EP0269851B1 - Support en aluminium ou en alliage d'aluminium pour des plaques offset et son procédé de fabrication - Google Patents

Support en aluminium ou en alliage d'aluminium pour des plaques offset et son procédé de fabrication Download PDF

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Publication number
EP0269851B1
EP0269851B1 EP87115715A EP87115715A EP0269851B1 EP 0269851 B1 EP0269851 B1 EP 0269851B1 EP 87115715 A EP87115715 A EP 87115715A EP 87115715 A EP87115715 A EP 87115715A EP 0269851 B1 EP0269851 B1 EP 0269851B1
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EP
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Prior art keywords
weight
electrolyte
alkali metal
support material
aluminium
Prior art date
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Expired - Lifetime
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EP87115715A
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German (de)
English (en)
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EP0269851A2 (fr
EP0269851A3 (en
Inventor
Michael Brenk
Renate Ernst
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Hoechst AG
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Hoechst AG
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Classifications

    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S205/00—Electrolysis: processes, compositions used therein, and methods of preparing the compositions
    • Y10S205/921—Electrolytic coating of printing member, other than selected area coating

Definitions

  • the invention relates to an improved carrier material based on aluminum or its alloys for offset printing plates.
  • the invention also relates to a method for producing the carrier material.
  • Carrier materials for offset printing plates are provided either by the consumer directly or by the manufacturer of precoated printing plates on one or both sides with a radiation (light) sensitive layer (reproduction layer), with the help of which a printing image is generated in a photomechanical way.
  • the layer support After a printing form has been produced from the printing plate, the layer support carries the image areas which will guide the color during later printing and at the same time forms the hydrophilic image background for the lithographic printing process at the areas which are free of image (non-image areas) during later printing.
  • Aluminum which is roughened on the surface by known methods by dry brushing, wet brushing, sandblasting, chemical and / or electrochemical treatment, is used particularly frequently as the base material for such layer supports.
  • electrochemically roughened substrates in particular are subjected to an anodization step to build up a thin oxide layer.
  • electrolytes such as H2SO4, H3PO4, H2C2O4, H3BO3, amidosulfonic acid, sulfosuccinic acid, sulfosalicylic acid or mixtures thereof.
  • the oxide layers built up in these electrolytes or electrolyte mixtures differ in structure, layer thickness and resistance to chemicals.
  • H2SO4 containing electrolytes produced aluminum oxide layers are amorphous and usually have a layer weight of about 0.5 to 10 g / m2 in offset printing plates, corresponding to a layer thickness of about 0.15 to 3.0 microns.
  • a disadvantage of the use of such an anodized substrate, in particular for offset printing plates, is the relatively low resistance of the oxide layers produced in H2SO4 electrolytes to alkaline solutions, such as are increasingly being used, for example, in the processing of presensitized offset printing plates, preferably in contemporary developer solutions for irradiated ones negative- or in particular positive-working radiation-sensitive layers.
  • these aluminum oxide layers often tend to more or less irreversible adsorption of substances from the applied reproduction layers, which can lead, for example, to a coloration of the oxide layers (“fogging”).
  • fluorescence a coloration of the oxide layers
  • the so anodized Beams are relatively dark and mechanical abrasion levels are poor.
  • the anodic oxidation of aluminum in phosphorus oxygen acids and aqueous electrolytes optionally containing further compounds is also known and is described, for example, in DE-A 32 06 470, where the prior art is also discussed in detail.
  • the plates produced in this way are somewhat lighter in appearance than those anodized with sulfuric acid and, for example, also have better abrasion resistance and alkali resistance, but the plates are not yet silvery - as desired and tend to be under-exposed.
  • Electroless alkaline treatments of aluminum oxide surfaces are also known, e.g. from DD-A 208 176, JP-A 58/177497 and JP-A 56/051388 and DE-A 32 19 922.
  • JP-A 57/085998 and JP-A 57/085996 describe a method for anodizing solar energy collectors in which an electrolyte is used which, in addition to an alkali metal hydroxide, also contains an acid and sodium phosphate, a polyhydric alcohol or a fluoride. Because of the additives, this electrolyte has a pH which is too low to be used in the process according to the invention. Therefore, under practical conditions it is not possible to achieve oxide layers as thick as those for lithographic ones Purposes would be desirable. The addition of fluoride also increases the corrosiveness of the electrolyte, which leads to an unsightly gray surface.
  • EP-A 0 048 988 describes a multi-stage process for coloring the surface of aluminum, in which strip-shaped patterns are produced. Material is used that was previously anodized.
  • the coloring step - uses an electrolyte that contains alkali metal ions and additives that lead to the stripe pattern. Alkali metal phosphates or borates or alkaline earth metal compounds and an acid with which the pH is adjusted below 5.0 are mentioned as additives.
  • alkaline electrolytes are known to form a thin, but very dense, electrically insulating barrier layer that prevents an oxide layer that is sufficiently thick for lithographic purposes from being built up (see, for example, Wernick and Pinner, "The Surface Treatment and Finishing of Aluminum and its Alloys ", Vol. 1, pp. 304ff., Robert Draper Ltd., Teddington 1972).
  • JP-A 53/011843 recommends an electrolyte that can be acidic or alkaline and contains chloride.
  • An aluminum material treated with this electrolyte has an unsightly, irregularly gray surface due to the corrosive chloride ions.
  • the object of the present invention is to provide a carrier material based on aluminum or its alloys, which at the same time has a higher resolution of the plates coated with a light-sensitive layer, high contrast between non-image areas and image areas, high oxide layer weight, high abrasion resistance, high alkali resistance and good adhesion between the support and the photosensitive layer.
  • the invention is based on a plate, foil or tape-shaped carrier material for offset printing plates made of bright rolled, mechanically and / or chemically or mechanically and electrochemically roughened aluminum or its alloys anodized in alkaline solutions.
  • the characteristic of the invention is that the carrier material has a reflectometer value at 60 ° (measured according to DIN 67530, 1982) of> 5, an abrasion of the oxide layer of ⁇ 0.5 g / m2 and an alkali resistance of> 140 s.
  • the carrier material preferably has a reflectometer value of ⁇ 15.
  • the preferred value for the abrasion of the oxide layer is ⁇ 0.3 g / m2 and that of the alkali resistance is ⁇ 160 s.
  • the carrier material preferably has an oxide basis weight of> 0.8 g / m 2.
  • the manufacture of the carrier material is based on a process in which plate, foil or strip-shaped aluminum or its alloys are roughened mechanically and / or chemically or mechanically and electrochemically and anodized in an aqueous alkaline electrolyte at a voltage greater than 36 V. will. It is characteristic that the applied voltage is set in a range from 42 to below 50 V and that the pH value is in the range greater than or equal to 12.5 to less than or equal to 13.4.
  • the electrolyte contains sodium hydroxide.
  • the electrolyte contains a strongly alkaline salt such as alkali metal octyl sulfate, carbonate, aluminate, borate, silicate or phosphate of a weak acid.
  • the alkali metal salt in 1% by weight aqueous solution has a pH of at least 10.5.
  • the electrolyte also contains 0.1 to 20% by weight, preferably 0.5 to 10% by weight, of solids.
  • the anhydrous solids content of the electrolyte is too at least 60% by weight preferably from alkali metal hydroxide.
  • the rest can consist of a weak acid alkali metal salt, surfactants and aluminum ions, these components not being essential for the operation of the process.
  • Alkali metal salts of weak acids form alkaline solutions in water.
  • those salts are selected in the process according to the invention whose 1% by weight aqueous solutions (of the anhydrous salts) have a pH of at least 10.5.
  • some alkali metal carbonates, alkali metal silicates and alkali metal phosphates and alkali metal aluminates are suitable.
  • surfactants are relatively uncritical. It should be a substance that does not decompose too quickly under the conditions of anodic oxidation so that the electrolyte does not have to be regenerated too often.
  • sodium octyl sulfate can be added. An amount of one percent by weight is sufficient, but more can be used without adverse consequences.
  • Aluminum ions are brought into the electrolyte anyway by dissolving the anode material during the anodizing process. They can also be added to the electrolyte before the start of the anodization in order to change the relative composition of the electrolyte in the course of the anodization by dissolving the anode material to diminish. However, an increased content of aluminum ions in the electrolyte reduces the current flow during anodization. Aluminum ions can be added until the weight ratio of alkali metal hydroxide to aluminum ions is about 6: 1, but it makes sense to use less. Aluminum can be added to the electrolyte, for example, in the form of alkali metal aluminate.
  • the concentration ranges of the electrolyte components are checked at regular intervals, since they are of crucial importance for an optimal process, and the electrolyte is then regenerated discontinuously or continuously.
  • the process according to the invention itself can be carried out batchwise or in particular continuously.
  • Good electrolyte circulation is preferred in the practice of the invention. This can be generated by stirring or pumping around the electrolyte.
  • care must be taken that the electrolyte is conducted as parallel as possible to the strip to be treated under turbulent flow at high speed while ensuring good material and heat exchange.
  • the flow rate of the electrolyte relative to the strip is then expediently more than 0.3 m / s.
  • Direct current is used in particular as the type of current, however alternating current or a combination of these types of current (e.g. direct current with superimposed alternating current or asymmetrical types of current) can also be used.
  • the voltages are generally between 2 and 50 V, the current densities between 3 and 50 A / dm2, the temperatures between 10 and 50 ° C and the time periods between 5 and 500 seconds.
  • the oxide layer weight to be achieved by the method according to the invention increases with increasing current density and longer anodizing time, but the current yield decreases with increasing duration of the anodizing.
  • the strongly alkaline electrolyte is very aggressive and aluminum oxide can dissolve quickly, surprisingly oxide layer weights of 2 g / m2 and more can be achieved here.
  • the oxide layer's weight also increases the resistance of the oxide layer to mechanical abrasion.
  • the correction contrast due to corrections, the appearance of light areas on a tinted background
  • the "fog" are largely independent of the electrolyte concentration.
  • the mechanical abrasion values generally become more favorable.
  • oxide layers achieved in this way combine all the advantages known per se from supports anodized in phosphoric acid, such as, for. B. a bright, shiny silver color, a very good alkali resistance and low tendency to fog with the advantage of an anodized in sulfuric acid, which consists in its relatively high oxide layer weight and the associated favorable values of mechanical abrasion.
  • Suitable base materials for the material to be oxidized according to the invention include those made of aluminum or one of its alloys, which have, for example, more than 98.5% by weight of Al and proportions of Si, Fe, Ti, Cu and Zn. These aluminum support materials are roughened, optionally after a preliminary cleaning, mechanically (e.g. by brushing and / or with abrasive treatments) and electrochemically (e.g. by AC treatment in aqueous HCl, HNO3 or in salt solutions) or only electrochemically. All process steps can be carried out batchwise, but they are preferably carried out continuously.
  • the process parameters are in the following ranges: the temperature of the electrolyte between 20 and 60 ° C., the active substance (acid, salt) concentration between 2 and 100 g / l (in the case of salts also higher), the current density between 15 and 250 A / dm2, the dwell time between 3 and 100 s and the electrolyte flow rate on the surface of the workpiece to be treated between 5 and 100 cm / s; AC is usually used as the type of current, but modified types of current such as AC with different amplitudes of the current strength are also possible for the anode and cathode currents.
  • the average roughness depth R z of the roughened surface is in the range from about 1 to 15 ⁇ 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.
  • 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 stage of anodic oxidation of the aluminum support material can also be followed by one or more post-treatment stages, although this is often not necessary, particularly in the present process.
  • 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.
  • 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 resins, dyes or plasticizers.
  • the following light-sensitive compositions or compounds can be used in the coating of the carrier materials produced by the process according to the invention: positive-working, o-quinonediazides, in particular o-naphthoquinonediazides such as naphthoquinone- (1,2) -diazid- (2) -sulfonic acid esters or amides, which can be of low or higher molecular weight, as a photosensitive compound-containing reproduction layers, for example in the DE-C 854 890, 865 109, 879 203, 894 959, 938 233, 1 109 521, 1 144 705, 1 118 606, 1 120 273, 1 124 817 and 2 331 377 and EP-A 0 021 428 and 0
  • an orthocarboxylic acid ester group or a carboxylic acid amide acetal group and optionally contain a binder; negatively working layers made of photopolymerizable monomers, photoinitiators, binders and optionally other additives; the monomers used 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.
  • Negative-working layers according to DE-A 30 36 077 which contain a diazonium salt polycondensation product or an organic azido compound as a photosensitive compound and a high molecular weight polymer with pendant alkenylsulfonyl or cycloalkenylsulfonylurethane groups as a binder.
  • 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.
  • a bright rolled aluminum sheet with a thickness of 0.3 mm is degreased with an aqueous alkaline pickling solution at a temperature of 50 to 70 ° C.
  • the electrochemical roughening of the aluminum surface takes place with alternating current in an electrolyte containing HCl.
  • the subsequent anodic oxidation is carried out in the following electrolytes: 1.
  • the voltage for all settings was 42 V (direct current), which enables easy handling in practice.
  • the anodization results are summarized in Table I.
  • the table proves that oxide layers of 0.8 and preferably 2 g / m 2 and more can be achieved with the electrolytes according to the invention and that the supports have only a low abrasion.
  • the alkali resistance, measured with the zincate test, is excellent for all carriers, and all show a silvery surface with a good 60 ° reflectometer value measured according to DIN 67 530 and with the aforementioned good properties.
  • alkaline electrolytes according to the invention often tend to form an insulating barrier layer during anodization, which allows only a small current flow at moderate voltages and therefore does not allow the build-up of sufficiently thick oxide layers within practical times.
  • the carriers usually do not show the desired gloss, which brings the previously mentioned positive properties.
  • the voltage in the comparative tests was 42 V here too. For most electrolytes, this relatively high voltage was necessary in order to force a sufficiently high current flow.
  • the comparative experiments were carried out with the following electrolytes: A. Sodium acetate 20.5 g / l (pH 8) not according to the invention, alkali metal hydroxide pH too low, none B. sodium 33 g / l (pH 11.5) not according to the invention, alkali metal hydroxide pH too low, none C. Sodium bicarbonate 10 g / l (pH 8.6) not according to the invention, alkali metal hydroxide pH too low, none D. Lithium hydroxide 5.8 g / l (pH 11.9) not according to the invention, pH too low E.
  • An aluminum substrate produced in accordance with Example 8 is provided with the following negative-working photosensitive layer: 0.70 parts by weight of the polycondensation product from 1 mol of 3-methoxy-diphenylamine-4-diazonium sulfate and 1 mol of 4,4'-bis-methoxymethyl-diphenyl ether, precipitated as mesitylene sulfonate, 3.40 parts by weight of 85% phosphoric acid, 3.00 parts by weight of a modified epoxy resin obtained by reacting 50 parts by weight of an epoxy resin with a molecular weight below 1000 and 12.8 parts by weight of benzoic acid in ethylene glycol monomethyl ether in the presence of benzyltrimethylammonium hydroxide, 0.44 part by weight of finely ground heliogen blue G (CI74 100) 62.00 parts by volume of ethylene glycol monomethyl ether, 30.60 parts by volume of tetrahydrofuran and 8.00 parts by volume of butyl acetate.
  • a modified epoxy resin obtained by
  • the printing plate produced in this way can be developed quickly and free of fog.
  • the print run with a printing form produced in this way is 130,000.
  • a carrier material produced in accordance with Comparative Example V7 and coated with the same formulation can only be developed under difficult conditions. After development, a yellow haze remains in the non-image areas, which may be caused by adhering particles of the diazonium compound. If a carrier material according to comparative example V3 is used, then after printing about 90,000 prints, a clear gloss is found in the non-image areas, which increases with increasing circulation. After 100,000 prints, the print quality has dropped to a level that is no longer accepted in practice.
  • An aluminum substrate produced as described in Example 10 is coated with the following positive-working photosensitive solution: 6.00 parts by weight cresol-formaldehyde novolak (with a softening range of 105 to 120 ° C according to DIN 53 181) 1.10 parts by weight of the 4- (2-phenyl-prop-2-yl) phenyl ester Naphthoquinone- (1,2) -diazide- (2) -sulfonic acid- (4), 0.81 part by weight of polyvinyl butyral, 0.75 part by weight of naphthoquinone- (1,2) -diazide- (2) -sulfonic acid chloride- (4), 0.08 part by weight of crystal violet, 91.36 parts by weight of solvent mixture of 4 parts by volume of ethylene glycol monomethyl ether, 5 parts by volume of tetrahydrofuran and 1 part by volume of butyl acetate.
  • the coated tape is dried in the drying tunnel at temperatures up to 120 ° C.
  • the printing plate thus produced is exposed under a positive template and developed with a developer of the following composition: 5.30 parts by weight of Na2SiO3 ⁇ 9 H20, 3.40 parts by weight of Na3PO4 ⁇ 12 H20, 0.30 parts by weight of NaH2PO4 (anhydrous), 91.00 parts by weight of water.
  • the printing form obtained is perfect in terms of copying and printing technology and has an excellent resolution.
  • the print run is 150,000.
  • a corresponding plate made from the carrier material of comparative example V6 shows a blue haze in the non-image areas. With prolonged exposure to the developer, there is a clear light-dark shading in the non-image areas, which indicates an attack by the developer solution of the oxide.
  • An aluminum substrate produced according to the information in Example 16 is provided with the following negative-working photosensitive layer: 16.75 parts by weight of an 8.0% solution of the reaction product of a polyvinyl butyral with a molecular weight of 70,000 to 80,000, consisting of 71% by weight of vinyl butyral, 2% by weight of vinyl acetate and 27% by weight of vinyl alcohol Units, with propylene sulfonyl isocyanate, 2.14 parts by weight of 2,6-bis- (4-azido-benzene) -4-methylcyclohexanone, 0.23 parts by weight of (R) Rhodamine 6 GDN extra and 0.21 part by weight of 2-benzoylmethylene-1-methyl- ⁇ -naphthothiazoline in 100 parts by weight of ethylene glycol monomethyl ether and 50 parts by weight of tetrahydrofuran.
  • the dry layer weight is 0.75 g / m2.
  • the reproduction layer is exposed under a negative original for 35 s using a metal halide lamp with a power of 5 kW.
  • the exposed layer is covered with a plush pad with a developer solution of the composition 5 parts by weight of sodium lauryl sulfate 1 part by weight of Na2SiO3 ⁇ 5 H2O 94 parts by weight of water treated, the non-image areas are removed.
  • the print run of the plate in a printing press is 170,000.
  • the copy layer has a markedly reduced adhesion, which leads to parts of the layer becoming detached from the image areas after only about 120,000 prints.
  • a support anodized according to Example 5 is coated with the following solution to produce an electrophotographic offset printing plate: 10.00 parts by weight of 2,5-bis (4'-diethylaminophenyl) -1,3,4, -oxdiazole 10.00 parts by weight of a copolymer of styrene and maleic anhydride with a softening point of 210 ° C. 0.02 part by weight (R) Rhodamine FB (CI 45 170) 300.00 parts by weight of ethylene glycol monomethyl ether
  • 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 developed with an electrophotographic suspension developer which also contains a dispersion of 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 a boiling range of 185 to 210 ° C represents.
  • an electrophotographic suspension developer which also contains a dispersion of 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 a boiling range of 185 to 210 ° C represents.
  • the developer is fixed and the plate is poured out into a solution for 60 s 35 parts by weight of Na2SiO3 ⁇ 9 H2O, 140 parts by weight of glycerin, 550 parts by weight of ethylene glycol and 140 parts by weight of ethanol submerged.
  • the plate is then rinsed off with a powerful water jet, the areas of the photoconductor layer which are not covered with toner being removed, and the plate is then ready for printing.
  • the non-image areas of the plate show good hydrophilicity and show no signs of attack even after exposure to alkaline solutions. Several tens of thousands of good prints can be achieved with the printing form.
  • An aluminum sheet prepared according to the information in Example 2 is immersed in a further treatment step (additional hydrophilization) in a 0.2% aqueous solution of polyvinylphosphonic acid at 50 ° C. for 20 s. After drying, the substrate material additionally hydrophilized in this way is further processed as described in Example 19, it being possible to further improve the ink-repelling effect of the non-image areas.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Printing Plates And Materials Therefor (AREA)

Claims (14)

  1. Matériau de support sous forme de plaque, feuille ou bande pour plaques d'impression offset, à base d'aluminium ou d'un de ses alliages, laminé-brillant, grainé mécaniquement et/ou chimiquement ou mécaniquement et électrochimiquement, et anodisé dans des solutions alcalines, caractérisé en ce qu'il présente un indice réflectométrique > 5 à un angle d'incidence de 60° (mesuré selon DIN 67 530, 1982), une abrasion de la couche d'oxyde de < 0,5 g/m² et une résistance aux alcalis de > 140 s.
  2. Matériau de support selon la revendication 1, caractérisé en ce qu'il présente un indice réflectométrique ≧ 15 à 60° (mesuré selon DIN 67 530).
  3. Matériau de support selon la revendication 1 ou 2, caractérisé en ce qu'il présente une abrasion de la couche d'oxyde de ≦ 0,3 g/m².
  4. Matériau de support selon l'une des revendications 1 à 3, caractérisé en ce qu'il présente une résistance aux alcalis de ≧ 160 s.
  5. Matériau de support selon l'une des revendications 1 à 4, caractérisé en ce qu'il présente un poids d'oxyde par unité de surface > 0,8 g/m².
  6. Procédé pour la fabrication d'un matériau de support selon une ou plusieurs des revendications 1 à 5, dans lequel de l'aluminium ou l'un de ses alliages, sous forme de plaque, feuille ou bande, est grainé mécaniquement et/ou chimiquement, ou mécaniquement et électrochimiquement, et anodisé à une tension de plus de 36 V dans un électrolyte aqueux-alcalin, caractérisé en ce que la tension appliquée est ajustée dans une plage allant de 42 à moins de 50 V, et en ce que le pH se situe dans l'intervalle allant de ≧ 12,5 à ≦ 13,4.
  7. Procédé selon la revendication 6, caractérisé en ce que l'électrolyte contient de l'hydroxyde de sodium.
  8. Procédé selon la revendication 6 ou 7, caractérisé en ce que l'électrolyte contient un sel à forte réaction alcaline d'un acide faible, tel qu'un octylsulfate, carbonate, aluminate, borate, silicate ou phosphate de métal alcalin.
  9. Procédé selon la revendication 8, caractérisé en ce que le sel de métal alcalin, en solution aqueuse à 1 % en poids, a un pH d'au moins 10,5.
  10. Procédé selon une ou plusieurs des revendications 6 à 9, caractérisé en ce que l'électrolyte contient des substances tensioactives.
  11. Procédé selon une ou plusieurs des revendications 6 à 10, caractérisé en ce que l'on effectue l'anodisation avec une densité de courant de 3 à 50 A/dm², à une température comprise entre 10 et 50°C, pendant une durée de 5 à 500 s, en particulier de 10 à 300 s.
  12. Procédé selon une ou plusieurs des revendications 6 à 11, caractérisé en ce que l'électrolyte contient de 0,1 à 20 % en poids d'hydroxyde de métal alcalin, un sel à réaction fortement alcaline d'un acide faible, des substances tensioactives et des ions aluminium.
  13. Procédé selon la revendication 12, caractérisé en ce que l'électrolyte contient de 0,5 à 10 % en poids d'hydroxyde de métal alcalin, un sel à réaction fortement alcaline d'un acide faible, des substances tensioactives et des ions aluminium.
  14. Procédé selon une ou plusieurs des revendications 6 à 13, caractérisé en ce que l'on effectue une hydrophilisation après l'anodisation.
EP87115715A 1986-11-06 1987-10-27 Support en aluminium ou en alliage d'aluminium pour des plaques offset et son procédé de fabrication Expired - Lifetime EP0269851B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863637764 DE3637764A1 (de) 1986-11-06 1986-11-06 Traegermaterial auf der basis von aluminium oder dessen legierungen fuer offsetdruckplatten sowie verfahren zu dessen herstellung
DE3637764 1986-11-06

Publications (3)

Publication Number Publication Date
EP0269851A2 EP0269851A2 (fr) 1988-06-08
EP0269851A3 EP0269851A3 (en) 1989-07-19
EP0269851B1 true EP0269851B1 (fr) 1993-06-09

Family

ID=6313269

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87115715A Expired - Lifetime EP0269851B1 (fr) 1986-11-06 1987-10-27 Support en aluminium ou en alliage d'aluminium pour des plaques offset et son procédé de fabrication

Country Status (4)

Country Link
US (1) US4853093A (fr)
EP (1) EP0269851B1 (fr)
JP (1) JPS63134292A (fr)
DE (2) DE3637764A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5132196A (en) * 1989-08-29 1992-07-21 Minolta Camera Kabushiki Kaisha Photosensitive member having a colored aluminum oxide layer
US5269904A (en) * 1992-06-05 1993-12-14 Northrop Corporation Single tank de-oxidation and anodization process
US5513766A (en) * 1993-11-30 1996-05-07 Sandoz Ltd. Aluminum etching
GB9326150D0 (en) * 1993-12-22 1994-02-23 Alcan Int Ltd Electrochemical roughening method
JP3522923B2 (ja) * 1995-10-23 2004-04-26 富士写真フイルム株式会社 ハロゲン化銀感光材料
WO2003023088A1 (fr) * 2001-09-07 2003-03-20 The Board Of Regents For Oklahoma State University Enlevement de films silicates organiquement modifies de substrats metalliques
US7780838B2 (en) 2004-02-18 2010-08-24 Chemetall Gmbh Method of anodizing metallic surfaces
JP5580948B1 (ja) * 2013-09-27 2014-08-27 日本ペイント株式会社 アルミニウム缶の表面処理方法
KR20160049119A (ko) * 2014-10-24 2016-05-09 현대자동차주식회사 주조용 알루미늄 합금 표면 처리용 전해액 및 주조용 알루미늄 합금 표면 처리방법

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2287148A (en) * 1938-05-20 1942-06-23 Ralph F Taber Wear and hardness testing instrument
US4166777A (en) * 1969-01-21 1979-09-04 Hoechst Aktiengesellschaft Corrosion resistant metallic plates particularly useful as support members for photo-lithographic plates and the like
GB1243741A (en) * 1969-01-31 1971-08-25 Peter Neufeld Anodising of aluminium in alkaline borate solutions
JPS4935239A (fr) * 1972-08-07 1974-04-01
JPS52120238A (en) * 1976-04-03 1977-10-08 Nippon Light Metal Co Process for coloring aluminum or aluminum alloy
JPS5431047A (en) * 1977-08-11 1979-03-07 Shokosha Kk Baseesurface treatment of aluminum and alloys thereof
DE2811396A1 (de) * 1978-03-16 1979-09-27 Hoechst Ag Verfahren zur anodischen oxidation von aluminium und dessen verwendung als druckplatten-traegermaterial
US4278737A (en) * 1978-08-04 1981-07-14 United States Borax & Chemical Corporation Anodizing aluminum
US4188270A (en) * 1978-09-08 1980-02-12 Akiyoshi Kataoka Process for electrolytically forming glossy film on articles of aluminum or alloy thereof
JPS5651388A (en) * 1979-10-02 1981-05-08 Fuji Photo Film Co Ltd Manufacture of supporting body for lithographic press plate
JPS6014838B2 (ja) * 1980-09-30 1985-04-16 ワイケイケイ株式会社 アルミニウム表面に着色筋目模様を形成する方法
JPS5785998A (en) * 1980-11-13 1982-05-28 Shiyoukoushiya:Kk Production of absorptive plate for solar heat energy
JPS5785996A (en) * 1980-11-13 1982-05-28 Shiyoukoushiya:Kk Production of absorptive plate for solar heat energy
JPS58177497A (ja) * 1982-04-10 1983-10-18 Tateyama Alum Kogyo Kk アルミニウムまたはアルミニウム合金の着色方法
JPS58210144A (ja) * 1982-06-01 1983-12-07 Fuji Photo Film Co Ltd 平版印刷版支持体用アルミニウム合金
SU1222714A1 (ru) * 1984-04-05 1986-04-07 Днепропетровский завод шахтной автоматики Электролит дл анодировани алюмини
JPH05311843A (ja) * 1992-05-01 1993-11-22 Mitsubishi Rayon Co Ltd カラータイル被覆の形成方法

Also Published As

Publication number Publication date
JPS63134292A (ja) 1988-06-06
EP0269851A2 (fr) 1988-06-08
DE3786149D1 (en) 1993-07-15
DE3637764A1 (de) 1988-05-11
EP0269851A3 (en) 1989-07-19
US4853093A (en) 1989-08-01

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