EP0184756B1 - Electrolyte pour le traitement électrochimique des plaques métalliques et procédé de fabrication de plaques métalliques anodisées, de préférence pour l'application comme supports de plaques d'impression - Google Patents

Electrolyte pour le traitement électrochimique des plaques métalliques et procédé de fabrication de plaques métalliques anodisées, de préférence pour l'application comme supports de plaques d'impression Download PDF

Info

Publication number
EP0184756B1
EP0184756B1 EP85115292A EP85115292A EP0184756B1 EP 0184756 B1 EP0184756 B1 EP 0184756B1 EP 85115292 A EP85115292 A EP 85115292A EP 85115292 A EP85115292 A EP 85115292A EP 0184756 B1 EP0184756 B1 EP 0184756B1
Authority
EP
European Patent Office
Prior art keywords
acid
electrolyte
process according
organic
layer
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
EP85115292A
Other languages
German (de)
English (en)
Other versions
EP0184756A2 (fr
EP0184756A3 (en
Inventor
Stephan J. Platzer
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.)
CNA Holdings LLC
Original Assignee
Hoechst Celanese Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hoechst Celanese Corp filed Critical Hoechst Celanese Corp
Publication of EP0184756A2 publication Critical patent/EP0184756A2/fr
Publication of EP0184756A3 publication Critical patent/EP0184756A3/de
Application granted granted Critical
Publication of EP0184756B1 publication Critical patent/EP0184756B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • 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
    • C25D11/30—Anodisation of magnesium 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
    • C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32

Definitions

  • the present invention relates to the use of an electrolyte in the production of printing plate supports on aluminum or its alloys.
  • the present invention also relates to a method for producing such printing plate supports
  • the treated metal plates have increased corrosion resistance and are suitable for use in planographic printing, among other things.
  • they When used as a support for planographic printing plates, they are notable for increased adhesive strength of the photosensitive layers, longer print runs, less wear on the image and non-image areas, longer shelf life and improved hydrophilicity in the non-image areas. This is especially true when using aluminum or aluminum alloys.
  • Anodic oxidation is an electrolytic process in which the metallic workpiece is treated as an anode and treated in a suitable electrolyte.
  • electrical current flows from a cathode through the electrolyte to the metallic workpiece, the surface of the metal is converted to one of its oxide forms with decorative, protective, or other properties.
  • the cathode is made of metal or graphite, and the only significant reaction that occurs on it is the evolution of hydrogen.
  • the oxide layer is formed from the solution side, that is, outside the metal, so that the oxide formed is directly adjacent to the metal.
  • the oxygen required for oxide formation comes from the respective electrolyte.
  • Oxide layers produced on aluminum anodically are divided into two main classes:
  • barrier layer which is created when the electrolyte used has only a slight ability to dissolve the oxide layer.
  • These layers are essentially non-porous. The thickness is limited to approximately 13 ANolt. After reaching this limit thickness, the layer forms an effective barrier layer against further ion or electron flow. The current drops to a low value and the oxide formation stops. Boric and tartaric acid are used as electrolytes for this process.
  • the oxide layer does not reach its final limit thickness if the electrolyte exerts a noticeable solution on the oxide: current continues to flow and the oxide layer contains a «porous» structure.
  • Porous structures can be quite thick, that is, they can reach a thickness of a few 10 wm, but a thin barrier layer made of oxide is always retained at the boundary between metal and oxide.
  • Sulfuric acid is used as the electrolyte in most cases, and phosphoric acid is also frequently used.
  • Anodically produced aluminum oxide layers are harder than oxide layers obtained under the influence of air.
  • US Pat. No. 3,227,639 describes the use of a mixture of sulfophthalic and sulfuric acids for producing protective and decorative anodic oxide layers on aluminum.
  • Other aromatic sulfonic acids are used in accordance with US Pat. No. 3,804,731 in a mixture with sulfuric acid.
  • Anodization is followed by an aftertreatment step in numerous processes in which the porous surface is sealed, as a result of which the final properties of the layer are determined.
  • pure water can be used for this at high temperatures. It is believed that part of the oxide layer is thereby dissolved and precipitated again as a voluminous hydroxide (or hydrated oxide) within the pores.
  • Other aqueous sealants contain metal salts, the oxides of which can be precipitated together with the aluminum oxide.
  • an organic acid (acetic acid, hydroxyacetic acid or aminoacetic acid) is added to a mixture of sulfuric and phosphoric acid in order to produce an anodic oxide layer on a plate which is then to be galvanized.
  • US Pat. No. 4,115,211 describes the anodic oxidation of aluminum by means of alternating current or superimposed alternating and direct current.
  • the electrolyte used contains a water-soluble acid and a water-soluble salt of a heavy metal.
  • the water-soluble acid can be oxalic, tartaric, citric, malonic, sulfuric, phosphoric, sulfamic or boric acid.
  • porous anodized layers are suitable for planographic printing, while non-porous anodized layers are unsuitable because the porous layer gives the non-image areas on the plate a surface with improved water flow and the adhesive strength of the Imaging material on the plate surface increased by the fact that it can penetrate into the pores.
  • US Pat. No. 3,511,661 describes aluminum foils for planographic printing which have been anodized in aqueous phosphoric acid, the oxide layers having a structure with pore-like openings, which has aluminum oxide cells, the average diameter of which is approximately 200 to 700 A, and on the surface of which a layer of about 10 to 200 mg / m 2 of aluminum phosphate is located.
  • an aluminum foil which has been anodized in a conventional manner is electrolytically aftertreated in an aqueous solution of sodium silicate in order to obtain a hydrophilic, abrasion and corrosion-resistant layer and thus a presensitized support suitable for planographic printing.
  • a conventional anodic oxidation which is carried out up to an oxide layer thickness of at least 0.2 pm, is followed by an aftertreatment with aqueous polyvinylphosphonic acid, at temperatures between 40 and 95.degree.
  • the treatment improves the adhesion of a subsequently applied coating, the shelf life of the plate and the hydrophilicity of the non-image areas after exposure and development and the print run.
  • US Pat. No. 4,399,021 describes a process for electrochemical treatment for the production of carrier plates made of aluminum or its alloys, polyphosphonic, polyphosphoric, polysulfonic and polycarboxylic acids being used in the electrolyte.
  • the method also strives for an even higher print run, the method being more economical than the conventional anodic oxidation, which is followed by a further operation for sealing and aftertreatment of the oxide layer before the Coating can be applied.
  • the invention is based on the use of an electrolyte in the production of a printing plate support made of aluminum or its alloys, the electrolyte containing at least one water-soluble acid which forms an insoluble organic complex on the surface.
  • the electrolyte as an acid is an organic phosphonic, phosphoric or sulfonic acid - or an at least tripasic carboxylic acid - selected from the group consisting of nitrilotriacetic, 1,2,4,5-benzenetetracarbon, diethylenediaminepentaacetic, ethylenediaminetetraacetic, or hydroxyethylenediaminetriacetic acid, copolymer of methyl vinyl ether and maleic anhydride, copolymer of methyl vinyl ether and maleic acid, alginic polyacrylic or polymethacrylic acid or a mixture of the acids and a base compatible with the acid and that the pH is 4 to 8.
  • the present invention also relates to a method using the electrolyte.
  • the process is operated with direct current.
  • the insoluble complex of metal oxide and organic component formed during electrolysis consists of a combination of anodically generated oxide and polyacid, which forms a protective layer on the metal with improved corrosion resistance.
  • the complex of metal oxide and organic component is well suited for anchoring light-sensitive layers.
  • Printing plate carrier materials produced according to the invention result in a longer shelf life, better printing properties and a longer print run than carriers produced using conventional methods.
  • the method according to the invention comprises the cleaning of the aluminum and then the anodic oxidation by means of direct current.
  • the electrolytic treatment takes place under such conditions that an insoluble complex of metal oxide and organic acid component is formed, which adheres firmly to the surface of the metal object.
  • An examination of the surface of the product produced according to the invention shows that it is essentially non-porous.
  • the carriers are cleaned before the electrochemical treatment according to the invention. This can be done using a variety of different solvents or aqueous alkaline solutions, the choice of which depends on the type of metal used and the purpose for which the support is to be used.
  • Typical alkaline degreasing agents are, for example, hot aqueous solutions which contain alkalis such as sodium hydroxide, potassium hydroxide, trisodium phosphate, sodium silicate, aqueous, alkaline products and wetting agents.
  • alkalis such as sodium hydroxide, potassium hydroxide, trisodium phosphate, sodium silicate, aqueous, alkaline products and wetting agents.
  • Such a mixture is e.g. B. ( R ) Ridolene 57 (manufacturer Amchem Products, Pennsylvania).
  • Degreasing treatments with solvents such as trichlorethylene, 1,1,1-trichloroethane and perchlorethylene have been performed less frequently for some time due to health and ecological concerns. Degreasing with solvents is done by dipping spray or steam treatment.
  • Suitable metals that can be treated according to the invention are aluminum and aluminum alloys.
  • As a carrier for planographic printing plates are z.
  • Typical aluminum alloys for planographic printing plates contain the following components (in% by weight):
  • the chemical composition of the alloy used probably also has a certain influence on the effectiveness of the electrolytic deposition of organic electrolytes.
  • Other alloy components that are not normally analyzed can also have an impact.
  • the surface of the metal to be treated can be smooth or roughened.
  • the roughening is done using known methods, such as. B. chemical roughening in alkaline or acidic etching solutions, dry brushing, wet brushing with abrasive suspensions, roughening with abrasive balls and electrochemical roughening. Each of these processes results in a different roughening and surface topography.
  • the best results are achieved if the cleaned surface is treated electrolytically immediately, that is before an air oxide layer can form.
  • the plate Before immersing the cleaned, degreased and possibly roughened plate in the organic electrolytic solution for electrolytic deposition, the plate should be etched to remove air oxide. The etching is done in a known manner, e.g. B. in one of the described acidic or alkaline media or electrolytes.
  • the plate can also be removed with an etchant, such as e.g. B. a solution of phosphoric and chromic acid. It is preferred to rinse the metal surface with water immediately after cleaning and, if necessary, to roughen it, and to subject it to the electrolytic treatment according to the invention while still wet, although satisfactory results are also achieved if the procedure is not so careful.
  • the cleaning and eventual roughening may be followed by a conventional anodic oxidation of the metal before the electrolyte is used.
  • organic electrolytes which are used according to the invention for increasing the corrosion resistance include aqueous solutions of sulfonic, phosphoric and carboxylic acids, which are at least three-base and can be mono- or polymeric, and mixtures thereof.
  • electrolytes include aqueous solutions of sulfonic, phosphoric and carboxylic acids, which are at least three-base and can be mono- or polymeric, and mixtures thereof.
  • sulfonic, phosphoric and carboxylic acids which are at least three-base and can be mono- or polymeric, and mixtures thereof.
  • Preferred electrolytes are therefore contain the condensation product of benzenephosphonic acid and formaldehyde, low molecular weight copolymers of methyl vinyl ether and maleic anhydride, copolymers of methyl vinyl ether and maleic acid, polyvinyl sulfonic acid, phytic acid, polyvinylphosphonic acid, Dodecylpolyoxyethylenphosphorklare, Diisopropylpolynaphthalinsulfonklare, 2-Ethylhexylpolyphosphorklare, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, or mixtures of several of these compounds.
  • condensation product of benzenephosphonic acid and formaldehyde, phytic acid, polyvinylphosphonic acid, 2-ethylhexylpolyphosphoric acid and mixtures of these compounds are particularly preferably used in planographic printing.
  • a very suitable electrolyte mixture is, for example, a mixture of phytic acid and polyvinylphosphonic acid.
  • the properties of the coated metal depend essentially on the concentration of the electrolyte and the electrolysis conditions, such as voltage, current density, time or temperature.
  • the electrolyte solution must contain a base which is compatible with the acid in a quantity such that the solution has a pH in the range from 4 to 8.
  • the pH value is between 6 and 7.
  • Bases suitable according to the invention are e.g. B. hydroxides such as sodium, lithium, potassium and ammonium hydroxide. It is possible that a harder anodic oxide layer will form in the specified pH range due to the decreasing solubility in aluminum oxide.
  • Plates intended for planographic printing are subjected to a test immediately after the electrolytic deposition of the complex of metal oxide and organic component, that is to say before the photosensitive layer has been applied.
  • the plates are stained wet or dry, with the second test being stricter. After staining, the plate is rinsed under running water or sprayed with water and lightly rubbed off. The ease and completeness with which the paint can be removed is a measure of the hydrophilicity of the plate surface.
  • plates with and without a light-sensitive coating are subjected to an aging treatment over different periods of time and at different temperatures. It is then examined to what extent they have retained their hydrophilic properties. Plates coated with various diazo compounds are examined after the treatment with regard to step wedge resistance, image resolution, retention of the hydrophilicity at the image background sites and easy developability. Suitable photosensitive materials are described below.
  • the printing plates and comparative samples are used in a printing press.
  • the differences in surface abrasion, the resolution of the grid wedge, the speed and purity of the freewheel and the height of the print run are assessed.
  • the electrolyte used is, for example, 1.5% polyvinylphosphonic acid, which has been adjusted to a pH of 6 with sodium hydroxide, at a temperature of 23 ° C. and a direct current of 60 volts, with a cleaned and etched aluminum plate of the 1050 type as anode and a carbon rod serves as a counter electrode.
  • the complex of aluminum oxide and organic compound that makes up the surface layer initially forms very quickly. After a second, the layer thickness is already more than 0.12 J.Lm. After three seconds it is up to 0.17 Am and after five seconds the increase in the layer thickness at 0.20 J.Lm stops slowly. Even after 120 seconds there is no further appreciable increase.
  • the voltage is kept practically constant during the entire period of electrolytic deposition.
  • the amperage is not an independent variable, but depends on the other process conditions, in particular the voltage and electrolyte concentration. The amperage begins to drop very shortly after the start of electrolysis.
  • the layer consisting of the complex of metal oxide and organic compound on the plate surface acts as a capacitor.
  • the dielectric strength is not exceeded during the electrolysis, there will be no further weight gain as the time progresses and the layer will be retained throughout. If the dielectric strength is exceeded, the layer is perforated and its integrity is lost.
  • the breakdown mentioned depends primarily on the voltage, with a potential of 70 V quickly breaks down. However, a certain breakdown is already registered at 30 V if the time is extended to over 250 seconds.
  • the concentration of the electrolyte used is between about 0.01% and the saturation limit and is essentially independent of its chemical composition. Solutions with a concentration of more than 30% are generally not used, while at concentrations close to the lower limit the conductivity of the solution is very low; in the case of 0.001% polyvinylphosphonic acid it is e.g. B. at 61 000 ⁇ . Nevertheless, even at a concentration of 0.05%, a layer of a complex of metal oxide and organic component is formed, thanks to which products are obtained which are different from known products, such as, for. B. aluminum plates, which were anodized in a conventional manner and then sealed under the influence of heat with a polyvinylphosphonic acid solution, are characterized by better corrosion resistance, durability, hydrophilicity and printing properties.
  • the current conductivity of the electrolyte increases rapidly with increasing concentration, which leads to shorter treatment times and lower voltage requirements.
  • the preferred concentration range is between about 0.8% and 5%.
  • the electrodeposited layer gives the material a corrosion resistance and printing properties that are superior to conventional materials.
  • Direct current is required for the method, but it can also be superimposed by alternating current. Pulsed direct current can also be used. Square waves from pulsed anodizing current sources are particularly suitable.
  • the amperage is greatest at the start of the electrical deposition and, over time, it decreases with increasing thickness of the layer composed of the complex of metal oxide and organic compound on the metallic carrier, thus reducing the current conductivity. Within 30 seconds it drops to a level at which the further power consumption is minimal. This contributes significantly to the economy of the process, since the desired useful layer has already been deposited at this point.
  • ampere number is therefore a dependent variable, the size of which is determined by the independent variables electrolyte composition, concentration and voltage. Current densities between about 1 and 5 Aldm 2 are characteristic of favorable process conditions and are therefore preferred.
  • the process can be carried out at temperatures from about -2 ° C (near the freezing point of the electrolyte) to about 60 ° C. Measured against the criteria of surface hardness, image adhesion, hydrophilicity and durability, the best results are obtained at 10 ° C, although the performance drop at temperatures between 10 ° C and room temperature, up to 40 ° C, is only very small. In order to carry out the process at very low temperatures, complex cooling devices would be necessary. For reasons of economy and because of the low power consumption, the preferred temperature range is around 10 to 35 ° C, in particular around 20 to 25 ° C.
  • More than 60% of the layer consisting of the complex of metal oxide and organic component is formed in the first 5 seconds of the electrolytic process.
  • a treatment time of more than 5 minutes is not necessary for planographic printing, since no further layer build-up takes place; it also does no harm as long as the voltage is kept low.
  • the treatment time is preferably about 0.16 to 1 minute.
  • the short period of time, the low temperature (room temperature, so that hardly any additional heating or cooling devices are required) and the low power consumption represent favorable economic factors in comparison to conventional anodizing processes, which as a rule also include additional heat treatment of the carrier material.
  • Iminoquinonediazides, o-quinonediazides and condensation products of aromatic diazonium compounds in combination with suitable binders are suitable as photosensitive mixtures which can be applied to the layers according to the invention from the complex of metal oxide and organic component for the production of printing forms.
  • Such connections are e.g. For example, see US-A 3 175 906, 3 046 118, 2 063 631, 2 667 415 and 3 867 147.
  • the mixtures described in the latter document are generally preferred.
  • photopolymer systems based on ethylenically unsaturated monomers with photoiniators, which may contain matrix polymer binders can be used. Photodimerization systems, such as. B.
  • Polyvinylcinnamate and systems based on diallyl phthalate prepolymers are also suitable. Such systems are described in U.S. Patents 3,497,356, 3,615,435, 3,926,643, 2,670,286, 3,376,138 and 3,376,139.
  • photosensitive systems suitable according to the invention relate to customary mixtures. In principle, all of the mixtures specified are suitable, but the diazo compounds are generally preferred since they generally adhere best to the complex of metal oxide and organic component and give a higher image resolution when printed.
  • Two plates of a 3003 aluminum alloy suitable for printing purposes and roughened in an abrasive suspension are treated for 30 seconds in a 1 N sodium hydroxide solution and rinsed with distilled water at room temperature.
  • the anodization takes place for 60 seconds with lead as counter electrode at a voltage of 30 V and a maximum of 5 A / dm 2 .
  • the dry layer weight is approximately 750 mg / m 2 .
  • the printing plates obtained are exposed with an exposure device (Berkey Ascor) through a suitable template so that a fully covered step 7 is obtained on a Stauffer wedge.
  • the plates are developed with a developer (Enco Negative Subtractive Developer) and then preserved (Enco Subtractive Finisher). Both plates are used in tough test conditions (excessive pressure on the plates and printing ink with strong abrasion properties) in a printing machine (Miehle).
  • the following conditions apply to printing: uncoated paper, dampening water with a pH value of 4.35, relative humidity 53%, non-alcoholic dampening system.

Claims (14)

1. Utilisation d'un électrolyte dans la fabrication de supports de plaques d'impression en aluminium ou en alliages d'aluminium, l'électrolyte contenant au moins un acide organique soluble dans l'eau, qui forme à la surface avec le métal un complexe métallo-organique insoluble, l'électrolyte contenant comme acide un acide phosphonique, phosphorique ou sulfonique organiques ou un acide carboxylique au moins triacide, choisi parmi l'acide nitrilotriacétique, l'acide 1,2,4,5-benzènetétracarboxylique, l'acide diéthylènediaminepenta-acétique, l'acide éthylènediaminetétra-acétique ou l'acide hydroxyéthylènediaminetriacétique copolymère de méthylvinyléther et d'anhydride maléique, copolymère de méthylvinyléther et d'acide maléique, acide alginique, acide polyacrylique ou acide polyméthacrylique ou un mélange des acides et une base compatible avec l'acide et dont le pH va de 4 à 8.
2. Utilisation d'un électrolyte selon la revendication 1, caractérisé en ce que l'acide phosphonique est un produit de condensation de l'acide benzènephosphonique et du formaldéhyde (acide polubenzène- phosphonique) ou l'acide polyvinylphosphonique.
3. Utilisation d'un électrolyte selon la revendication 1, caractérisé en ce que l'acide phosphorique organique est l'acide phytique (acide inositohexaphosphorique), l'acide dodécylpolyoxyéthylènephos- phorique ou l'acide 2-éthylhexylpolyphosphorique.
4. Utilisation d'un électrolyte selon la revendication 1, caractérisé en ce que l'acide sulfonique est l'acide polyvinylsulfonique, l'acide polystyrènesulfonique, l'acide poly-n-butylbenzènesulfonique, l'acide polydiisopropylbenzènesulfonique, l'acide tridécylbenzènesulfonique, l'acide trinonylnaphtalènedisulfo- nique, l'acide 2,2-dinitro-4,4-stilbenzènedisulfonique, l'acide diisopropylpolynaphtalènedisulfonique, l'acide dodécylnaphtalènedisulfonique, l'acide di-n-butylnaphtalènedisulfonique, l'acide polynaphtalène- sulfonique et l'acide polydécylbenzènesulfonique.
5. Utilisation d'un électrolyte selon l'une des revendications 1 à 4, caractérisée en ce que l'électrolyte contient comme base un hydroxyde de métal alcalin et/ou d'ammonium.
6. Utilisation d'un électrolyte selon l'une des revendications 1 à 5, caractérisé en ce que le pH est de 6 à 7.
7. Procédé de fabrication de supports de plaques d'impression en aluminium ou en alliages d'aluminium dans lequel on nettoie les plaques et ensuite on effectue un traitement électrochimique dans un électrolyte contenant au moins un acide organique soluble dans l'eau, traitement qui forme à la surface, avec le métal, un complexe métallo-organique insoluble, avec utilisation de courant continu, traitement dans lequel on utilise un électrolyte qui contient comme acide un acide phosphonique, un acide phosphorique ou un acide sulfonique organiques ou un acide carboxylique au moins triacide - choisi parmi l'acide nitrilotriacétique, l'acide 1,2,4,5-benzènetétracarboxylique, l'acide diéthylènediaminepenta-acétique, l'acide éthylènediaminetétra-acétique ou hydroxyéthylènediaminetriacétique, copolymère de méthylvinyléther et d'anhydride maléique, copolymère de méthylvinyléther et d'acide maléique, acide alginique, polyacrylique ou polyméthacrylique ou un mélange des acides, qui contient une base compatible avec l'acide et qui a un pH de 4 à 8.
8. Procédé selon la revendication 7, caractérisé en ce que l'on utilise un électrolyte qui contient comme acide phosphonique un produit de condensation de l'acide benzènephosphonique et du formaldéhyde (acide polybenzènephosphonique) ou l'acide polyvinylphosphonique.
9. Procédé selon la revendication 7, caractérisé en ce que l'on utilise comme acide phosphorique organique de l'acide phytique (acide inositohexaphosphorique), de l'acide dodécylpolyoxyéthylènephos- phorique ou de l'acide 2-éthylhexylpolyphosphorique.
10. Procédé selon la revendication 7, caractérisé en ce que l'on emploie comme acide sulfonique l'acide polyvinylsulfonique, l'acide polystyrènesulfonique, l'acide poly-n-butylbenzènesulfonique, l'acide polydiisopropylbenzènesulfonique, l'acide tridécylbenzènesulfonique, l'acide dinonylnaphtalènedisulfo- nique, l'acide 2,2-dinitro-4,4-stilbènedisulfonique, l'acide di-isopropylpolynaphtalènedisulfonique, l'acide dodécylnaphtalènedisulfonique, l'acide di-n-butylnaphtalènedisulfonique, l'acide polynaphtalènesulfoni- que et l'acide polydécylbenzènesulfonique.
11. Procédé selon l'une des revendications 7 à 10, caractérisé en ce que l'on emploie comme base un hydroxyde de métal alcalin et/ou d'ammonium.
12. Procédé selon l'une des revendications 7 à 11, caractérisé en ce que l'on ajuste le pH à une valeur de 6 à 7.
13. Procédé selon l'une des revendications 7 à 12, caractérisé en ce que l'on ajuste la concentration d'acide à 0,5 à 30 % et en ce que l'on effectue le traitement électrolytique sous une tension de 1 à 90 V, à une densité de courant de 1 à 10 A/dm2, pendant une durée de 0,08 à 5 minutes, à une température allant de - 2 à 60 °C.
14. Procédé selon la revendication 12, caractérisé en ce que l'on ajuste la concentration d'acide à une valeur de 0,8 % à 5 % et en ce que l'on effectue le traitement électrolytique sous une tension de 5 à 70 V, à une densité de courant de 1 à 5 A/dm2, pendant une durée de 0,16 à 1 minute, à une température allant de 10 à 35°C.
EP85115292A 1984-12-10 1985-12-02 Electrolyte pour le traitement électrochimique des plaques métalliques et procédé de fabrication de plaques métalliques anodisées, de préférence pour l'application comme supports de plaques d'impression Expired - Lifetime EP0184756B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US680029 1984-12-10
US06/680,029 US4578156A (en) 1984-12-10 1984-12-10 Electrolytes for electrochemically treating metal plates

Publications (3)

Publication Number Publication Date
EP0184756A2 EP0184756A2 (fr) 1986-06-18
EP0184756A3 EP0184756A3 (en) 1986-07-23
EP0184756B1 true EP0184756B1 (fr) 1990-03-07

Family

ID=24729363

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85115292A Expired - Lifetime EP0184756B1 (fr) 1984-12-10 1985-12-02 Electrolyte pour le traitement électrochimique des plaques métalliques et procédé de fabrication de plaques métalliques anodisées, de préférence pour l'application comme supports de plaques d'impression

Country Status (4)

Country Link
US (1) US4578156A (fr)
EP (1) EP0184756B1 (fr)
JP (1) JPS61139698A (fr)
DE (1) DE3576369D1 (fr)

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0778280B2 (ja) * 1988-07-28 1995-08-23 株式会社日立製作所 金属の防食表面処理方法
FR2665713A2 (fr) * 1989-12-01 1992-02-14 Rhone Poulenc Chimie Procede de traitement par voie electrochimique d'un materiau sous forme d'oxyde.
US6000121A (en) * 1992-04-30 1999-12-14 International Business Machines Corporation Method for manufacturing an enclosed disk drive
CH685300A5 (de) * 1992-08-05 1995-05-31 Alusuisse Lonza Services Ag Verfahren zur Vorbehandlung von Werkstoffen aus Metallen oder Metallegierungen.
US5368974A (en) * 1993-05-25 1994-11-29 Eastman Kodak Company Lithographic printing plates having a hydrophilic barrier layer comprised of a copolymer of vinylphosphonic acid and acrylamide overlying an aluminum support
BR9407676A (pt) * 1993-09-29 1997-02-04 Hoechst Celanese Corp Processo para melhorar placa de impressao litográfica placa de impressao litográfica e processo para melhorar a capacidade hidrófila de placa de impressao litográfica
DE69512321T2 (de) 1994-06-16 2000-05-11 Kodak Polychrome Graphics Llc Lithographische Druckplatten mit einer oleophilen bilderzeugenden Schicht
US7569285B2 (en) * 1996-10-17 2009-08-04 The Trustees Of Princeton University Enhanced bonding layers on titanium materials
US7815963B2 (en) 1996-10-17 2010-10-19 The Trustees Of Princeton University Enhanced bonding layers on titanium materials
US6328874B1 (en) * 1998-01-05 2001-12-11 Mcdonnell Douglas Corporation Anodically formed intrinsically conductive polymer-aluminum oxide composite as a coating on aluminum
DE19809802A1 (de) * 1998-03-09 1999-09-16 Binder Hans Verfahren zur Oberflächenbehandlung von Aluminium oder dergleichen
DE19912897A1 (de) * 1999-03-23 2000-09-28 Daimler Chrysler Ag Katalysator und Verfahren zur Herstellung eines Katalysators
US20060194008A1 (en) * 1999-09-22 2006-08-31 Princeton University Devices with multiple surface functionality
DE10022074A1 (de) * 2000-05-06 2001-11-08 Henkel Kgaa Elektrochemisch erzeugte Schichten zum Korrosionsschutz oder als Haftgrund
GB0117683D0 (en) * 2001-07-20 2001-09-12 Alcan Int Ltd Aluminium alloy sheet with roughened surface
JP4417106B2 (ja) * 2001-08-14 2010-02-17 ケロナイト・インターナショナル・リミテッド マグネシウム陽極酸化システム及び方法
US7820300B2 (en) * 2001-10-02 2010-10-26 Henkel Ag & Co. Kgaa Article of manufacture and process for anodically coating an aluminum substrate with ceramic oxides prior to organic or inorganic coating
US6916414B2 (en) 2001-10-02 2005-07-12 Henkel Kommanditgesellschaft Auf Aktien Light metal anodization
US7452454B2 (en) * 2001-10-02 2008-11-18 Henkel Kgaa Anodized coating over aluminum and aluminum alloy coated substrates
US7569132B2 (en) * 2001-10-02 2009-08-04 Henkel Kgaa Process for anodically coating an aluminum substrate with ceramic oxides prior to polytetrafluoroethylene or silicone coating
US7578921B2 (en) 2001-10-02 2009-08-25 Henkel Kgaa Process for anodically coating aluminum and/or titanium with ceramic oxides
CN100585024C (zh) * 2002-09-09 2010-01-27 克罗莱国际有限公司 镁及其合金的表面处理
US7235165B2 (en) * 2004-04-02 2007-06-26 Richard Lacey Electroplating solution and method for electroplating
US9701177B2 (en) 2009-04-02 2017-07-11 Henkel Ag & Co. Kgaa Ceramic coated automotive heat exchanger components
WO2013033810A1 (fr) * 2011-09-08 2013-03-14 Day4 Energy Inc. Formation d'une couche d'oxyde sur une surface conductrice plate
CN106320912B (zh) * 2016-08-30 2018-06-29 福建省邦尚环保科技有限公司 抗菌铝制门及其制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0048909A1 (fr) * 1980-09-26 1982-04-07 Hoechst Celanese Corporation Procédé pour l'oxydation anodique d'aluminium et son utilisation comme support d'une plaque d'impression

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3756826A (en) * 1971-11-15 1973-09-04 Aluminium Co Ating thereto treatment of aluminum preparatory to application of photosensitive co
JPS5789497A (en) * 1980-09-26 1982-06-03 Hoechst Co American Anodic oxidation of plate like, sheet like or strip like material made of aluminum or aluminum alloy
US4383897A (en) * 1980-09-26 1983-05-17 American Hoechst Corporation Electrochemically treated metal plates
DE3305354A1 (de) * 1983-02-17 1984-08-23 American Hoechst Corp., Somerville, N.J. Verfahren zur anodischen oxidation von aluminium mit gepulstem strom und dessen verwendung als druckplatten-traegermaterial

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0048909A1 (fr) * 1980-09-26 1982-04-07 Hoechst Celanese Corporation Procédé pour l'oxydation anodique d'aluminium et son utilisation comme support d'une plaque d'impression
EP0050216A2 (fr) * 1980-09-26 1982-04-28 American Hoechst Corporation Procédé pour l'oxydation anodique d'aluminium et son utilisation comme support pour planches d'imprimerie

Also Published As

Publication number Publication date
JPS61139698A (ja) 1986-06-26
DE3576369D1 (de) 1990-04-12
US4578156A (en) 1986-03-25
EP0184756A2 (fr) 1986-06-18
EP0184756A3 (en) 1986-07-23

Similar Documents

Publication Publication Date Title
EP0184756B1 (fr) Electrolyte pour le traitement électrochimique des plaques métalliques et procédé de fabrication de plaques métalliques anodisées, de préférence pour l'application comme supports de plaques d'impression
EP0154200B1 (fr) Procédé pour le traitement postérieur hydrophilisant en deux étapes de couches d'oxyde d'aluminium avec solutions aqueuses et leur utilisation pour la fabrication de supports pour plaques d'impression offset
EP0121880B1 (fr) Procédé en deux pas pour la préparation de matériaux anodisés d'aluminium en forme plane et leur utilisation dans la fabrication de planches à imprimer offset
EP0292801B1 (fr) Procédé de grainage électrochimique de l'aluminium pour supports pour plaques d'impression
EP0167751B1 (fr) Procédé de traitement de surfaces d'aluminium
DE3030815C2 (de) Elektrolytisches Körnungsverfahren
EP0105170B1 (fr) Procédé de posttraitement de couches d'oxyde d'aluminium avec des solutions aqueuses contenant du silicate alcalin et son application dans la fabrication des supports pour plaques d'impression
EP0089510B1 (fr) Matériau à base d'aluminium avec une couche superficielle hydrophile, un procédé pour sa préparation et son utilisation comme support pour des plaques d'impression lithographiques
DE4001466A1 (de) Verfahren zur elektrochemischen aufrauhung von aluminium fuer druckplattentraeger
EP0048909B1 (fr) Procédé pour l'oxydation anodique d'aluminium et son utilisation comme support d'une plaque d'impression
EP0093960B1 (fr) Procédé de grainage électrochimique de l'aluminium pour des supports de plaques d'impression
EP0162283B1 (fr) Procédé de grainage électrochimique d'aluminium pour supports de plaques d'impression dans un électrolyte composite aqueux
EP0268790B1 (fr) Procédé pour la modification par enlèvement de supports en aluminium ou en alliage de l'aluminium décapés en plusieurs étapes et utilisation de ceux-ci pour la fabrication de plaques offset
EP0162281B1 (fr) Procédé de grainage électrochimique d'aluminium pour supports de plaques d'impression dans un électrolyte composite aqueux
EP0151304B1 (fr) Procédé pour rendre rugueux électrolytiquement des plaques d'impression en aluminium dans un électrolyte composite aqueux
DE69935488T2 (de) Herstellung eines Trägers für Flachdruckplatte
DE3222967A1 (de) Verfahren zur abtragenden modifizierung von elektrochemisch aufgerauhten traegermaterialien aus aluminium nd deren verwendung bei der herstellung von offsetdruckplatten
EP0139111B1 (fr) Procédé d'oxidation anodique en deux étapes des matériaux de support en aluminium pour plaques d'impression offset
EP0089509B1 (fr) Procédé pour déposer par voie électrophorétique des revêtements sensibles aux rayonnements sur des supports métalliques et utilisation du matériau revêtu comme plaque d'impression lithographique
EP0082452B1 (fr) Procédé de grenage électrochimique d'aluminium avec un courant alternatif triphasé et son utilisation dans la fabrication des plaques à imprimer
DE3910450C2 (de) Verfahren zur Herstellung eines Druckplattenträgers aus Aluminium
EP0194429B1 (fr) Procédé de grainage électrochimique de l'aluminium pour substrats de plaques d'impression
EP0141056B1 (fr) Procédé d'oxydation anodique en une étape des matériaux supports en aluminium pour plaques d'impression offset
DE3217870A1 (de) Anodisierter (anodisch oxydierter) traeger fuer eine strahlungsempfindliche zusammensetzung
EP0536531B1 (fr) Procédé de grainage d'aluminium ou d'alliages d'aluminium pour supports plaques d'impression et une plaque d'impression

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): DE FR GB

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): DE FR GB

17P Request for examination filed

Effective date: 19861108

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: HOECHST CELANESE CORPORATION

17Q First examination report despatched

Effective date: 19880202

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB

REF Corresponds to:

Ref document number: 3576369

Country of ref document: DE

Date of ref document: 19900412

ET Fr: translation filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19911115

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19921118

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19930213

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19930831

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19931202

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19931202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19940901