orthocarboxylic acid ester group or a carboxylic acid amide acetal group) and optionally contain a binder.
  • acid e.g. an orthocarboxylic acid ester group or a carboxylic acid amide acetal group
  • optionally contain a binder e.g. an orthocarboxylic acid ester group or a carboxylic acid amide acetal group
  • 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-OSes 20 64 079 and 23 61 041.
  • a photo Initiators are suitable, inter alia, benzoin, benzoin ethers, multinuclear quinones, acridine derivatives, phenazine derivatives, quinoxaline derivatives, quinazoline derivatives or synergistic mixtures of different ketones.
  • soluble organic polymers can be used as binders, e.g. B. polyamides, polyesters, alkyd resins, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin or cellulose ether.
  • an anodized oxidized strip, foil or plate-shaped material made of aluminum or its alloys can be produced in a surprising manner by the process according to the invention, which has an abrasion-resistant, alkali-resistant and less porous surface in sufficient strength for many fields of application.
  • a printing plate carrier material produced by this method and provided with a light-sensitive layer shows no or at least reduced "fog".
  • This goal could be achieved in the process according to the invention by the combination of process features that were often judged to be rather detrimental to the achievement of this goal in the art, namely the use of a low total acid concentration, a targeted distribution of the sulfur and phosphoric acid proportions, a high A1 3+ - Ion concentration, a relatively high electrolyte temperature, a high current density and a high flow rate of the electrolyte. It is possible that some of the features of the method have already become known in certain sub-areas, but this does not apply to the combination of all features. Despite the relatively high electrolyte temperature, the back-dissolving capacity of the electrolyte is of the order of magnitude that can be observed at lower electrolyte temperatures. Likewise, the "burns" of the aluminum oxide, which are often feared due to the higher current density, surprisingly fail to materialize.
  • Blank aluminum strip with a thickness of 0.3 mm is degreased with an alkaline pickling solution (an aqueous solution of 20 g NaOH per liter solution) at an elevated temperature of about 50 to 70 ° C.
  • alkaline pickling solution an aqueous solution of 20 g NaOH per liter solution
  • the electrochemical roughening of the aluminum surface takes place in an apparatus created according to the teaching of DE-AS 22 34 424 with alternating current and in one HNO 3 containing electrolytes.
  • a similar device is used for the subsequent anodic oxidation with direct current, but the current is supplied via a contact roller.
  • the anodizing electrolyte contains 50 g H 2 S0 4 / ltr., 25 g H 3 PO 4 / 1tr. and 10 g Al 3+ / 1tr., the A1 3 + ion concentration by dissolving 123.5 g Al 2 (SO 4 ) 3. 18 H 2 O per liter. is produced.
  • a bath temperature of 35 ° C. and a current density of 8 A / dm 2 (direct current) approximately 3.1 g / m 2 of aluminum oxide can be obtained in an anodizing time of approximately 25 seconds.
  • the flow in the above-mentioned apparatus is turbulent for achieving a good mass and heat exchange, the flow rate of the electrolyte is more than 0.3 m / sec.
  • the weight of the photosensitive layer applied to the anodized support is approximately 3 g / m 2 .
  • a measure of the color acceptance of the surface is a color value difference x I - x II of 1 x 10 3 .
  • the zincate test gives a measurement time of about 38 seconds.
  • the "fog" of the printing plate support is low and the alkali resistance is good.
  • Roll-bright aluminum strip with a thickness of 0.3 mm is alkali-pickled and electrochemically roughened according to the instructions in Example 1.
  • the anodic oxidation takes place in a device created according to the teaching of DE-AS 22 34 424 with an electrolyte containing 50 g H 2 SO 4 / liter, 25 g H 3 PO 4 / liter. and 12 g Al 3+ / 1tr. contains, at a temperature of 55 ° C and a current density of 12 A / dm 2 .
  • the aluminum oxide surface thus obtained is, according to the teaching of DE-OS 25 32 769, with an aqueous solution of 2 g / ltr. Na-metasilicate anodized at 25 ° C and a current density of 0.9 A / dm 2 for 60 seconds.
  • a pickled and coated according to the information in Example 1 Rough aluminum strip material is in a device according to DE-AS 22 34 424 in an aqueous solution with 150 g H 2 S0 4 / ltr., 50 g H 3 P0 4 / ltr., 5 g Al 3+ / 1tr. (added as 61.75 g / ltr. Al 2 (SO 4) 3. 18 H 2 0) anodized.
  • a temperature of 40 ° C and a current density of 11 A / dm 2 about 2.5 g / m 2 of aluminum oxide can be built up in 25 seconds.
  • the dyeing test gives a color value difference x I - x II of 12. 10.
  • the alkali resistance in the zincate test is 31 sec.
  • An aluminum strip material with a thickness of 0.3 mm which was alkali-pickled and electrochemically roughened as described in Example 1, was anodically oxidized in a solution containing 50 g H 2 SO 4 / 1tr., 25 g H 3 PO 4 / 1tr. and 13 g Al 3+ / 1tr. contains.
  • the process is carried out in a device with less electrolyte movement and thus poorer material and heat exchange, for example a device as in DE-AS 16 21 115, column 3 , Lines 1 to 10 described.
  • oxide If the anodization is carried out at 55 ° C. and 12 A / dm 2 , about 3.4 g / m 2 of oxide are formed in 30 seconds. Due to the somewhat less favorable development conditions (increased temperature, low material and heat exchange), this oxide shows a color value difference x I - x II of 32 in the dye test. 10 3 and a somewhat lower alkali resistance tested in the zincate test (36 sec).
  • This example shows the wide range in the applicability of the anodizing electrolytes according to the invention, which bring about significant improvements in the oxide layer properties even under difficult anodizing conditions.
  • Rolled aluminum strip with a thickness of 0.3 mm is degreased with an alkaline solution, electrochemically roughened and anodized according to the instructions in Example 1.
  • the electrolyte in the anodic oxidation contains 25 g H 2 SO 4 / 1tr., 25 g H 3 P0 4 / 1tr. and 5 g Al 3+ / 1tr.
  • At 55 ° C bath temperature and 8 A / dm 2 current density approx. 1.95 g / m 2 oxide can be built up in 25 seconds.
  • the untreated material has an alkali resistance in the zincate test of 63 sec.
  • the surface is prepared for the subsequent sensitization by immersing the aluminum support in a 0.1% aqueous solution of polyvinylphosphonic acid (molecular weight about 100,000) at 60 ° C. for 4 minutes.
  • the photosensitive coating is carried out using 1.4 parts by weight of mixed condensate composed of 1 mol of 3-methoxydiphenylamine-4-diazonium sulfate and 1 mol of 4,4'-bis-methoximethyldiphenyl ether, prepared in 85% strength aqueous phosphoric acid and precipitated as mesitylene sulfonate , 0.2 part by weight of p-toluenesulfonic acid monohydrate, 3 parts by weight of polyvinyl butyral, (containing 69 to 71% polyvinyl butyral, 1% polyvinyl acetate and 24 to 27% polyvinyl alcohol units, the viscosity of a 5% solution in butanol at 20 ° C is 20 - 30 m Pa.
  • the diazo mixed condensate layer exposed under a negative is mixed with a mixture of 50 parts by weight of water, 15 parts by weight of isopropanol, 20 parts by weight of n-propanol, 12.5 parts by weight of n-propyl acetate, 1.5 Parts by weight of polyacrylic acid and 1.5 parts by weight of acetic acid developed.
  • a roughened aluminum strip prepared according to the instructions in Example 1 is made in an electrolyte from 50 g H 2 SO 4 / 1tr., 25 g H 3 PO 4 / 1tr. and 12 g Al 3+ / 1tr. anodized.
  • a bath temperature of 55 ° C and a current density of 12 A / dm 2 3.1 g / m 2 of aluminum oxide can be built up in 30 seconds.
  • An alkaline cleaned and electrochemically roughened aluminum strip according to the instructions of Example 1 is in an aqueous electrolyte with 100 g H 3 PO 4 / 1tr. anodically oxidized as the sole electrolyte acid.
  • a current density of 4 A / dm 2 0.85 g / m 2 of aluminum oxide can be built up in a device according to DE-AS 22 34 424 with a contact roller in about 25 seconds.
  • the alkali resistance measured in the zincate test is moderate (16 sec), the tendency to "color haze" formation in the dyeing test is very low (difference in color values x I - x II of about 1. 10 3 ).
  • the oxide layer which can still be built up without burns, shows a poor alkali resistance and thus clearly the disadvantages of using phosphoric acid as the sole anodizing electrolyte, but also indicates the advantage of the very low sensitivity to color fog.
  • An aluminum strip with a thickness of 0.3 mm is alkali pickled according to the information in Example 1, electrochemically roughened and anodized.
  • the anodic oxidation is carried out with an electrolyte of 150 g H 2 S0 4 / ltr. and 5 g A1 3+ / ltr. carried out.
  • the coloring test gives a difference in the color value fraction x I - x II of 27. 10 3 . In the zincate test, the oxide layer is already penetrated after 22 seconds.
  • example 2 shows the progress which can be achieved according to the invention in the dyeing test (ie reduced fog formation) and alkali resistance at a likewise increased temperature and current density.
  • the base coated with a light-sensitive mixture according to Example 1 shows a very strong "fog" after the copy.
  • the print run using the offset process only achieves about 95,000 prints in good quality.
  • Rolled aluminum strip is pretreated and anodized according to the instructions in Example 1.
  • the anodic oxidation takes place in an electrolyte containing 75 g H 2 SO 4 / 1tr. and 20 g Al 3+ / 1tr. contains (according to the teaching of DE-OS 28 11 396).
  • Example 1 aluminum strip sections which have been subjected to alkaline treatment and are electrochemically roughened are mixed in HZS04 or H2S04 / H3P04 mixtures of various concentrations with and without addition of aluminum ions (introduced as Al 2 (SO 4 ) 3. 18 H 2 0) for 30 seconds at 30 ° C. anodized with a current density of 8 A / dm 2 .
  • the composition of the anodizing electrolyte, conductivity and the oxide layer thicknesses produced and their coloring behavior are shown in the table. It turns out that the addition of aluminum ions generally favors the oxide thickness growth and contributes greatly to the reduction of the colorability, expressed by the difference in color value x I - x II .
  • the aluminum ion additive reduces the specific conductivity at higher total acid concentrations, however, at the lower acid concentrations preferred according to the invention, the conditions are unexpectedly mostly reversed and this additive improves the specific conductivity and thus also the economy of the process.

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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)
  • Inorganic Chemistry (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Electrochemical Coating By Surface Reaction (AREA)
EP79102982A 1978-08-23 1979-08-16 Procédé d'oxydation anodique d'aluminium et son application comme support de plaque d'impression Expired EP0008440B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19782836803 DE2836803A1 (de) 1978-08-23 1978-08-23 Verfahren zur anodischen oxidation von aluminium und dessen verwendung als druckplatten-traegermaterial
DE2836803 1978-08-23

Publications (3)

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EP0008440A2 true EP0008440A2 (fr) 1980-03-05
EP0008440A3 EP0008440A3 (en) 1980-04-30
EP0008440B1 EP0008440B1 (fr) 1981-11-04

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EP79102982A Expired EP0008440B1 (fr) 1978-08-23 1979-08-16 Procédé d'oxydation anodique d'aluminium et son application comme support de plaque d'impression

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US (1) US4229266A (fr)
EP (1) EP0008440B1 (fr)
JP (1) JPS5528400A (fr)
BR (1) BR7905415A (fr)
CA (1) CA1137918A (fr)
DE (2) DE2836803A1 (fr)
ES (1) ES8101130A1 (fr)
ZA (1) ZA794419B (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4396470A (en) * 1980-10-23 1983-08-02 Vickers P.L.C. Lithographic printing plates
EP0161461A3 (en) * 1984-04-13 1986-07-30 Hoechst Aktiengesellschaft Process for the anodic oxidation of aluminium and its use as a support material for offset printing plates
EP0179448A3 (en) * 1984-10-23 1986-08-27 Mitsubishi Chemical Industries Limited Photosensitive planographic printing plate
WO1989001871A1 (fr) * 1987-08-28 1989-03-09 Cookson Graphics Plc Methode de production d'une plaque d'impression lithographique pre-sensibilisee
US9797059B2 (en) 2012-05-30 2017-10-24 Mitsubishi Chemical Corporation Method for manufacturing mold and method for manufacturing molded article having fine uneven structure on surface

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH645409A5 (de) * 1980-09-08 1984-09-28 Schenk & Co Verfahren zum faerben von oxydschichten von aluminium oder aluminiumlegierungen mit organischen verbindungen.
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DE3206469A1 (de) * 1982-02-23 1983-09-01 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von traegermaterialien fuer offsetdruckplatten
DE3206470A1 (de) * 1982-02-23 1983-09-01 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von traegermaterialien fuer offsetdruckplatten
GB2119942B (en) * 1982-03-03 1985-09-11 Fuji Photo Film Co Ltd Method for preparing a lithographic printing plate and a light-sensitive material used therefor
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US4524125A (en) * 1982-08-13 1985-06-18 Polychrome Corporation Chemical etching of lithographic aluminum substrate
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JPS59227494A (ja) * 1983-06-09 1984-12-20 Fuji Photo Film Co Ltd 平版印刷版用支持体の製造方法
US4502925A (en) * 1984-06-11 1985-03-05 American Hoechst Corporation Process for aluminum surface preparation
US4647346A (en) * 1985-10-10 1987-03-03 Eastman Kodak Company Anodized aluminum support, method for the preparation thereof and lithographic printing plate containing same
DE3635303A1 (de) 1986-10-17 1988-04-28 Hoechst Ag Verfahren zur abtragenden modifizierung von mehrstufig aufgerauhten traegermaterialien aus aluminium oder dessen legierungen und deren verwendung bei der herstellung von offsetdruckplatten
DE3917188A1 (de) * 1989-05-26 1990-11-29 Happich Gmbh Gebr Verfahren zur erzeugung farbiger oberflaechen auf teilen aus aluminium oder aluminium-legierungen
DE4243164A1 (de) * 1992-12-19 1994-06-23 Deutsche Aerospace Airbus Verfahren zur anodischen Oxidation
EP0689096B1 (fr) 1994-06-16 1999-09-22 Kodak Polychrome Graphics LLC Plaques d'impression lithographiques utilisant une couche oléophile à formation d'image
DE19518587A1 (de) * 1995-05-20 1996-11-21 Tampoprint Gmbh Druckklischee und Verfahren zu dessen Herstellung
DE10149928C1 (de) * 2001-10-10 2002-12-12 Wkw Erbsloeh Automotive Gmbh Verfahren zum Glänzen von Aluminium und dessen Verwendung
US7273537B2 (en) * 2002-09-12 2007-09-25 Teck Cominco Metals, Ltd. Method of production of metal particles through electrolysis
US8309237B2 (en) * 2007-08-28 2012-11-13 Alcoa Inc. Corrosion resistant aluminum alloy substrates and methods of producing the same
US7732068B2 (en) * 2007-08-28 2010-06-08 Alcoa Inc. Corrosion resistant aluminum alloy substrates and methods of producing the same
DE102008019887A1 (de) * 2008-04-21 2009-10-22 OCé PRINTING SYSTEMS GMBH Verfahren zum Herstellen einer Tonerwalze durch elektrolytische Oxidation von Aluminium
CN103374740A (zh) * 2012-04-18 2013-10-30 靖江先锋半导体科技有限公司 铝镁合金的低粉尘阳极氧化表面处理工艺
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EP3445896B1 (fr) * 2016-04-18 2023-10-18 Fokker Aerostructures B.V. Procédé d'anodisation d'un article en aluminium ou en alliage de celui-ci

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EP0161461A3 (en) * 1984-04-13 1986-07-30 Hoechst Aktiengesellschaft Process for the anodic oxidation of aluminium and its use as a support material for offset printing plates
EP0179448A3 (en) * 1984-10-23 1986-08-27 Mitsubishi Chemical Industries Limited Photosensitive planographic printing plate
WO1989001871A1 (fr) * 1987-08-28 1989-03-09 Cookson Graphics Plc Methode de production d'une plaque d'impression lithographique pre-sensibilisee
US9797059B2 (en) 2012-05-30 2017-10-24 Mitsubishi Chemical Corporation Method for manufacturing mold and method for manufacturing molded article having fine uneven structure on surface

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JPS5528400A (en) 1980-02-28
DE2961253D1 (en) 1982-01-14
ES483570A0 (es) 1980-12-01
DE2836803A1 (de) 1980-03-06
EP0008440B1 (fr) 1981-11-04
ZA794419B (en) 1980-08-27
US4229266A (en) 1980-10-21
EP0008440A3 (en) 1980-04-30
CA1137918A (fr) 1982-12-21
BR7905415A (pt) 1980-05-20
ES8101130A1 (es) 1980-12-01

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