EP0161608B1 - Verfahren zur Nachbehandlung von Aluminiumoxidschichten mit Phosphoroxo-Anionen enthaltenden wässrigen Lösungen und deren Verwendung bei der Herstellung von Offsetdruckplattenträgern - Google Patents

Verfahren zur Nachbehandlung von Aluminiumoxidschichten mit Phosphoroxo-Anionen enthaltenden wässrigen Lösungen und deren Verwendung bei der Herstellung von Offsetdruckplattenträgern Download PDF

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Publication number
EP0161608B1
EP0161608B1 EP85105492A EP85105492A EP0161608B1 EP 0161608 B1 EP0161608 B1 EP 0161608B1 EP 85105492 A EP85105492 A EP 85105492A EP 85105492 A EP85105492 A EP 85105492A EP 0161608 B1 EP0161608 B1 EP 0161608B1
Authority
EP
European Patent Office
Prior art keywords
acid
layers
aqueous solution
anions
aluminum
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
EP85105492A
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German (de)
English (en)
French (fr)
Other versions
EP0161608A1 (de
Inventor
Ulrich Dr. Dipl.-Chem. Simon
Reiner Beutel
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.)
Hoechst AG
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Hoechst AG
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Publication date
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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41NPRINTING 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
    • B41N3/00Preparing for use and conserving printing surfaces
    • B41N3/03Chemical or electrical pretreatment
    • B41N3/038Treatment with a chromium compound, a silicon compound, a phophorus compound or a compound of a metal of group IVB; Hydrophilic coatings obtained by hydrolysis of organometallic compounds
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02Anodisation
    • C25D11/04Anodisation of aluminium or alloys based thereon
    • C25D11/18After-treatment, e.g. pore-sealing
    • C25D11/24Chemical after-treatment
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S205/00Electrolysis: processes, compositions used therein, and methods of preparing the compositions
    • Y10S205/921Electrolytic coating of printing member, other than selected area coating

Definitions

  • the invention relates to an aftertreatment process for roughened and anodically oxidized aluminum, in particular of support materials for offset printing plates with aqueous solutions containing phosphorus oxo anions.
  • 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 of a template is generated photomechanically.
  • the layer support carries the image points which will guide the color during later printing and at the same time forms the hydrophilic background for the lithographic printing process at the non-image points (non-image points) during later printing.
  • Aluminum is used in particular as the base material for such substrates. It is roughened according to known methods by dry brushing, wet brushing, sandblasting, chemical and / or electrochemical treatment. In order to increase the abrasion resistance, the roughened substrate can also be subjected to an anodization step to build up a thin oxide layer.
  • the carrier materials in particular anodically oxidized carrier materials based on aluminum, are subjected to a further treatment step to improve the layer adhesion, to increase the hydrophilicity and / or to facilitate the developability of the radiation-sensitive layers before the application of a radiation-sensitive layer for example the following methods.
  • the US-A 3 808 000 describes similarly.
  • stage b) phosphoric acid (H 3 P0 4 ), sodium dihydrogen phosphate (NaH 2 P0 4 ), disodium hydrogen phosphate (Na 2 HP0 4 ), trisodium phosphate (Na 3 P0 4 ), phosphorous acid (H 3 P0 3 ), disodium phosphite (Na 2 HPO 3 ), diphosphoric acid (H 4 P 2 0 7 ), sodium pyrophosphate (Na 4 P 2 0 7 ), triphosphoric acid (H5P 3 0 10 ), sodium triphosphate (Na 5 P 3 O 10 ), Polyphosphoric acid (H n + 2 P n 0 3n + 1 ), hexasodium tetrapolyphosphate (Na 6 P 4 0 13 ), hexasodium metaphosphate [Na 6 (P0 3 ) 61 , disodium monofluorophosphate (Na 2 PO 2 F) and potassium
  • DE-A 2 609 577 describes a process for producing sealed anodic oxide thin layers on aluminum and aluminum alloys prior to their coating, the oxide layer being treated in an aqueous solution which contains phosphorus compounds at at least 80.degree.
  • the main phosphorus compounds used are orthophosphoric acid, phosphorous acid and salts of the acids mentioned, and phosphorus compounds of tungsten or molybdic acid.
  • the purpose of the treatment is to prevent hairline cracks in these oxide layers, for example to improve the application of paint.
  • the object of the present invention is to propose a method for the aftertreatment of flat aluminum, which can be carried out in addition to anodic oxidation of the aluminum and leads to a surface on the aluminum oxide thus produced, which in particular meets the practical requirements of a high-performance printing plate described at the outset and already known dipping methods improved in effect.
  • the invention is based on the known process for the production of sheet, film or strip materials based on chemically, mechanically and / or electrochemically roughened and anodically oxidized aluminum or one of its alloys, the aluminum oxide layers of which contain an aqueous solution containing phosphorus oxo anions be treated.
  • the process according to the invention is then characterized in that the aftertreatment of the aluminum oxide layer is not carried out electrolytically by immersion treatment in an aqueous solution containing hexametaphosphate anions.
  • the aqueous solution generally contains 1 to 300 g / l of hexametaphosphate anions, preferably 3 to 150 g / l and in particular 5 to 100 g / l.
  • the aftertreatment is carried out discontinuously or preferably continuously in the modern belt systems.
  • the treatment times are expediently in the range from 0.5 to 120 seconds and the treatment temperatures are from 15 to 80 ° C., in particular from 20 to 75 ° C.
  • the procedure used changes the previously generated surface topography (such as roughness and oxide pores) practically not or only insignificantly, so that the method according to the invention is particularly suitable for the treatment of materials in which the retention of this topography plays a major role, for example for printing plate support materials.
  • Suitable base materials for the material to be treated according to the invention include those made of aluminum or one of its alloys, which have, for example, a content of more than 98.5% by weight of Al and proportions of Si, Fe, Ti, Cu and Zn.
  • the flat aluminum is first mechanically, if necessary after pre-cleaning, (for example by brushing and / or with an abrasive treatment); roughened chemically (e.g. by etching agents) and / or electrochemically (e.g. by alternating current treatment in aqueous acid or salt solutions).
  • the electrochemical roughening is preferably carried out in the process according to the invention, but these aluminum carrier materials can also be roughened mechanically (for example by brushing with wire or nylon brushes and / or with an abrasive treatment) even before the electrochemical stage. All process steps can be carried out discontinuously with plates or foils, but they are preferably carried out continuously with tapes.
  • the process parameters in particular in the case of a continuous process, in the electrochemical roughening stage lie in the following ranges: the temperature of the aqueous electrolyte generally containing 0.3 to 5.0% by weight of acid (s) (also higher in the case of salts) 20 and 60 ° C, the current density between 3 and 200 A / dm 2 , the residence time of a material point to be roughened in the electrolyte between 3 and 100 seconds and the electrolyte flow rate on the surface of the material to be roughened between 5 and 100 cm / sec; in the batchwise process, the required current densities tend to be in the lower part and the dwell times are in the upper part of the ranges specified, and the flow of the electrolyte can also be dispensed with.
  • alternating current of a frequency of 50 to 60 Hz is usually used as the type of current, but modified types of current such as alternating current with different amplitudes of the current strength for the anode and cathode current, lower frequencies, current interruptions or superimposition of two currents of different frequency and waveform are also possible.
  • the average roughness depth R 2 of the roughened surface is in the range from 1 to 15 ⁇ m, in particular from 1.5 to 8.0 ⁇ m.
  • the aqueous electrolyte contains acid (s), in particular HCl and / or HN0 3 , aluminum ions in the form of aluminum salts, in particular Al (N0 3 ) 3 and / or AICI 3 can also be added to it; the addition of certain other acids and salts such as boric acid or borates or of corrosion inhibitors such as amines is also known.
  • the pre-cleaning includes, for example, treatment with aqueous NaOH solution with or without Degreasing agents and / or complexing agents, trichlorethylene, acetone, methanol or other commercially available aluminum stains.
  • the roughening or, in the case of several roughening stages, also between the individual stages, an abrasive treatment can additionally be carried out, in particular a maximum of 2 g / m 2 being removed (up to 5 g / m 2 between the stages);
  • aqueous solutions of alkali metal hydroxide or aqueous solutions of alkaline salts or aqueous acid solutions based on HN0 3 , H 2 SO 4 or H 3 PO 4 are used as abrasive solutions.
  • non-electrochemical treatments are also known which essentially only have a rinsing and / or cleaning effect and, for example, for removing deposits formed during roughening ("Schmant") or simply for Serve removal of electrolyte residues; For example, dilute aqueous alkali hydroxide solutions or water are used for these purposes.
  • anodic oxidation of the aluminum follows in a further process step, for example to improve the abrasion and adhesion properties of the surface of the carrier material.
  • the usual electrolytes such as H 2 S0 4 , H 3 P0 4 , H 2 C 2 0 4 , amidosulfonic acid, sulfosuccinic acid, sulfosalicylic acid or mixtures thereof can be used for anodic oxidation; in particular, H 2 S0 4 and H 3 P0 4 are used alone, in a mixture and / or in a multi-stage anodizing process; an aqueous solution containing H 2 S0 4 and A1 3 + ions is particularly preferably used.
  • the oxide layer weights are generally in particular between 1 and 8 g / m 2 (corresponding to about 0.3 to 2.5 ⁇ m layer thickness).
  • the materials produced according to the invention are preferably 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 imagewise surface from which printing can take place.
  • photoconductive layers such as z. B. in DE-C 1 117 391, 1 522 497, 1 572 312, 2 322 046 and 2 322 047 are described, applied to the carrier materials produced according to the invention, whereby highly light-sensitive, electrophotographic printing plates are formed.
  • coated offset printing plates obtained from the carrier materials produced 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, preferably an aqueous developer solution.
  • offset printing plates whose base support materials have been post-treated by the two-stage process according to the invention, are distinguished in particular by a lower tendency to form color fog compared to those plates in which the same base material has been post-treated with other aqueous solutions containing phosphorus oxo anions (see the following comparative experiments).
  • This special effect of the hexametaphosphate anions in a pure immersion treatment was not predictable, since the whole group of anions shows a similar effect in the electrochemical treatment.
  • An aluminum strip is electrochemically roughened in an aqueous solution containing 1.4% of HN0 3 and 6% of Al (N0 3 ) 3 using alternating current (115 A / dm 2 at 35 ° C.) and in an aqueous H 2 S0 4 and Al 3 + - ion containing solution anodized with direct current.
  • the oxide layer which has a layer weight of approximately 2.5 g / m 2 , is immersed for 15 seconds at a temperature of 45 to 50 ° C. in an aqueous solution of pH 7 containing hexasodium hexametaphosphate (Na 6 P 6 0 18 ).
  • the changes in the dye adsorption obtained with increasing proportions of this salt are shown in the table.
  • the comparative example is carried out without an aftertreatment.
  • Example 1 The procedure of Example 1 is followed, but roughened in an aqueous solution containing 0.9% of HCl.
  • Example 2 The procedure is as in Example 1, but the Na 6 P 6 O 18 solution additionally contains 10 g / 1 of citric acid and thus a pH of 2.5.
  • Example 2 The procedure is as in Example 2, but the Na 6 P 6 O 18 solution additionally contains 10 g / l of citric acid and thus a pH of 2.5.
  • Example 1 V5 to V12
  • Example 2 V13 to V20
  • the effect is affected by a change in pH, e.g. B. with the addition of citric acid, significantly increased again; it also occurs with the addition of other, not too strong acids, in the pH range from 1 to 5 in a similar order of magnitude.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Printing Plates And Materials Therefor (AREA)
EP85105492A 1984-05-16 1985-05-06 Verfahren zur Nachbehandlung von Aluminiumoxidschichten mit Phosphoroxo-Anionen enthaltenden wässrigen Lösungen und deren Verwendung bei der Herstellung von Offsetdruckplattenträgern Expired EP0161608B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843418111 DE3418111A1 (de) 1984-05-16 1984-05-16 Verfahren zur nachbehandlung von aluminiumoxidschichten mit phosphoroxo-anionen enthaltenden waessrigen loesungen und deren verwendung bei der herstellung von offsetdruckplattentraegern
DE3418111 1984-05-16

Publications (2)

Publication Number Publication Date
EP0161608A1 EP0161608A1 (de) 1985-11-21
EP0161608B1 true EP0161608B1 (de) 1987-08-12

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Family Applications (1)

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EP85105492A Expired EP0161608B1 (de) 1984-05-16 1985-05-06 Verfahren zur Nachbehandlung von Aluminiumoxidschichten mit Phosphoroxo-Anionen enthaltenden wässrigen Lösungen und deren Verwendung bei der Herstellung von Offsetdruckplattenträgern

Country Status (7)

Country Link
US (1) US4650739A (enrdf_load_stackoverflow)
EP (1) EP0161608B1 (enrdf_load_stackoverflow)
JP (1) JPS60253597A (enrdf_load_stackoverflow)
BR (1) BR8502292A (enrdf_load_stackoverflow)
CA (1) CA1271958A (enrdf_load_stackoverflow)
DE (2) DE3418111A1 (enrdf_load_stackoverflow)
ZA (1) ZA853680B (enrdf_load_stackoverflow)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07119151B2 (ja) * 1987-12-07 1995-12-20 富士写真フイルム株式会社 平版印刷版用支持体
US5230988A (en) * 1991-03-12 1993-07-27 Fuji Photo Film Co., Ltd. Method of making lithographic printing plate
ATE336390T1 (de) * 1998-12-22 2006-09-15 Fuji Photo Film Co Ltd Verfahren zur herstellung einer lichtempfindlichen flachdruckplatte
JP4868020B2 (ja) * 2008-12-26 2012-02-01 株式会社デンソー アルミニウムの陽極酸化方法、および陽極酸化アルミニウム

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL273557A (enrdf_load_stackoverflow) * 1961-01-25
BE630566A (enrdf_load_stackoverflow) * 1962-04-03
US3373021A (en) * 1964-01-29 1968-03-12 Harris Intertype Corp Presensitized positive working lithographic plate
US3511661A (en) * 1966-07-01 1970-05-12 Eastman Kodak Co Lithographic printing plate
ZA6807938B (enrdf_load_stackoverflow) * 1967-12-04
CH526399A (de) * 1968-12-06 1972-08-15 Hasek Josef Verfahren zur Herstellung einer Offsetdruckplatte
US3679419A (en) * 1969-05-20 1972-07-25 Azoplate Corp Light-sensitive diazo condensate containing reproduction material
GB1410768A (en) * 1971-10-22 1975-10-22 Vickers Ltd Lithographic printing plates comprising anodised aluminium
BE792852A (fr) * 1971-12-17 1973-06-15 Henkel & Cie Gmbh Procede de traitement de surfaces d'aluminium par oxydation suivie d'une densification
US3808000A (en) * 1972-03-28 1974-04-30 Grace W R & Co Printing plate and method of preparation
CA1011279A (en) * 1972-07-27 1977-05-31 Yoshiaki Miyosawa Method of after-treatment for lithographic printing plates
US4116695A (en) * 1974-09-12 1978-09-26 Fuji Photo Film Co., Ltd. Method of producing a support for a printing plate
JPS51101741A (ja) * 1975-03-06 1976-09-08 Yoshida Kogyo Kk Taishokuseiyokyokusankahimakunotosoho
JPS52150104A (en) * 1976-06-07 1977-12-13 Fuji Photo Film Co Ltd Photoosensitive lithographic press plate material
DE3006094A1 (de) * 1980-02-19 1981-08-20 Hoechst Ag, 6000 Frankfurt Verfahren zum konservieren von flachdruckformen
DE3126636A1 (de) * 1981-07-06 1983-01-27 Hoechst Ag, 6000 Frankfurt Hydrophilierte traegermaterialien fuer offsetdruckplatten, ein verfahren zu ihrer herstellung und ihre verwendung
DE3206470A1 (de) * 1982-02-23 1983-09-01 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von traegermaterialien fuer offsetdruckplatten
US4414311A (en) * 1982-03-18 1983-11-08 American Hoechst Corporation Cathodic deposition of light sensitive components
JPS58193194A (ja) * 1982-05-06 1983-11-10 Fuji Photo Film Co Ltd 平版印刷版用版画保護剤
JPS59214651A (ja) * 1983-05-20 1984-12-04 Fuji Photo Film Co Ltd 感光性平版印刷版を用いた製版方法

Also Published As

Publication number Publication date
BR8502292A (pt) 1986-01-21
US4650739A (en) 1987-03-17
ZA853680B (en) 1985-12-24
DE3560465D1 (en) 1987-09-17
EP0161608A1 (de) 1985-11-21
CA1271958A (en) 1990-07-24
DE3418111A1 (de) 1985-11-21
JPS60253597A (ja) 1985-12-14
JPH0545437B2 (enrdf_load_stackoverflow) 1993-07-09

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