EP0082453B1 - Procédé de traitement anodique de l'aluminium et son application comme support pour plaques d'impression - Google Patents

Procédé de traitement anodique de l'aluminium et son application comme support pour plaques d'impression Download PDF

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Publication number
EP0082453B1
EP0082453B1 EP19820111544 EP82111544A EP0082453B1 EP 0082453 B1 EP0082453 B1 EP 0082453B1 EP 19820111544 EP19820111544 EP 19820111544 EP 82111544 A EP82111544 A EP 82111544A EP 0082453 B1 EP0082453 B1 EP 0082453B1
Authority
EP
European Patent Office
Prior art keywords
acid
electrolyte
sulfonic acid
poly
polymeric polybasic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP19820111544
Other languages
German (de)
English (en)
Other versions
EP0082453A1 (fr
Inventor
Thomas Nicolas Gillich
John E. Walls
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
American Hoechst 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
Priority claimed from US06/333,586 external-priority patent/US4388156A/en
Priority claimed from US06/333,585 external-priority patent/US4381226A/en
Application filed by American Hoechst Corp filed Critical American Hoechst Corp
Publication of EP0082453A1 publication Critical patent/EP0082453A1/fr
Application granted granted Critical
Publication of EP0082453B1 publication Critical patent/EP0082453B1/fr
Expired legal-status Critical Current

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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
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/02—Electrolytic coating other than with metals with organic materials
    • 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
    • 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
    • C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids

Definitions

  • the present invention relates to a process for the anodic treatment of aluminum in an electrolyte containing an organic phosphonic, sulfonic or carboxylic acid and the use of the process product as a printing plate support material.
  • Surfaces created in such a method are also suitable for capacitors, dielectric purposes, and other applications where a barrier layer is useful.
  • Anodized layers produced with phosphoric acid have many good properties that make them suitable for use in offset printing.
  • the film produced by anodic oxidation is rather “soft" and has a relatively low abrasion resistance; this is a disadvantage when long print runs are required.
  • Anodized layers produced with sulfuric acid are much harder, have a relatively higher abrasion resistance and therefore result in mechanically more resistant offset printing plates, with which long print runs can be achieved. Both methods have found their way into practice, the respective plates are commercially successful in different sub-areas.
  • the sulfuric acid process is also easier to use for the production of thicker anodized layers than the phosphoric acid process which, because of the greater solubility of the film produced by anodic oxidation in the electrolyte, has a tendency to self- limit shows.
  • the sulfuric acid process also has certain disadvantages, so there are layers which are not always entirely satisfactory for offset printing substrates, since they tend to not delineate oleophilic and hydrophilic areas sharply enough, so that often with these layers, except for the thinnest, processes must be applied by the z. B. the color acceptance in the non-image areas is prevented.
  • This necessary treatment of the anodically produced layer can occasionally be problematic when, for example, it is necessary to produce presensitized offset printing plates in which the adhesion of the radiation-sensitive coating to the support is of primary importance during and after the development of the exposed layer. If such treatments which modify the surface of the carrier material are carried out on the layer produced by anodic oxidation, it is important to find a compromise between achieving sufficient hydrophilicity in the non-image areas and at the same time satisfactory behavior of the image areas. These treatments can thus give results which are desirable for offset printing, and they are known for both the planographic printing plates anodized with phosphoric acid and for the anodized with sulfuric acid and are customary in practice.
  • the older, non-prepublished EP-A 0 048 909 and 0 050 216 describe processes for the anodic oxidation of plate, sheet or strip material made of aluminum or its alloys, which are contained in an aqueous electrolyte containing at least one polybasic organic acid be performed. If necessary, mechanical, chemical and / or electrochemical roughening can take place before the oxidation.
  • the polybasic organic acids include monomeric or polymeric phosphonic, sulfonic or organic carboxylic acids such as phytic acid, tridecyl-benzoisulfonic acid, nitrilotriacetic acid, polyvinylphosphonic acid, polybenzenesulfonic acid or polyacrylic acid.
  • the electrolyte can also contain an inorganic acid such as phosphoric acid.
  • the process products are preferably used as a carrier material in the production of printing plates bearing a radiation-sensitive layer.
  • the invention is based on the process for the anodic treatment of plate, sheet or strip material made of aluminum or its alloys in an electrolyte containing at least one polymeric polybasic organic phosphonic, sulfonic or carboxylic acid, optionally after preceding mechanical, chemical and / or electrochemical roughening.
  • the process according to the invention is then characterized in that the electrolyte in non-aqueous form contains at least one organic solvent with a dipole moment of at least 1.5 Debye.
  • polymer means that a basic molecular unit having at least one acid function occurs several times in the total molecule.
  • the method thus relates to the electrolytic deposition of a layer on aluminum, the aluminum to be treated being switched as the anode and any inert metal (such as lead or steel) or graphite as the cathode.
  • a possibly pulsating direct voltage is then applied to the previously degreased and optionally roughened carrier through a non-aqueous electrolyte.
  • the electrolyte contains at least one of the acids, which is dissolved in the organic solvent or the solvent mixture, which allows a current to flow due to its dipole moment, but which does not undergo any electrochemical reactions at the anode or at the cathode.
  • non-aqueous electrolyte precludes the formation of oxides of aluminum and only allows the formation of a non-oxide layer in the manner of an "organometallic" complex.
  • a layer produced in this way is highly non-porous and very thin. This results in a very good surface on the aluminum base material, through which better adhesion of coatings to the aluminum support material is achieved than with conventionally anodized surfaces.
  • the plates which can be used in the practice of this invention can be made of aluminum or aluminum alloys such as those with more than 98.5% Al and components such as Mn, Fe, Si, Cu, Zn and / or Ti.
  • the aluminum strip or the aluminum plate or foil is first freed of its rolling fat, for which purpose it is treated with a suitable degreasing agent, e.g. B. by putting it in a warm dip with 1,1.1-trichloroethane. Trichloroethene, methylene chloride or perchloroethene or is immersed in an aqueous alkaline solution. Then, if necessary, chemical, electrochemical and / or mechanical roughening, for. B.
  • the surface is then rinsed with water and rinsed with the organic solvent to be used in the electrolysis bath. This is to prevent water from entering the electrolysis bath.
  • the carrier material is then treated electrolytically according to the invention.
  • Polymeric polybasic acids suitable for the process according to the invention are, for example: the condensation product of benzenephosphonic acid and formaldehyde (polybenzenephosphonic acid), alginic acid, hydrolyzed copolymers of methylvinyl ether and maleic anhydride, copolymers of methylvinyl ether and maleic acid, polyvinylsulfonic acid, polystyrene sulfonic acid, poly-n-butylbenzene sulfonic acid from Butylbenzenesulfonic acid and formaldehyde) poly-diisopropylbenzenesulfonic acid (condensation product from diisopropyl-benzenesulfonic acid and formaldehyde), polyvinylphosphonic acid, poly-diisopropyl-naphthalenedisulfonic acid (condensation product from diisopropyl-naphthalenedisulfonic acid and formaldehyde), poly
  • Such organic solvents are suitable for the invention which have a dipole moment of at least 1.5, preferably of at least 1.7, including (dipole moment in brackets): formamide (3.22), dimethyl sulfoxide (3.96), aniline (1.53) dimethylformamide (3.82), mono- (2.27), di- (2.81), triethanolamine (3.57) and tetrahydrofuran (1.70).
  • formamide 3.22
  • dimethyl sulfoxide 3.96
  • aniline 1.53 dimethylformamide
  • mono- (2.27 di- (2.81)
  • triethanolamine 3.57
  • tetrahydrofuran (1.70).
  • the values for DMSO and DMF were taken from the CRC Handbook of Chemistry and Physics, CRC Press - Boca Raton (USA), 62nd edition 1981/82, pp. E-60 to E-62, and the other values from the Physikalisch-Chemische Taschenbuch , Academic Publishing House Becker & Erler - Leipzig, 1945,
  • the acid can in principle be present in the non-aqueous solution in an amount of 0.01% to the saturation point, preferably in an amount of 0.8 to 5%.
  • the electrolysis temperature is generally kept at -5 to 60 ° C, in particular at 10 to 40 ° C and preferably at 20 to 30 ° C.
  • the voltage is expediently between 5 and 120 V, preferably between 10 and 60 V and in particular between 20 and 40 V.
  • the electrolysis time should be sufficient to give the carrier a charge of 1 to 150 C / dm 2 , preferably 30 to 90 C / dm 2 and in particular from 40 to 70 C / dm 2 supply.
  • the distance between the cathode and anode is generally 1 to 25 cm, preferably between 3 and 15 cm and in particular between about 4 and 10 cm.
  • a field of application for a material anodically treated by the method according to the invention is in particular its use as a carrier material in the production of printing plates bearing a radiation-sensitive layer.
  • the carrier is coated by the consumer with one of the known radiation-sensitive compositions.
  • An aluminum plate in bright rolled condition is treated for 30 seconds at room temperature in an aqueous NaOH solution.
  • the plate cleaned and chemically roughened in this way, is rinsed well with water and, without drying, is then immediately rinsed with dimethyl sulfoxide (DMSO).
  • DMSO dimethyl sulfoxide
  • the plate is dissolved in a solution of DMSO and 20 g / l of a copolymer of methyl vinyl ether and maleic acid.
  • DMSO dimethyl sulfoxide
  • 3,867,147 containing a polycondensation product of 1 mol of 3-methoxydiphenylamine-4-diazonium sulfate and 1 mol of 4,4'-bis-methoxymethyl-diphenyl ether is described , Phosphoric acid, an epoxy resin and a dye in a solvent mixture of ethylene glycol monomethyl ether, tetrahydrofuran and butyl acetate and spin-dried.
  • the exposure is then carried out under a test negative in such a way that a fully covered step 6 results on the 21-step Stauffer step wedge.
  • the exposed plate is developed and checked for functionality. After inking, the plate shows a very clean background area (non-image areas) that remains clean without any problems.
  • the anodized plate achieves a 25% higher print run.
  • An aluminum plate is mechanically wet-roughened using a known method using abrasive / nylon brushes and then treated in an aqueous NaOH solution for 30 seconds.
  • the roughened plate is rinsed well with water and immediately rinsed thoroughly with formamide.
  • the plate coated with the organic solvent is immersed in a solution containing formamide and 15 g / l polyvinylphosphonic acid.
  • a lead electrode which acts as a cathode at a distance of about 5 cm from the aluminum plate.
  • the aluminum serves as an anode, to which a voltage of 20 V from rectified alternating current is applied for a period of 60 seconds at room temperature.
  • the anodized plate is rinsed well and patted dry.
  • the anodically produced layer When the anodically produced layer is removed, its layer weight is determined to be 90 mg / m 2 .
  • a plate produced in the same way shows a very hydrophilic surface both in the wet and in the dry coloring test.
  • the reaction time in the SnCig test is 127 seconds, the reaction time in the zincate test 187 seconds.

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

Claims (9)

1. Procédé de traitement anodique d'un matériau sous forme de plaques, de feuilles ou de bandes, en aluminium ou en ses alliages, dans un électrolyte contenant au moins un polyacide phosphonique, sulfonique, ou carboxylique organique, polymère, éventuellement après avoir rendu la surface rugueuse par voie mécanique, chimique et/ou électrochimique, caractérisé en ce que l'électrolyte contient sous forme non aqueuse au moins un solvant organique avec un moment dipolaire d'au moins 1,5 Debye.
2. Procédé selon la revendication 1, caractérisé en ce que le solvant organique a un moment dipolaire d'au moins 1,7 Debye.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'électrolyte contient de 0,01 % en poids jusqu'à la saturation du polyacide organique polymère.
4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que l'électrolyte contient de 0,8 à 5 % en poids du polyacide organique polymère.
5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que l'électrolyte contient comme solvant du formamide, du diméthylsul- foxyde, de l'aniline, du diméthylformamide, de la monoéthanolamine, de la diéthanolamine, de la tri-éthanolamine et/ou du tétrahydrofuranne.
6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que l'électrolyte contient comme polyacide phosphonique polymère l'acide polybenzène phosphonique ou l'acide polyvinylphosphonique.
7. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que l'électrolyte contient comme polyacide sulfonique polymère l'acide polyvinylsulfonique, l'acide polystyrène sulfonique, l'acide poly-n-butyl-benzène sulfonique, l'acide poly-diisopropyl-benzène sulfonique, l'acide poly-diisopropyl-naphtalène disulfonique, l'acide poly-décylbenzène sulfonique ou l'acide polynaphtalène sulfonique.
8. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que l'électrolyte contient comme polyacide carboxylique organique polymère, l'acide alginique, un copolymère hydrolysé d'éther méthylvinylique et d'anhydride maléique, un copolymère d'éther méthylvinylique et d'acide maléique, l'acide polyacrylique ou l'acide poly- méthacrylique.
9. Utilisation du procédé selon l'une des revendications 1 à 8, pour la préparation d'un matériau de support de plaques d'impression portant une couche sensible aux radiations.
EP19820111544 1981-12-23 1982-12-13 Procédé de traitement anodique de l'aluminium et son application comme support pour plaques d'impression Expired EP0082453B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US06/333,586 US4388156A (en) 1981-12-23 1981-12-23 Aluminum electrolysis in non-aqueous monomeric organic acid
US06/333,585 US4381226A (en) 1981-12-23 1981-12-23 Electrochemical treatment of aluminum in non-aqueous polymeric polybasic organic acid containing electrolytes
US333586 1981-12-23
US333585 1981-12-23

Publications (2)

Publication Number Publication Date
EP0082453A1 EP0082453A1 (fr) 1983-06-29
EP0082453B1 true EP0082453B1 (fr) 1985-06-26

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Family Applications (1)

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EP19820111544 Expired EP0082453B1 (fr) 1981-12-23 1982-12-13 Procédé de traitement anodique de l'aluminium et son application comme support pour plaques d'impression

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EP (1) EP0082453B1 (fr)
DE (1) DE3264455D1 (fr)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3331993A (en) * 1964-10-21 1967-07-18 Westinghouse Electric Corp Electrolytic capacitor with highly pure titanium electrode and method for making
CH475364A (de) * 1966-09-13 1969-07-15 Minoltacamera Kabushiki Kaisha Verfahren zur anodischen Oxydation von Aluminium bzw. Aluminiumlegierungen
ZA6807938B (fr) * 1967-12-04
US3796644A (en) * 1972-05-03 1974-03-12 Sprague Electric Co Electrolytic formation process for aluminum capacitor electrodes

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EP0082453A1 (fr) 1983-06-29
DE3264455D1 (en) 1985-08-01

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