EP1002644B1 - Production d'un support pour plaque d'impression lithographique - Google Patents

Production d'un support pour plaque d'impression lithographique Download PDF

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Publication number
EP1002644B1
EP1002644B1 EP19990203617 EP99203617A EP1002644B1 EP 1002644 B1 EP1002644 B1 EP 1002644B1 EP 19990203617 EP19990203617 EP 19990203617 EP 99203617 A EP99203617 A EP 99203617A EP 1002644 B1 EP1002644 B1 EP 1002644B1
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EP
European Patent Office
Prior art keywords
treatment
substrate
aluminium
salt
aqueous solution
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
EP19990203617
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German (de)
English (en)
Other versions
EP1002644A3 (fr
EP1002644A2 (fr
Inventor
Tu Vinh Chau
Felton Rudolph Mayers
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.)
Agfa Gevaert NV
Original Assignee
Agfa Graphics NV
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
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Publication of EP1002644A3 publication Critical patent/EP1002644A3/fr
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Publication of EP1002644B1 publication Critical patent/EP1002644B1/fr
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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
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/20—Electrolytic after-treatment
    • 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
    • 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
    • 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
    • C25D11/12—Anodising more than once, e.g. in different baths

Definitions

  • This invention relates to a method for the production of a metallic support for use as a substrate for a lithographic printing plate. More specifically, the invention provides a method for the surface treatment of a metallic sheet, most particularly an aluminium sheet, whereby a substrate having particularly favourable lithographic properties may be obtained.
  • aluminium substrates intended for use as support materials for lithographic printing plates and their precursors have generally been subjected to surface treatments prior to application of a light sensitive coating material. These treatments serve to improve the lithographic properties of the aluminium, in particular, its hydrophilicity. This is important during printing operations, since the basis of lithography is the ability of the lithographic plate to accept ink in image areas whilst rejecting ink and accepting water in background (non-image) areas, so that the printed image remains free from dirt and other contamination in said background areas.
  • the light-sensitive coating of a lithographic printing plate precursor is imagewise exposed to radiation in order to change the solubility characteristics of the coating in the radiation-struck areas. The soluble areas are subsequently dissolved away by treatment with a developing solution, to expose the aluminium surface which must be capable of rejecting ink and accepting water.
  • a typical surface treatment comprises an initial graining treatment, wherein the aluminium surface is roughened by either mechanical or electrochemical means, and a subsequent anodising treatment, by means of which a layer of aluminium oxide is formed on the surface of the aluminium.
  • Anodising treatments may, for example, be carried out by passing a grained aluminium web through a bath of a suitable anodising acid, such as sulphuric or phosphoric acid, or a mixture thereof, whilst an electric current flows through the anodising bath and the web serves as the anode.
  • post-anodic dip - is generally applied in order to improve specific lithographic printing properties of the substrate, such as clean up of background areas, coating adhesion or corrosion resistance, and will typically involve passing the aluminium through a solution, often an aqueous solution, of the chosen reagent.
  • aqueous solutions containing, for example, sodium carbonate or bicarbonate, poly(acrylic acid) or various aqueous-soluble copolymers.
  • the present invention seeks to provide a means whereby the costly and time-consuming substrate treatment steps involved in the preparation of suitable aluminium support materials for use in the preparation of lithographic printing plate precursors may be reduced in number and simplified, thereby facilitating substantial cost savings.
  • US-A-4,554,216 discloses a two-stage anodic oxidation process for aluminium, which is employed as a support material for offset-printing plates.
  • the surface of the substrate is treated with an aqueous electrolyte which comprises dissolved oxoanions of boron, vanadium, molybdenum, tingsten and/or carbon, at a voltage between about 10 and 100 V.
  • WO-A-92/22688 discloses a method for electrochemically roughening an aluminium metal sheet for use as a lithographic plate support by subjecting the sheet in an electrolyte to an alternating current treatment.
  • the treatment is performed in the presence of at least one added component, present in the sheet or in the electrolyte, selected from Hg, Ga, In, Sn, Bi, Tl, Cd, Pb, Zn and Sb.
  • GB-A-2,129,442 discloses a surface treatment method, which comprises forming a white or grayish white substance in micropores of the annodically oxidized film of aluminium or aluminium alloy.
  • This method comprises the step wherein the article is dipped in a solution containing one or more salts selected from calcium salts, magnesium salts, barium salts, strontium salts, zinc salts, lead salts, titanium salts and aluminium salts or electrolyzed with this solution.
  • the electrolysis may be carried out according to direct-current electrolysis, alternating-current electrolysis or electrolysis by a current with a waveform having the same effect as a direct-current or alternating-current.
  • a process for the manufacture of a support for a lithographic printing plate precursor comprising at least the steps of:
  • Said metallic substrate may comprise any conducting metallic substrate but, most preferably, it comprises aluminium or an aluminium alloy containing small amounts of, for example, manganese, nickel, cobalt, zinc, iron, silicon or zirconium.
  • Said substrate is generally provided in the form of a continuous web or roll of metal or metal alloy.
  • said substrate is subjected to a degreasing treatment prior to said treatment with an aqueous solution of a salt of Zr or Hf.
  • Said degreasing treatment is most conveniently carried out by means of an aqueous alkaline solution.
  • said treatment involves passing said substrate through a bath containing a 5-20% w/v solution of, for example, sodium or potassium hydroxide.
  • said substrate is rinsed with water prior to further treatment.
  • Said treatment of said surface or surfaces with an aqueous solution comprising a salt of Zr or Hf is preferably carried out by immersing said substrate in an aqueous solution, preferably containing from 0.001% to 5.0% (w/w) (more preferably from 0.01% to 1.0%) of said salt at a preferred temperature of from 5° to 80°C (more preferably from 15° to 40°C) for a preferred dwell time of from 1 second to 60 minutes (more preferably from 15 seconds to 5 minutes) at a pH of between 0 and 13 (preferably from 1 to 5, and most preferably in the region of 3).
  • Said aqueous solution also preferably contains aluminium ions in an amount of from 0.1 to 50,000 ppm; said aluminium ions may be added to said aqueous solution in the form of any convenient aluminium salt or, in the case of an aluminium substrate, may be present as a result of dissolution from said substrate.
  • Suitable salts used for the said treatment are salts of zirconium, or hafnium.
  • Said salts may include the metal either as the cation, for example in halide, sulphate or nitrate salts, or as part of a complexed anion.
  • Particularly favourable results are achieved with salts of zirconium or hafnium, such as hafnium sulphate, zirconium phosphate, hafnium acetate, and zirconium fluoride.
  • the hafnium, or zirconium salt comprises a salt wherein the metal is present in a metal-complex anion, such as a fluorozirconate anion.
  • the alkali metal fluorozirconates particularly potassium hexafluorozirconate.
  • additives may be incorporated in said aqueous solution containing a Zr or Hf salt.
  • polymers or copolymers of organic acids may be employed for this purpose, with particularly favourable results being achieved with poly(acrylic acid) or the copolymer of acrylic acid with vinyl phosphonic acid.
  • Said materials may be added in an amount of from 0.001% to 5.0% (w/w) (preferably from 0.01% to 1.0%) to the treatment bath.
  • the application of the constant voltage or constant current is preferably realised by applying a constant d.c., pulsed d.c., a.c. (sine and square waveforms), biased a.c. or half wave 1-6 phases rectified a.c. voltage of from 0.1 to 1000 V (preferably from 1 V to 100 V) across the treatment bath, using the substrate as one electrode and another electrical conductor, such as platinum, aluminium, carbon, stainless steel or mild steel as the other electrode.
  • the aluminium substrate may form the cathode and the other electrical conductor may provide the anode; preferably, however, the aluminium substrate forms the anode, with the other electrical conductor providing the cathode.
  • a surface film develops on said substrate, said film having a thickness of from 0.001 to 100 ⁇ m.
  • said surface film may be produced with a textured surface finish.
  • said substrate may be subjected to a graining treatment prior to said treatment with an aqueous solution of a salt of Zr or Hf.
  • Said graining treatment may involve mechanical graining, wherein the surface of the substrate is subjected to mechanical forces which may, for example, be achieved by the use of a slurry of very small metal balls or via brush graining techniques.
  • electrochemical graining may be employed; said technique comprises passing a substrate through a solution of a mineral or organic acid, or a mixture thereof, such as a mixture of hydrochloric and acetic acids, whilst applying an electric current to the acid solution.
  • Typical graining conditions would involve the use of a bath of aqueous hydrochloric acid at a concentration of from 1-10 g/l and a temperature of 5-50°C, with a dwell time of from 1-60 seconds and an applied potential of from 1-40 V. The grained substrate is then rinsed with water prior to further processing.
  • said grained substrate Following electrochemical graining, said grained substrate would be subjected to a desmutting treatment in order to remove byproducts formed during the course of said electrograining treatment, and deposited on the surface of the substrate.
  • a desmutting treatment in order to remove byproducts formed during the course of said electrograining treatment, and deposited on the surface of the substrate.
  • the process involves treatment of the grained substrate with an aqueous acid or alkali according to the methods well known in the art.
  • the substrate is rinsed with water following desmutting.
  • the support provided by the method of the present invention may subsequently be coated with a light-sensitive coating to give a lithographic printing plate precursor.
  • coatings of the types well known to those skilled in the art may be applied for this purpose, for example, positive-working coatings incorporating quinone diazide derivatives, negative-working coatings incorporating diazo or azide resins or photocrosslinkable resins or silver halide based coatings.
  • the coatings may be applied by any of the standard coating techniques known to the skilled person, such as curtain coating, dip coating, meniscus coating, reverse roll coating, and the like.
  • the thus-obtained lithographic printing plate precursor may then be imagewise exposed and the non-image areas can be developed away to provide a lithographic printing plate which is subsequently used on a printing press to produce copies.
  • Lithographic printing plates produced from aluminium supports obtained by the method of the present invention show good abrasion resistance, corrosion resistance, staining resistance and scumming resistance, both on plate development and on press.
  • the surface film produced by the treatment according to the method of the present invention shows excellent coating adhesion in the image areas. Additionally, the plate exhibits very good exposure latitude and solvent resistance.
  • a salt of this type may be incorporated in an anodising bath typically containing mineral acids such as sulphuric, phosphoric, nitric, hydrofluoric or chromic acids, or organic acids such as oxalic, tartaric, citric, acetic or oleic acids, or mixtures of these acids, thereby providing a support material which shows the advantageous properties previously discussed when incorporated in a lithographic printing plate.
  • mineral acids such as sulphuric, phosphoric, nitric, hydrofluoric or chromic acids
  • organic acids such as oxalic, tartaric, citric, acetic or oleic acids, or mixtures of these acids, thereby providing a support material which shows the advantageous properties previously discussed when incorporated in a lithographic printing plate.
  • further additions of materials such as polymers or copolymers of organic acids, typically poly(acrylic acid) or the copolymer of acrylic acid with vinylphosphonic acid, may also be incorporated in the said ano
  • the inventors have found that the same advantageous properties are also evident when conventionally grained and anodised aluminium substrate is subjected to the said electrochemical treatment in a solution incorporating a salt of zirconium or hafnium, optionally in the presence of further additives, such as polymers or copolymers of organic acids, as previously exemplified.
  • Such a process does not, however, provide all the benefits of reduced processing as previously described, although dwell time is substantially reduced when compared with a standard immersion treatment.
  • the resulting substrate shows improved properties when compared with a conventionally grained and anodised substrate which has been subjected to a prior art post-anodic dip treatment.
  • a conventionally degreased, grained and desmutted aluminium substrate was immersed for 120 seconds in a bath fitted with a carbon electrode, and containing an aqueous solution of potassium hexafluorozirconate (5 g/l) at room temperature.
  • a constant d.c. voltage of 15 V was applied across the carbon electrode and the aluminium electrode which was formed by the aluminium substrate, the carbon electrode serving as the cathode and the aluminium electrode as the anode.
  • the resulting substrate was rinsed with water and coated with a solution of a naphthoquinone diazide photosensitive resin and a cresol novolak support resin in 2-methoxypropanol to produce a light-sensitive coating layer, and the coated substrate was baked at 130oC for 5 minutes.
  • the resulting lithographic printing plate precursor was imagewise exposed to UV light at 100-300 mJ/cm 2 and the non-image areas were developed away with an aqueous alkaline developer solution by immersion for 30 seconds at 20°C.
  • the resulting lithographic printing plate was rinsed with water and dried in a stream of cool air and subsequently produced 250,000 excellent quality copies on a Drent Web Offset press. The plate showed excellent resistance to abrasion, corrosion and staining/scumming, both during development and on press.
  • a conventionally degreased aluminium substrate was immersed for 10 seconds in a bath fitted with a carbon electrode, and containing an aqueous solution of potassium hexafluorozirconate (5 g/l) at room temperature.
  • a constant d.c. voltage of 15 V was applied across the carbon electrode and the aluminium electrode which was formed by the aluminium substrate, the carbon electrode serving as the cathode and the aluminium electrode as the anode.
  • the resulting substrate was coated, baked, exposed and developed in exactly the same manner as described for Example 1 to provide a lithographic printing plate which produced 250,000 excellent quality copies on a Drent Web Offset press.
  • the plate showed excellent resistance to abrasion, corrosion and staining/scumming, both during development and on press.
  • a conventionally degreased, grained, desmutted and anodised aluminium substrate was immersed for 5 seconds in a bath fitted with a carbon electrode, and containing an aqueous solution of potassium hexafluorozirconate (5 g/l) at room temperature.
  • An a.c. voltage of 15 V was applied across the carbon electrode and the aluminium electrode which was formed by the aluminium substrate, the carbon electrode serving as the cathode and the aluminium electrode as the anode.
  • the resulting substrate was coated, baked, exposed and developed in exactly the same manner as described for Example 1 to provide a lithographic printing plate which produced 250,000 excellent quality copies on a Drent Web Offset press.
  • the plate showed excellent resistance to abrasion, corrosion and staining/scumming, both during development and on press.
  • a conventionally degreased, grained and desmutted aluminium substrate was immersed for 120 seconds in a bath fitted with a carbon electrode, and containing an aqueous solution of zirconium sulphate (5 g/l) at room temperature.
  • a rectified a.c. voltage of 15 V was applied across the carbon electrode and the aluminium electrode which was formed by the aluminium substrate, the carbon electrode serving as the cathode and the aluminium electrode as the anode.
  • the resulting substrate was coated, baked, exposed and developed in exactly the same manner as described for Example 1 to provide a lithographic printing plate which produced 250,000 excellent quality copies on a Drent Web Offset press.
  • the plate showed excellent resistance to abrasion, corrosion, and staining/scumming, both during development and on press.

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

Claims (24)

  1. Procédé pour la fabrication d'un support pour un précurseur de plaque d'impression lithographique, ledit procédé comprenant au moins les étapes consistant à :
    (a) procurer un substrat métallique ;
    (b) traiter au moins une surface dudit substrat avec une solution aqueuse comprenant un sel tout en appliquant une tension constante ou un courant constant,
    caractérisé en ce que ledit sel comprend un sel de zirconium ou un sel de hafnium.
  2. Procédé tel que défini à la revendication 5, dans lequel ledit substrat métallique comprend de l'aluminium ou un alliage d'aluminium contenant de petites quantités d'au moins un membre choisi parmi le groupe comprenant le manganèse, le nickel, le cobalt, le zinc, le fer, le silicium ou le zirconium.
  3. Procédé tel que défini à la revendication 1 ou 2, dans lequel ledit sel comprend le sulfate, le phosphate, le nitrate, l'acétate, le fluorure ou le chlorure de zirconium ou de hafnium.
  4. Procédé tel que défini à la revendication 1 ou 2, dans lequel ledit sel comprend un anion complexé de zirconium ou de hafnium
  5. Procédé tel que défini à la revendication 4, dans lequel ledit sel comprend un fluorozirconate de métal alcalin.
  6. Procédé tel que défini à la revendication 5, dans lequel ledit fluorozirconate de métal alcalin comprend de l'hexafluorozirconate de potassium.
  7. Procédé tel que défini dans l'une quelconque des revendications précédentes, dans lequel ladite solution aqueuse englobe en outre un polymère ou un copolymère d'un acide organique.
  8. Procédé tel que défini à la revendication 7, dans lequel ledit polymère ou ledit copolymère comprend de l'acide polyacrylique ou un copolymère d'acide acrylique avec de l'acide vinylphosphonique.
  9. Procédé tel que défini dans l'une quelconque des revendications précédentes, dans lequel ladite solution aqueuse contient des ions aluminium en une quantité de 0,1 à 50.000 ppm.
  10. Procédé tel que défini dans l'une quelconque des revendications précédentes, dans lequel ladite solution aqueuse contient ledit sel à concurrence de 0,001 % à 5,0 % (en poids/poids).
  11. Procédé tel que défini dans l'une quelconque des revendications précédentes, dans lequel ledit traitement de l'étape (b) est mis en oeuvre à une température de 5° à 80°c.
  12. Procédé tel que défini dans l'une quelconque des revendications précédentes, dans lequel ledit traitement de l'étape (b) est mis en oeuvre pendant un laps de temps de séjour de 15 secondes à 5 minutes.
  13. Procédé tel que défini dans l'une quelconque des revendications précédentes, dans lequel ledit traitement de l'étape (b) est mis en oeuvre à un pH de 1 à 5.
  14. Procédé tel que défini dans l'une quelconque des revendications précédentes, dans lequel ladite application d'une tension constante ou de courant constant est mise en oeuvre en appliquant une tension en courant continu constant, une tension en courant continu pulsé, une tension courant alternatif (forme d'onde sinusoïdale ou carrée), une tension en courant alternatif polarisé ou encore une tension en courant alternatif monophasé à hexaphasé redressé à une alternance de 0,1 à 1000 V à travers le bain de traitement.
  15. Procédé tel que défini à la revendication 14, dans lequel ledit courant alternatif est appliqué à une fréquence de 30 à 70 Hz.
  16. Procédé tel que défini à la revendication 14 ou 15, dans lequel le substrat comprend une électrode, l'autre électrode comprenant du platine, de l'aluminium, de carbone, de l'acier inoxydable ou de l'acier doux.
  17. Procédé tel que défini à la revendication 16, dans lequel ledit substrat comprend de l'aluminium et forme l'anode.
  18. Procédé tel que défini dans l'une quelconque des revendications précédentes, dans lequel ledit substrat est soumis à un traitement de dégraissage avant ledit traitement de l'étape (b).
  19. Procédé tel que défini dans la revendication 18, dans lequel ledit traitement de dégraissage est mis en oeuvre au moyen d'une solution alcaline aqueuse.
  20. Procédé tel que défini dans l'une quelconque des revendications précédentes, dans lequel ledit substrat est soumis à un traitement de grainage avant ledit traitement de l'étape (b).
  21. Procédé tel que défini à la revendication 20, dans lequel ledit substrat est soumis à un traitement de décapage après ledit traitement de grainage.
  22. Procédé tel que défini dans l'une quelconque des revendications précédentes, dans lequel ledit procédé comprend en outre l'étape (c) après l'étape (b) consistant à :
    (c) appliquer un revêtement photosensible sur la surface traitée ou sur les surfaces traitées dudit support.
  23. Procédé tel que défini dans l'une quelconque des revendications précédentes, dans lequel ledit traitement de l'étape (b) est mis en oeuvre dans un bain d'anodisation comprenant ladite solution aqueuse qui comprend en outre un acide minéral ou un acide organique ou encore un mélange desdits acides.
  24. Procédé tel que défini dans l'une quelconque des revendications précédentes, dans lequel ledit traitement de l'étape (b) est mis en oeuvre sur un substrat grainé et anodisé comprenant de l'aluminium, ou un de ses alliages, comme défini à la revendications 2.
EP19990203617 1998-11-16 1999-11-01 Production d'un support pour plaque d'impression lithographique Expired - Lifetime EP1002644B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9825043 1998-11-16
GBGB9825043.4A GB9825043D0 (en) 1998-11-16 1998-11-16 Production of support for lithographic printing plate

Publications (3)

Publication Number Publication Date
EP1002644A2 EP1002644A2 (fr) 2000-05-24
EP1002644A3 EP1002644A3 (fr) 2004-01-14
EP1002644B1 true EP1002644B1 (fr) 2007-03-14

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EP (1) EP1002644B1 (fr)
JP (1) JP2000147751A (fr)
DE (1) DE69935488T2 (fr)
GB (2) GB9825043D0 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101871117A (zh) * 2010-06-30 2010-10-27 湖南大学 一种p型半导体纳米材料CuxSe/TiO2纳米管阵列及其制备方法
CN101871117B (zh) * 2010-06-30 2011-11-23 湖南大学 一种p型半导体纳米材料CuxSe/TiO2纳米管阵列制备方法

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DE69935488D1 (de) 2007-04-26
EP1002644A3 (fr) 2004-01-14
EP1002644A2 (fr) 2000-05-24
JP2000147751A (ja) 2000-05-26
GB2343681A (en) 2000-05-17
DE69935488T2 (de) 2007-11-29
GB9925555D0 (en) 1999-12-29

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