EP0154200B1 - Process for a two-step hydrophilizing aftertreatment of aluminium oxide layers with aqueous solutions, and their use in the production of supports for off-set printing plates - Google Patents

Process for a two-step hydrophilizing aftertreatment of aluminium oxide layers with aqueous solutions, and their use in the production of supports for off-set printing plates Download PDF

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Publication number
EP0154200B1
EP0154200B1 EP19850101401 EP85101401A EP0154200B1 EP 0154200 B1 EP0154200 B1 EP 0154200B1 EP 19850101401 EP19850101401 EP 19850101401 EP 85101401 A EP85101401 A EP 85101401A EP 0154200 B1 EP0154200 B1 EP 0154200B1
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EP
European Patent Office
Prior art keywords
post
alkaline earth
acid
treatment
earth metal
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Expired
Application number
EP19850101401
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German (de)
French (fr)
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EP0154200A1 (en
Inventor
Ulrich Dr. Dipl.-Chem. Simon
Reiner Beutel
Gerhard Dr. Dipl.-Chem. Sprintschnik
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Hoechst AG
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Hoechst AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/20—Electrolytic after-treatment
    • 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
    • B41N3/038—Treatment 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
    • 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
    • C25D11/24—Chemical after-treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31667—Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product

Definitions

  • the invention relates to an aftertreatment process for roughened and anodically oxidized aluminum, in particular of carrier materials for offset printing plates with aqueous solutions.
  • Backing 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 aid of which a printing image of a template is generated by photomechanical means.
  • 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.
  • the carrier exposed in the non-image areas must have a high affinity for water, i. H. be highly hydrophilic in order to absorb water quickly and permanently during the lithographic printing process and to be sufficiently repellent to the bold printing ink.
  • the adhesion of the radiation-sensitive layer before or the printing parts of the layer after the irradiation must be sufficient.
  • 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 complexing agents also include salts of organic carboxylic acids such as maleic acid, fumaric acid, citric acid or tartaric acid.
  • Non-prepublished DE-A 32 32 485 describes a process for the aftertreatment of roughened and anodized aluminum supports for printing plates, which is carried out in two stages a) with an aqueous alkali metal silicate solution and b) with an aqueous alkaline earth metal salt solution.
  • 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 hydrophilizing aftertreatments with silicates or hydrophilic organic polymers improved in effect, in particular with regard to the alkali resistance of the layers.
  • the invention is based on the known method for producing plate. Foil-like or tape-like materials based on chemically, mechanically and / or electrochemically roughened and anodically oxidized aluminum or one of its alloys, the aluminum oxide layers of which are treated with an alkali metal silicate and at least one hydrophilic organic, phosphorus-containing polymer, in each case in aqueous solution.
  • the process according to the invention is then characterized in that the aftertreatment of the aluminum oxide layer a) is first carried out in an aqueous solution containing alkali metal silicate and b) subsequently in an aqueous solution containing at least one organic polymer with vinylphosphonic acid and / or vinylmethylphosphinic acid units.
  • the solution in the aftertreatment step a) additionally contains alkaline earth metal ions.
  • stage a) with the additionally occurring alkaline earth metal ions is - for the first time - however without subsequent implementation of stage b) - in the simultaneously filed European patent application 8510-14027 (EP-A - 0 154 201) with the title “Process for the post-treatment of aluminum oxide layers with aqueous solutions containing alkali metal silicate and their use in the production of offset printing plate supports.
  • water-soluble alkaline earth metal salts preferably calcium or strontium salts
  • the compounds which provide alkaline earth metal ions which also includes hydroxides in addition to the acid-derived compounds, in particular nitrates.
  • the aqueous solution in the aftertreatment stage a) contains 0.5 to 30% by weight, in particular 1 to 15% by weight, of alkali metal silicate (such as sodium metasilicate or the sodium and sodium silicates contained in the “water glass”). tetrasilicates) and optionally 0.001 to 0.5% by weight, in particular 0.005 to 0.3% by weight, of alkaline earth metal ions (such as Ca 2+ or Sr 2+ ).
  • this aqueous solution can also contain at least one complexing agent for alkaline earth metal ions such as hydroxycarboxylic acids, amino carboxylic acids, nitrogen or hydroxy compounds containing hydroxyl or carboxyl groups (e.g. levulinic acid, ethylenediaminetetraacetic acid) or their salts).
  • at least one complexing agent for alkaline earth metal ions such as hydroxycarboxylic acids, amino carboxylic acids, nitrogen or hydroxy compounds containing hydroxyl or carboxyl groups (e.g. levulinic acid, ethylenediaminetetraacetic acid) or their salts).
  • the polymers in the aftertreatment stage b) also include copolymers which, in addition to vinylphosphonic acid and / or vinylmethylphosphinic acid units, also have other units which can be copolymerized with them, such as acrylic acid-acrylamide or vinyl acetate units.
  • the aqueous solution in the aftertreatment stage b) contains 0.01 to 10% by weight, in particular 0.02 to 5% by weight, of at least one of the organic, phosphorus-containing polymers.
  • the post-treatment stages can be carried out individually or both as immersion treatment and / or electrochemically, the latter procedure often bringing about a further increase in the alkali resistance and / or improvement in the adsorption behavior of the material.
  • the electrochemical process variant is carried out in particular with direct or alternating current, trapezoidal, rectangular or triangular current or overlapping forms of these types of current; the current density is generally 0.1 to 10 Aldm 2 and / or the voltage is 1 to 100 V, the rest of the parameters depend on z. B. from electrode spacing or the electrolyte composition.
  • the aftertreatment of the materials can be carried out discontinuously or continuously in 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. It is assumed that a firmly adhering cover layer forms in the pores of the aluminum oxide layer, which protects the oxide from attacks.
  • 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 those materials in which the maintenance of this topography plays a major role, for example for printing plate support materials.
  • the post-treatment stages according to the invention are surprisingly effective only in the order claimed, but not in the reverse order.
  • 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 if necessary after pre-cleaning, is first mechanically (e.g. by brushing and / or with abrasive treatment), chemically (e.g. by etching agent) and / or electrochemically (e.g. B. roughened by AC treatment in aqueous acid or salt solutions).
  • Electrochemical roughening is preferably carried out in the process according to the invention, but these aluminum support materials can also be roughened mechanically before the electrochemical stage (for example by brushing with wire or nylon brushes and / or with an abrasive treatment). 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 Aldm 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.
  • acid also higher in the case of salts
  • alternating current with a frequency of 50 to 60 Hz is 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 z 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 (NO 3 ) 3 and / or AlCl 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.
  • Pre-cleaning includes, for example, treatment with aqueous NaOH solution with or without degreasing agent and / or complexing agents, trichlorethylene, acetone, methanol or other commercially available aluminum stains.
  • the 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 (between the stages up to 5 g / m 2 );
  • 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 which essentially have only a rinsing and / or cleaning effect and, for example, for removing deposits ( «Schmant») formed during roughening or simply for removal serve from 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 SO 4 , H 3 PO 4 , H 2 C 2 0 4 , amidosulfonic acid, sulfosuccinic acid, sulfosalicylic acid or mixtures thereof can be used for the anodic oxidation; in particular, H 2 SO 4 and H 3 P0 4 are used alone, in a mixture and / or in a multi-stage anodizing process.
  • 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.
  • photo-semiconducting layers as they e.g. B. in DE-C-11 17391, 15 22 497, 15 72 312, 23 22 046 and 23 22 047 are described, to those produced according to the invention Carrier materials are applied, which creates highly light-sensitive, electrophotographic printing plates.
  • 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, compared to plates in which the same base material has been post-treated with aqueous solutions containing only alkali metal silicates or phosphorus-containing organic polymers, are characterized by improved hydrophilicity of the non-image areas and a lower tendency to form color fog and improved alkali resistance.
  • the alkali resistance of the surface is determined by immersing a piece of plate not provided with a radiation-sensitive layer in an aqueous dilute NaOH solution for a certain period of time (for example 30 minutes) and then visually assessing the oxide layer.
  • the values a to e mean no (a) to strong (e) oxide layer attack, only whole steps are given.
  • a radiation-sensitive layer either a negative-working layer containing a reaction product of polyvinyl butyral with propenylsulfonyl isocyanate, a polycondensation product of 1 mol of 3-methoxy-diphenylamine-4-diazonium sulfate and 1 mol of 4,4'-bismethoxymethyl-diphenyl ether is precipitated as mesitylene sulfonate, H 3 P0 4 , Viktoriareinblau FGA and phenylazodiphenylamine or a positive working with a content of a cresol-formaldehyde novolak, 4- (2-phenylprop-2-yl) phenyl ester of the naphthoquinone- (1,2) -diazid- (2nd ) -sulfonic acid- (4), polyvinyl butyral, naphthoquinone- (1,2) -diazide- (2) -sulfonic
  • An aluminum strip is electrochemically roughened in an aqueous solution containing 1.4% of HNO 3 and 6% of Al (NO 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 untreated oxide layer is rated 3 in dye adsorption and a in alkali resistance.
  • V 1 The procedure of V 1 is followed, but roughened in an aqueous solution containing 0.9% of HCl; dye adsorption is rated 5 and alkali resistance a.
  • V 1 The procedure of V 1 is followed, but test pieces of the tape are after-treated in an aqueous solution containing 4% of Na 2 Si0 3 for 30 seconds at 40 ° C. by dipping; the post-treated oxide layer is rated 3.5 in dye adsorption and a in alkali resistance.
  • test pieces of the strip are after-treated in an aqueous solution containing 4% of Na 2 Si0 3 for 30 seconds at 40 ° C. by dipping; the post-treated oxide layer is rated 3 in dye adsorption and a in alkali resistance.
  • test pieces of the strip are aftertreated electrochemically (40 V DC) for 30 seconds at 25 ° C. in an aqueous solution containing 4% of Na 2 Si0 3 ; the post-treated oxide layer is rated 1 in dye adsorption and a in alkali resistance.
  • test pieces of the strip are aftertreated electrochemically (40 V DC) for 30 seconds at 25 ° C. in an aqueous solution containing 4% of Na 2 Si0 3 ; the post-treated oxide layer is rated 1.5 in dye adsorption and a in alkali resistance.
  • V 1 The procedure of V 1 is followed, but test pieces of the tape are after-treated by immersion at 60 ° C. for 30 seconds in an aqueous solution containing 0.5% of polyvinylphosphonic acid; the post-treated oxide layer is rated 1.5 in dye adsorption and d in alkali resistance.
  • test pieces of the tape are after-treated by immersion at 60 ° C. for 30 seconds in an aqueous solution containing 0.5% of polyvinylphosphonic acid; the post-treated oxide layer is rated 2 in dye adsorption and e in alkali resistance.
  • test pieces of the strip are after-treated electrochemically (50 V DC) for 30 seconds at 25 ° C. in an aqueous solution containing 0.5% polyvinylphosphonic acid; the post-treated oxide layer is rated 1 in dye adsorption and a in alkali resistance.
  • test pieces of the tape are after-treated electrochemically (50 V DC) for 30 seconds at 25 ° C. in an aqueous solution containing 0.5% of polyvinylphosphonic acid; the post-treated oxide layer is rated 1 in dye adsorption and d in alkali resistance.
  • the procedure is V 3 and then V 7; the two-stage post-treated oxide layer is rated 0.5 in dye adsorption and b in alkali resistance.
  • the procedure is V 4 and then V 8; the two-stage post-treated oxide layer is rated 0.5 in dye adsorption and b in alkali resistance.
  • Example 1 The procedure of Example 1 is followed, but in the first stage the aqueous solution additionally contains 0.1% of Sr 2 ' ions (in the form of Sr (N0 3 ) 2 ); the two-stage post-treated oxide layer is rated 0.5 in dye adsorption and a in alkali resistance.
  • Example 1 The procedure of Example 1 is followed, but in the first stage the aqueous solution additionally contains 0.1% of Sr 2Y ions (in the form of Sr (OH) 2 ) and 0.1% of levulinic acid; the two-stage post-treated oxide layer is rated 0.5 in dye adsorption and a in alkali resistance.
  • the procedure is V 3 and then V 9; the two-stage post-treated oxide layer is rated 1 in dye adsorption and a in alkali resistance.
  • the procedure is V 4 and then V 10; the two-stage post-treated oxide layer is rated 1.5 in dye adsorption and b in alkali resistance.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Electrochemistry (AREA)
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Description

Die Erfindung betrifft ein Nachbehandlungsverfahren für aufgerauhtes und anodisch oxidiertes Aluminium, insbesondere von Trägermaterialien für Offsetdruckplatten mit wäßrigen Lösungen.The invention relates to an aftertreatment process for roughened and anodically oxidized aluminum, in particular of carrier materials for offset printing plates with aqueous solutions.

Trägermaterialien für Offsetdruckplatten werden entweder vom Verbraucher direkt oder vom Hersteller vorbeschichteter Druckplatten ein-oder beidseitig mit einer strahlungs(licht)empfindlichen Schicht (Reproduktionsschicht) versehen, mit deren Hilfe ein druckendes Bild einer Vorlage auf photomechanischem Wege erzeugt wird. Nach Herstellung dieser Druckform aus der Druckplatte trägt der Schichtträger die beim späteren Drucken farbführenden Bildstellen und bildet zugleich an den beim späteren Drucken bildfreien Stellen (Nichtbildstellen) den hydrophilen Bilduntergrund für den lithographischen Druckvorgang.Backing 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 aid of which a printing image of a template is generated by photomechanical means. After this printing form has been produced from the printing plate, 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.

An einen Schichtträger für Reproduktionsschichten zum Herstellen von Offset- 'druckplatten sind deshalb folgende Anforderungen zu stellen :

  • Die nach der Bestrahlung (Belichtung) relativ löslicher gewordenen Teile der strahlungsempfindlichen Schicht müssen durch eine Entwicklung leicht zur Erzeugung der hydrophilen Nichtbildstellen rückstandsfrei vom Träger zu entfernen sein.
The following requirements must therefore be placed on a layer support for reproduction layers for the production of offset printing plates:
  • The parts of the radiation-sensitive layer which have become relatively more soluble after the irradiation (exposure) must be easy to remove from the support without residue by development to produce the hydrophilic non-image areas.

Der in den Nichtbildstellen freigelegte Träger muß eine große Affinität zu Wasser besitzen, d. h. stark hydrophil sein, um beim lithographischen Druckvorgang schnell und dauerhaft Wasser aufzunehmen und gegenüber der fetten Druckfarbe ausreichend abstoßend zu wirken.The carrier exposed in the non-image areas must have a high affinity for water, i. H. be highly hydrophilic in order to absorb water quickly and permanently during the lithographic printing process and to be sufficiently repellent to the bold printing ink.

Die Haftung der strahlungsempfindlichen Schicht vor bzw. der druckenden Teile der Schicht nach der Bestrahlung muß in einem ausreichenden Maß gegeben sein.The adhesion of the radiation-sensitive layer before or the printing parts of the layer after the irradiation must be sufficient.

Als Basismaterial für derartige Schichtträger wird insbesondere Aluminium eingesetzt. Es wird nach bekannten Methoden .durch Trockenbürstung, Naßbürstung, Sandstrahlen, chemische und/oder elektrochemische Behandlung oberflächlich aufgerauht. Zur Steigerung der Abriebfestigkeit kann das aufgerauhte Substrat noch einem Anodisierungsschritt zum Aufbau einer dünnen Oxidschicht unterworfen werden.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.

In der Praxis werden die Trägermaterialien, insbesondere anodisch oxidierte Trägermaterialien auf der Basis von Aluminium, oftmals zur Verbesserung der Schichthaftung, zur Steigerung der Hydrophilie und/oder zur Erleichterung der Entwickelbarkeit der strahlungsempfindlichen Schichten vor dem Aufbringen einer strahlungsempfindlichen Schicht einem weiteren Behandlungsschritt unterzogen, dazu zählen beispielsweise die folgenden Methoden :

  • In der DE-C-907147 (= US-A-2 714 066), der DE-B-14 71 707 (= US-A-3 181 461 und US-A-3 280 734) oder der DE-A-25 32 769 (= US-A-3 902 976) werden Verfahren zur Hydrophilierung von Druckplattenträgermaterialien auf der Basis von gegebenenfalls anodisch oxidiertem Aluminium beschrieben, in denen diese Materialien ohne oder mit Einsatz von elektrischem Strom mit wäßriger Natriumsilikat-Lösung behandelt werden.
In practice, the carrier materials, in particular anodically oxidized carrier materials based on aluminum, are often 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:
  • In DE-C-907147 (= US-A-2 714 066), DE-B-14 71 707 (= US-A-3 181 461 and US-A-3 280 734) or DE-A- 25 32 769 (= US-A-3 902 976) describes processes for hydrophilizing printing plate support materials based on optionally anodized aluminum, in which these materials are treated with aqueous sodium silicate solution without or with the use of electric current.

Aus der DE-C-11 34 093 (= US-A-3 276 868) und der DE-C-16 21 478 (= US-A-4 153 461) ist es bekannt, Polyvinylphosphonsäure oder Mischpolymerisate auf der Basis von Vinylphosphonsäure, Acrylsäure und Vinylacetat zur Hydrophilierung von Druckplattenträgermaterialien auf der Basis von gegebenenfalls anodisch oxidiertem Aluminium einzusetzen. Gemäß der EP-A-0 048 909 (= US-A-4 399 021) kann man ein solches Nachbehandlungsverfahren nicht nur durch Tauchbehandlung, sondern auch mit Einsatz von elektrischem Strom durchführen. Ein vergleichbar einsetzbares Polymeres ist auch die Polyvinylmethylphosphinsäure nach der DE-A-31 26 627 (= ZA-A-82/4357).From DE-C-11 34 093 (= US-A-3 276 868) and DE-C-16 21 478 (= US-A-4 153 461) it is known to use polyvinylphosphonic acid or copolymers based on vinylphosphonic acid , Acrylic acid and vinyl acetate for the hydrophilization of printing plate support materials based on optionally anodized aluminum. According to EP-A-0 048 909 (= US-A-4 399 021), such an aftertreatment process can be carried out not only by immersion treatment but also with the use of electric current. A comparable usable polymer is also the polyvinylmethylphosphinic acid according to DE-A-31 26 627 (= ZA-A-82/4357).

Diese Nachbehandlungsverfahren führen zwar oftmals zu ausreichenden Ergebnissen, können jedoch nicht allen, häufig sehr komplexen Anforderungen an ein Druckplattenträgermaterial gerecht werden, so wie sie heute von der Praxis an Hochleistungsdruckplatten gestellt werden. So kann beispielsweise nach der Behandlung mit Alkalimetallsilikaten, die zu guter Entwickelbarkeit und Hydrophilie führen, eine gewisse Verschlechterung der Lagerfähigkeit von darauf aufgebrachten Reproduktionsschichten auftreten. Bei der Behandlung von Trägern mit wasserlöslichen organischen Polymeren führt deren gute Löslichkeit besonders in wäßrig-alkalischen Entwicklern, wie sie überwiegend zum Entwickeln von positiv-arbeitenden Reproduktionsschichten verwendet werden, zur Abschwächung der hydrophilierenden Wirkung. Auch ist die Alkaliresistenz, die insbesondere bei Einsatz von Hochleistungsentwicklern auf dem Gebiet der positiv-arbeitenden Reproduktionsschichten gefordert wird, nicht in genügendem Maße gegeben. Gelegentlich kommt es auch, abhängig von der chemischen Zusammensetzung der Reproduktionsschichten, zu einer Schleierbildung in den Nichtbildstellen, die durch adsorptive Effekte hervorgerufen werden dürfte. Im Stand der Technik sind auch bereits Modifizierungen der Silikatisierungsverfahren und auch der Behandlungen mit hydrophilen Polymeren beschrieben worden, dazu zählen beispielsweise : die härtende Nachbehandlung von durch Tauchbehandlung in wäßrigen Alkalisilikatlösungen hergestellten Silikatschichten auf Druckplattenträgern aus Aluminium mit einer wäßrigen Ca(N03)s-Lösung oder allgemein einer Erdalkalisalz-Lösung nach den US-A-2 882 153 und US-A-2882154, wobei in der Regel Erdalkalisalzkonzentrationen von mehr als 3 Gew.- % angewandt werden ; die Trägermaterialien werden nur chemisch oder mechanisch aufgerauht und nicht anodisch oxidiert,Although these post-treatment processes often lead to sufficient results, they cannot meet all, often very complex, requirements for a printing plate support material, as are currently placed on high-performance printing plates in practice. For example, after treatment with alkali metal silicates, which lead to good developability and hydrophilicity, a certain deterioration in the storage life of reproductive layers applied thereon may occur. In the treatment of carriers with water-soluble organic polymers, their good solubility, particularly in aqueous alkaline developers, as are used predominantly for the development of positive-working reproduction layers, leads to a weakening of the hydrophilizing effect. The alkali resistance, which is required in particular when using high-performance developers in the field of positive-working reproduction layers, is not sufficient. Occasionally, depending on the chemical composition of the reproductive layers, fogging occurs in the non-image areas, which is likely to be caused by adsorptive effects. In the prior art, modifications of the silicatization processes and also the treatments with hydrophilic polymers have already been described, these include, for example: the curing aftertreatment of silicate layers produced by immersion treatment in aqueous alkali silicate solutions on aluminum printing plate supports with an aqueous Ca (N0 3 ) s solution or generally an alkaline earth salt solution according to US-A-2,882,153 and US-A-2,882,154, generally using alkaline earth salt concentrations of more than 3% by weight; the carrier materials are only chemically or mechanically roughened and not anodically oxidized,

ein Verfahren gemäß der DE-A-22 23 850 (= US-A-3 824 159) zur Beschichtung von Aluminiumformstücken, -blechen, -gußstücken oder -folien (u. a. auch für Offsetdruckplatten, aber speziell für Kondensatoren), bei dem eine anodische Oxidation in einem wäßrigen Elektrolyten aus einem Alkalisilikat und einem organischen Komplexbildner durchgeführt wird ; zu den Komplexbildnern zählen neben Aminen, Aminosäuren, Sulfonsäuren, Phenolen und Glykolen auch Salze organischer Carbonsäuren wie Maleinsäure, Fumarsäure, Citronensäure oder Weinsäure.
das Verfahren zur Herstellung von kornartigen oder gemaserten Oberflächen auf Aluminium nach der DE-B-26 51 346 (GB-A-1 523 030), das direkt auf Aluminium mit Wechselstrom in einem Elektrolyten durchgeführt wird, der in wäßriger Lösung 0,01 bis 0,5 Mol/I eines Alkalimetall- oder Erdalkalimetallhydroxids oder -salzes (z. B. einem Silikat) und gegebenenfalls 0,01 bis 0,5 Mol/I eines Sperrschichtbildners enthält, zu den Sperrschichtbildnern sollen u. a. Citronensäure, Weinsäure, Bernsteinsäure, Milchsäure, Äpfelsäure oder deren Salze gehören,a method according to DE-A-22 23 850 (= US-A-3 824 159) for coating aluminum moldings, sheets, castings or foils (including for offset printing plates, but especially for capacitors), in which an anodic Oxidation is carried out in an aqueous electrolyte from an alkali silicate and an organic complexing agent; In addition to amines, amino acids, sulfonic acids, phenols and glycols, the complexing agents also include salts of organic carboxylic acids such as maleic acid, fumaric acid, citric acid or tartaric acid.
the process for the production of grain-like or grained surfaces on aluminum according to DE-B-26 51 346 (GB-A-1 523 030), which is carried out directly on aluminum with alternating current in an electrolyte which is in aqueous solution from 0.01 to Contains 0.5 mol / l of an alkali metal or alkaline earth metal hydroxide or salt (e.g. a silicate) and optionally 0.01 to 0.5 mol / l of a barrier layer former. Among the barrier layer former are citric acid, tartaric acid, succinic acid, lactic acid , Malic acid or its salts,

Aluminiumträgermaterialien für Offsetdruckplatten gemäß der DE-A-31 26 636 (= US-A-4 427 765), die auf einer anodisch erzeugten Aiuminiumoxidschicht eine hydrophile Beschichtung eines komplexartigen Umsetzungsprodukts aus a) einem wasserlöslichen Polymeren wie Polyvinylphosphonsäure und b) einem Salz eines mindestens zweiwertigen Metallkations wie Zn2+ tragen, oderAluminum carrier materials for offset printing plates according to DE-A-31 26 636 (= US-A-4 427 765) which, on an anodized aluminum oxide layer, a hydrophilic coating of a complex reaction product of a) a water-soluble polymer such as polyvinylphosphonic acid and b) a salt of at least one wear divalent metal cations such as Zn 2+ , or

das Verfahren zur Herstellung von Aluminiumträgermaterialien, insbesondere für Offsetdruckplatten, nach der EP-A-0 089 510 (= US-A-4 376 814), bei dem das normalerweise anodisch oxidierte flächige Aluminium einstufig mit einer wäßrigen Lösung eines Gehalts an a) beispielsweise einem Natriumsilikat und b) einem alkalisch reagierenden Natrium- oder Ammoniumsalz eines hydrophilen Polymeren wie-Polyvinylphosphonsäure nachbehandelt wird.the process for the production of aluminum support materials, in particular for offset printing plates, according to EP-A-0 089 510 (= US-A-4 376 814), in which the normally anodically oxidized flat aluminum, for example, in one step with an aqueous solution containing a) a sodium silicate and b) an alkaline sodium or ammonium salt of a hydrophilic polymer such as polyvinyl phosphonic acid.

Diese bekannten Modifizierungen von hydrophilierenden Nachbehandlungen mit Silikaten oder bestimmten hydrophilen organischen Polymeren - sofern sie überhaupt auf Druckplattenträger aus Aluminium übertragen werden können bzw. für diese sinnvoll sind - führen jedoch noch nicht zu einer Oberfläche, die für Hochleistungsdruckplatten geeignet ist, d. h. sie sind noch nicht anwendungstechnisch so verbessert, daß sie den weiter oben dargestellten Anforderungen in vollem Umfang genügen, oder die Verfahren sind in der vorbereitenden Herstellung von verschiedensten Lösungen mit definierten pH-Werten und deren Überwachung zu aufwendig.However, these known modifications of hydrophilizing aftertreatments with silicates or certain hydrophilic organic polymers - insofar as they can be transferred to printing plate supports made of aluminum at all or are sensible for them - do not yet lead to a surface which is suitable for high-performance printing plates, i.e. H. they have not yet been improved in terms of application technology in such a way that they fully meet the requirements set out above, or the processes are too complex to prepare and monitor a wide variety of solutions with defined pH values.

In der prioritätsälteren. nicht-vorveröffentlichten DE-A 32 32 485 wird ein Verfahren zur Nachbehandlung von aufgerauhten und anodisch oxidierten Aluminiumträgern für Druckplatten beschrieben, das zweistufig a) mit einer wäßrigen Alkalimetallsilikatlösung und b) mit einer wäßrigen Erdalkalimetallsalzlösung durchgeführt wird.In the older one. Non-prepublished DE-A 32 32 485 describes a process for the aftertreatment of roughened and anodized aluminum supports for printing plates, which is carried out in two stages a) with an aqueous alkali metal silicate solution and b) with an aqueous alkaline earth metal salt solution.

Aufgabe der vorliegenden Erfindung ist es, ein Verfahren zur Nachbehandlung von flächigem Aluminium vorzuschlagen, das zusätzlich zu einer anodischen Oxidation des Aluminiums durchgeführt werden kann und zu einer Oberfläche auf dem so erzeugten Aluminiumoxid führt, die insbesondere den eingangs dargestellten Praxisanforderungen an eine Hochleistungsdruckplatte genügt und die bereits bekannten hydrophilierenden Nachbehandlungen mit Silikaten oder hydrophilen organischen Polymeren in der Wirkung verbessert, insbesondere bezüglich der Alkaliresistenz der Schichten.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 hydrophilizing aftertreatments with silicates or hydrophilic organic polymers improved in effect, in particular with regard to the alkali resistance of the layers.

Die Erfindung geht aus von dem bekannten Verfahren zur Herstellung von platten-. folien-oder bandförmigen Materialien auf der Basis von chemisch, mechanisch und/oder elektrochemisch aufgerauhtem und anodisch oxidiertem Aluminium oder einer seiner Legierungen, deren Aluminiumoxidschichten mit einem Alkalimetallsilikat und mindestens einem hydrophilen organischen, Phosphor enthaltenden Polymeren, jeweils in wäßriger Lösung, nachbehandelt werden. Das erfindungsgemäße Verfahren ist dann dadurch gekennzeichnet, daß die Nachbehandlung der Aluminiumoxidschicht a) zuerst in einer wäßrigen, Alkalimetallsilikat enthaltenden Lösung und b) anschließend in einer wäßrigen, mindestens ein organisches Polymeres mit Vinylphosphonsäure-und/oder Vinylmethylphosphinsäure-Einheiten enthaltenden Lösung durchgeführt wird. In einer bevorzugten Ausführungsform enthält die Lösung in der Nachbehandlungsstufe a) zusätzlich noch Erdalkalimetallionen.The invention is based on the known method for producing plate. Foil-like or tape-like materials based on chemically, mechanically and / or electrochemically roughened and anodically oxidized aluminum or one of its alloys, the aluminum oxide layers of which are treated with an alkali metal silicate and at least one hydrophilic organic, phosphorus-containing polymer, in each case in aqueous solution. The process according to the invention is then characterized in that the aftertreatment of the aluminum oxide layer a) is first carried out in an aqueous solution containing alkali metal silicate and b) subsequently in an aqueous solution containing at least one organic polymer with vinylphosphonic acid and / or vinylmethylphosphinic acid units. In a preferred embodiment, the solution in the aftertreatment step a) additionally contains alkaline earth metal ions.

Die Ausführungsform der Stufe a) mit den zusätzlich vorkommenden Erdalkalimetallionen wird - jedoch ohne nachfolgende Durchführung der Stufe b) - erstmals in der gleichzeitig eingereichten europäischen Patentanmeldung 8510-14027 (EP-A-0 154 201) mit dem Titel « Verfahren zur Nachbehandlung von Aluminiumoxidschichten mit Alkalimetallsilikat enthaltenden wäßrigen Lösungen und deren Verwendung bei der Herstellung von Offsetdruckplattenträgern beschrieben.The embodiment of stage a) with the additionally occurring alkaline earth metal ions is - for the first time - however without subsequent implementation of stage b) - in the simultaneously filed European patent application 8510-14027 (EP-A - 0 154 201) with the title “Process for the post-treatment of aluminum oxide layers with aqueous solutions containing alkali metal silicate and their use in the production of offset printing plate supports.

Als Erdalkalimetallionen liefernde Verbindungen werden im allgemeinen wasserlösliche Erdalkalimetallsalze, bevorzugt Calcium- oder Strontiumsalze, eingesetzt, wozu neben den sich von Säuren ableitenden Verbindungen wie insbesondere Nitraten auch Hydroxide zu zählen sind. In bevorzugten Ausführungsformen enthält die wäßrige Lösung in der Nachbehandlungsstufe a) 0,5 bis 30 Gew.- %, insbesondere 1 bis 15 Gew.- % an Alkalimetallsilikat (wie Na-metasilikat oder die im «Wasserglas» enthaltenden Na- tri- und -tetrasilikate) und gegebenenfalls 0.001 bis 0.5 Gew.- %, insbesondere 0.005 bis 0.3 Gew.- % an Erdalkalimetallionen (wie Ca2+ oder Sr2+). Zusätzlich kann diese wäßrige Lösung noch mindestens einen Komplexbildner für Erdalkalimetallionen wie Hydroxycarbonsäuren, Aminocarbonsäuren, Hydroxy- oder Carboxylgruppen enthaltende Stickstoffverbindungen oder Phenole (z. B. Lävulinsäure, Ethylendiamintetraessigsäure oder deren Salze) enthalten.In general, water-soluble alkaline earth metal salts, preferably calcium or strontium salts, are used as the compounds which provide alkaline earth metal ions, which also includes hydroxides in addition to the acid-derived compounds, in particular nitrates. In preferred embodiments, the aqueous solution in the aftertreatment stage a) contains 0.5 to 30% by weight, in particular 1 to 15% by weight, of alkali metal silicate (such as sodium metasilicate or the sodium and sodium silicates contained in the “water glass”). tetrasilicates) and optionally 0.001 to 0.5% by weight, in particular 0.005 to 0.3% by weight, of alkaline earth metal ions (such as Ca 2+ or Sr 2+ ). In addition, this aqueous solution can also contain at least one complexing agent for alkaline earth metal ions such as hydroxycarboxylic acids, amino carboxylic acids, nitrogen or hydroxy compounds containing hydroxyl or carboxyl groups (e.g. levulinic acid, ethylenediaminetetraacetic acid) or their salts).

Zu den Polymeren in der Nachbehandlungsstufe b) zählen neben den Homopolymerisaten Polyvinylmethylphosphinsäure und insbesondere Polyvinylphosphonsäure auch Copolymerisate, die neben Vinylphosphonsäure- und/oder Vinylmethylphosphinsäure-Einheiten auch andere, mit diesen copolymerisierbare Einheiten wie Acrylsäure-Acrylamid- oder Vinylacetat-Einheiten aufweisen. In einer bevorzugten Ausführungsform enthält die wäßrige Lösung in der Nachbehandlungsstufe b) 0,01 bis 10 Gew.- %, insbesondere 0,02 bis 5 Gew.- % mindestens eines der organischen, Phosphor enthaltenden Polymeren.In addition to the homopolymers polyvinylmethylphosphinic acid and in particular polyvinylphosphonic acid, the polymers in the aftertreatment stage b) also include copolymers which, in addition to vinylphosphonic acid and / or vinylmethylphosphinic acid units, also have other units which can be copolymerized with them, such as acrylic acid-acrylamide or vinyl acetate units. In a preferred embodiment, the aqueous solution in the aftertreatment stage b) contains 0.01 to 10% by weight, in particular 0.02 to 5% by weight, of at least one of the organic, phosphorus-containing polymers.

Die Nachbehandlungsstufen können einzeln oder auch beide als Tauchbehandlung und/oder auch elektrochemisch durchgeführt werden, wobei oftmals die letztere Verfahrensweise nochmals eine gewisse Steigerung in der Alkaliresistenz und/oder Verbesserung des Adsorptionsverhaltens des Materials bringt. Die elektrochemische Verfahrensvariante wird insbesondere mit Gleich- oder Wechselstrom, Trapez-, Rechteck- oder Dreieicksstrom oder Überlagerungsformen dieser Stromarten durchgeführt ; die Stromdichte liegt dabei im allgemeinen bei 0,1 bis 10 Aldm2 und/oder die Spannung bei 1 bis 100 V, im übrigen hängen die Parameter auch z. B. von Elektrodenabstand oder der Elektrolytzusammensetzung ab. Die Nachbehandlung der Materialien kann diskontinuierlich oder kontinuierlich in den modernen Bandanlagen durchgeführt werden, die Behandlungszeiten liegen dabei jeweils zweckmäßig im Bereich von 0,5 bis 120 sec und die Behandlungstemperaturen bei 15 bis 80 °C, insbesondere bei 20 bis 75 °C. Es wird angenommen, daß sich in den Poren der Aluminiumoxidschicht eine festhaftende Deckschicht bildet, die das Oxid vor Angriffen schützt. Die angewandte Verfahrensweise verändert die vorher erzeugte Oberflächentopographie (wie Rauhigkeit und Oxidporen) praktisch nicht oder nur unwesentlich, so daß das erfindungsgemäße Verfahren besonders zur Behandlung solcher Materialien geeignet ist, bei denen die Beibehaltung dieser Topographie eine große Rolle spieit, beispielsweise für Druckplattenträgermaterialien.The post-treatment stages can be carried out individually or both as immersion treatment and / or electrochemically, the latter procedure often bringing about a further increase in the alkali resistance and / or improvement in the adsorption behavior of the material. The electrochemical process variant is carried out in particular with direct or alternating current, trapezoidal, rectangular or triangular current or overlapping forms of these types of current; the current density is generally 0.1 to 10 Aldm 2 and / or the voltage is 1 to 100 V, the rest of the parameters depend on z. B. from electrode spacing or the electrolyte composition. The aftertreatment of the materials can be carried out discontinuously or continuously in 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. It is assumed that a firmly adhering cover layer forms in the pores of the aluminum oxide layer, which protects the oxide from attacks. 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 those materials in which the maintenance of this topography plays a major role, for example for printing plate support materials.

Wie aus den weiter unten dargestellten Vergleichsversuchen hervorgeht, sind die erfindungsgemäßen Nachbehandlungsstufen überraschenderweise nur in der beanspruchten Reihenfolge, nicht jedoch in umgekehrter Reihenfolge so gut wirksam.As can be seen from the comparative experiments shown below, the post-treatment stages according to the invention are surprisingly effective only in the order claimed, but not in the reverse order.

Zu den geeigneten Grundmaterialien für das erfindungsgemäß zu behandelnde Material zählen solche aus Aluminium oder einer seiner Legierungen, die beispielsweise einen Gehalt von mehr als 98,5 Gew.- % an AI und Anteile an Si, Fe, Ti, Cu und Zn aufweisen. Insbesondere für die Herstellung von Druckplattenträgermaterialien wird das flächige Aluminium, gegebenenfalls nach einer Vorreinigung, zuerst mechanisch (z. B. durch Bürsten und/oder mit Schleifmittel-Behandlung), chemisch (z. B. durch Ätzmittel) und/oder elektrochemisch (z. B. durch Wechselstrombehandlung in wäßrigen Säure- oder Salzlösungen) aufgerauht. Bevorzugt wird im erfindungsgemäßen Verfahren die elektrochemische Aufrauhung durchgeführt, diese Aluminiumträgermaterialien können aber auch noch vor der elektrochemischen Stufe mechanisch (z. B. durch Bürsten mit Draht- oder Nylonbürsten und/oder mit Schleifmittel-Behandlung) aufgerauht werden. Alle Verfahrensstufen können diskontinuierlich mit Platten oder Folien durchgeführt werden, sie werden aber bevorzugt kontinuierlich mit Bändern durchgeführt.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. In particular for the production of printing plate support materials, the flat aluminum, if necessary after pre-cleaning, is first mechanically (e.g. by brushing and / or with abrasive treatment), chemically (e.g. by etching agent) and / or electrochemically (e.g. B. roughened by AC treatment in aqueous acid or salt solutions). Electrochemical roughening is preferably carried out in the process according to the invention, but these aluminum support materials can also be roughened mechanically before the electrochemical stage (for example by brushing with wire or nylon brushes and / or with an abrasive treatment). All process steps can be carried out discontinuously with plates or foils, but they are preferably carried out continuously with tapes.

Im allgemeinen liegen die Verfahrensparameter, insbesondere bei kontinuierlicher Verfahrensführung, in der elektrochemischen Aufrauhstufe in folgenden Bereichen : die Temperatur des im allgemeinen 0,3 bis 5,0 Gew.- % an Säure(n) (bei Salzen auch höher) enthaltenden wäßrigen Elektrolyten zwischen 20 und 60°C, die Stromdichte zwischen 3 und 200 Aldm2, die Verweilzeit eines aufzurauhenden Materialpunkts im Elektrolyten zwischen 3 und 100 sec und die Elektrolytströmungsgeschwindigkeit an der Oberfläche des aufzurauhenden Materials zwischen 5 und 100 cm/sec ; beim diskontinuierlich durchgeführten Verfahren liegen die erforderlichen Stromdichten eher im unteren Teil und die Verweilzeiten eher im oberen Teil der jeweils angegebenen Bereiche, auf die Strömung des Elektrolyten kann dabei auch verzichtet werden. Als Stromart wird meistens normaler Wechselstrom einer Frequenz von 50 bis 60 Hz eingesetzt, es sind jedoch auch modifizierte Stromarten wie Wechselstrom mit unterschiedlichen Amplituden der Stromstärke für den Anoden- und Kathodenstrom, niedrigere Frequenzen, Stromunterbrechungen oder Überlagerungen von zwei Strömen unterschiedlicher Frequenz und Wellenform möglich. Die mittlere Rauhtiefe Rz der aufgerauhten Oberfläche liegt dabei im Bereich von 1 bis 15 µm, insbesondere von 1,5 bis 8,0 wm. Wenn der wäßrige Elektrolyt Säure(n), insbesondere HCI und/oder HN03 enthält, kann man ihm auch noch Aluminiumionen in Form von Aluminiumsalzen, insbesondere Al(NO3)3 und/oder AlCl3 zusetzen ; auch der Zusatz bestimmter weiterer Säuren und Salze wie Borsäure oder Boraten oder von Korrosionsinhibitoren wie Aminen ist bekannt.In general, 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 Aldm 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. Normally, alternating current with a frequency of 50 to 60 Hz is 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 z of the roughened surface is in the range from 1 to 15 μm, in particular from 1.5 to 8.0 μm. If the aqueous electrolyte contains acid (s), in particular HCl and / or HN0 3 , aluminum ions in the form of aluminum salts, in particular Al (NO 3 ) 3 and / or AlCl 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.

Die Vorreinigung umfaßt beispielsweise die Behandlung mit wäßriger NaOH-Lösung mit oder ohne Entfettungsmittel und/oder Komplexbildnern, Trichlorethylen, Aceton, Methanol oder anderen handelsüblichen sogenannten Aluminiumbeizen. Der Aufrauhung oder bei mehreren Aufrauhstufen auch noch zwischen den einzelnen Stufen kann noch zusätzlich eine abtragende Behandlung nachgeschaltet werden, wobei insbesondere maximal 2 g/m2 abgetragen werden (zwischen den Stufen auch bis zu 5 g/m2); als abtragend wirkende Lösungen werden im allgemeinen wäßrige Alkalihydroxidlösungen bzw. wäßrige Lösungen von alkalisch reagierenden Salzen oder wäßrige Säurelösungen auf der Basis von HN03, H2S04 oder H3P04 eingesetzt. Neben einer abtragenden Behandlungsstufe zwischen der Aufrauhstufe und einer nachfolgenden Anodisierstufe sind auch solche nicht-elektrochemischen Behandlungen bekannt, die im wesentlichen lediglich eine spülende und/oder reinigende Wirkung haben und beispielsweise zur Entfernung von bei der Aufrauhung gebildeten Belägen (« Schmant ») oder einfach zur Entfernung von Elektrolytresten dienen ; im Einsatz sind für diese Zwecke beispielsweise verdünnte wäßrige Alkalihydroxidlösungen oder Wasser.Pre-cleaning includes, for example, treatment with aqueous NaOH solution with or without degreasing agent and / or complexing agents, trichlorethylene, acetone, methanol or other commercially available aluminum stains. The 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 (between the stages up to 5 g / m 2 ); In general, 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. Next In a removal treatment stage between the roughening stage and a subsequent anodizing stage, such non-electrochemical treatments are also known which essentially have only a rinsing and / or cleaning effect and, for example, for removing deposits («Schmant») formed during roughening or simply for removal serve from electrolyte residues; For example, dilute aqueous alkali hydroxide solutions or water are used for these purposes.

Nach dem elektrochemischen Aufrauhverfahren schließt sich in einer weiteren Verfahrensstufe eine anodische Oxidation des Aluminiums an, um beispielsweise die Abrieb- und die Haftungseigenschaften der Oberfläche des Trägermaterials zu verbessern. Zur anodischen Oxidation können die üblichen Elektrolyte wie H2SO4, H3PO4, H2C204, Amidosulfonsäure, Sulfobernsteinsäure, Sulfosalicylsäure oder deren Mischungen eingesetzt werden ; insbesondere werden H2SO4 und H3P04 allein, in Mischung und/oder in einem mehrstufigen Anodisierprozeß verwendet. Die Oxidschichtgewichte liegen dabei im allgemeinen insbesondere zwischen 1 und 8 g/m2 (entsprechend etwa 0,3 bis 2,5 µm Schichtdicke).After the electrochemical roughening process, 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 SO 4 , H 3 PO 4 , H 2 C 2 0 4 , amidosulfonic acid, sulfosuccinic acid, sulfosalicylic acid or mixtures thereof can be used for the anodic oxidation; in particular, H 2 SO 4 and H 3 P0 4 are used alone, in a mixture and / or in a multi-stage anodizing process. The oxide layer weights are generally in particular between 1 and 8 g / m 2 (corresponding to about 0.3 to 2.5 μm layer thickness).

Die erfindungsgemäß hergestellten Materialien werden bevorzugt als Träger für Offsetdruckplatten verwendet, d. h. es wird entweder beim Hersteller von vorsensibilisierten Druckplatten oder direkt vom Verbraucher eine strahlungsempfindliche Beschichtung ein- oder beidseitig auf das Trägermaterial aufgebracht. Als strahlungs-(licht)empfindliche Schichten sind grundsätzlich alle Schichten geeignet, die nach dem Bestrahlen (Belichten), gegebenenfalls mit einer nachfolgenden Entwicklung und/oder Fixierung eine bildmäßige Fläche liefern, von der gedruckt werden kann.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. In principle, 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.

Neben den auf vielen Gebieten verwendeten Silberhalogenide enthaltenden Schichten sind auch verschiedene andere bekannt, wie sie z. B. in « Light-Sensitive Systems » von Jaromir Kosar, John Wiley & Sons Verlag, New York 1965 beschrieben werden : die Chromate und Dichromate enthaltenden Kolloidschichten (Kosar, Kapitel 2) ; die ungesättigte Verbindungen enthaltenden Schichten, in denen diese Verbindungen beim Belichten isomerisiert, umgelagert, cyclisiert oder vernetzt werden (Kosar, Kapitel 4) : die photopolymerisierbare Verbindungen enthaltenden Schichten, in denen Monomere oder Präpolymere gegebenenfalls mittels eines Initiators beim Belichten polymerisieren (Kosar, Kapitel 5) ; und die o-Diazo-chinone wie Naphthochinondiazide, p-Diazo-chinone oder Diazoniumsalz-Kondensate enthaltenden Schichten (Kosar, Kapitel 7). Zu den geeigneten Schichten zählen auch die elektrophotographischen Schichten, d. h. solche die einen anorganischen oder organischen Photoleiter enthalten. Außer den lichtempfindlichen Substanzen können diese Schichten selbstverständlich noch andere Bestandteile wie z. B. Harze, Farbstoffe oder Weichmacher enthalten. Insbesondere können die folgenden lichtempfindlichen Massen oder Verbindungen bei der Beschichtung der nach dem erfindungsgemäßen Verfahren hergestellten Trägermaterialien eingesetzt werden :

  • positiv-arbeitende, o-Chinondiazide. insbesondere o-Naphthochinondiazide wie Naphthochinon-(1, 2)-diazid-(2)-sulfonsäureester oder -amide, die nieder- oder höhermolekular sein können, als lichtempfindliche Verbindung enthaltende Reproduktionsschichten, die beispielsweise in den DE-C-854 890, 865 109, 879 203, 894 959, 938 233, 1 109 521, 1 144 705, 1 118 606. 1 120 273, 1 124 817 und 2 331 377 und den EP-A-0 021 428 und 0 055 814 beschrieben werden :
  • negativ-arbeitende Reproduktionsschichten mit Kondensationsprodukten aus aromatischen Diazoniumsalzen und Verbindungen mit aktiven Carbonylgruppen, bevorzugt Kondensationsprodukte aus Diphenylamindiazoniumsalzen und Formaldehyd, die beispielsweise in den DE-C-596 731, 1 138 399, 1 138 400, 1 138 401, 1 142 871, 1 154 123, den US-A-2 679 498 und 3 050 502 und der GB-A-712 606 beschrieben werden ;
  • negativ-arbeitende, Mischkondensationsprodukte aromatischer Diazoniumverbindungen enthaltende Reproduktionsschichten, beispielsweise nach der DE-C-20 65 732, die Produkte mit mindestens je einer Einheit aus a) einer kondensationsfähigen aromatischen Diazoniumsalzverbindung und b) einer kondensationsfähigen Verbindung wie einem Phenolether oder einem aromatischen Thioether, verbunden durch ein zweibindiges, von einer kondensationsfähigen Carbonylverbindung abgeleitetes Zwischenglied wie einer Methylengruppe aufweisen ;
  • positiv-arbeitende Schichten nach der DE-A-26 10 842, der DE-C-27 18 254 oder der DE-A-29 28 636, die eine bei Bestrahlung Säure abspaltende Verbindung, eine monomere oder polymere Verbindung, die mindestens eine durch Säure abspaltbare C-O-C-Gruppe aufweist (z. B. eine Orthocarbonsäureestergruppe oder eine Carbonsäureamidacetalgruppe) und gegebenenfalls ein Bindemittel enthalten ;
  • negativ-arbeitende Schichten aus photopolymerisierbaren Monomeren, Photoinitiatoren, Bindemitteln und gegebenenfalls weiteren Zusätzen : als Monomere werden dabei beispielsweise Acryl- und Methacrylsäureester oder Umsetzungsprodukte von Diisocyanaten mit Partialestern mehrwertiger Alkohole eingesetzt, wie es beispielsweise in den US-A-2 760 863 und 3060 023 und den DE-A-20 64 079 und 23 61 041 beschrieben wird ;
  • negativ-arbeitende Schichten gemäß der DE-A-30 36 077, die als lichtempfindliche Verbindung ein Diazoniumsalz-Polykondensationsprodukt oder eine organische Azidoverbindung und als Bindemittel ein hochmolekulares Polymeres mit seitenständigen Alkenylsulfonyl- oder Cycloalkenylsulfonylurethan-Gruppen enthalten.
In addition to the layers containing silver halides used in many fields, various others are also known, such as e.g. As described in “Light-Sensitive Systems” by Jaromir Kosar, John Wiley & Sons Verlag, New York 1965: the colloid layers containing chromates and dichromates (Kosar, Chapter 2); the layers containing unsaturated compounds in which these compounds are isomerized, rearranged, cyclized or crosslinked during exposure (Kosar, Chapter 4): the layers containing photopolymerizable compounds in which monomers or prepolymers optionally polymerize during exposure using an initiator (Kosar, Chapter 5 ); and the layers containing o-diazo-quinones such as naphthoquinonediazides, p-diazo-quinones or diazonium salt condensates (Kosar, Chapter 7). The suitable layers also include the electrophotographic layers, ie those which contain an inorganic or organic photoconductor. In addition to the light-sensitive substances, these layers can of course also other components such. B. contain resins, dyes or plasticizers. In particular, the following light-sensitive compositions or compounds can be used in the coating of the carrier materials produced by the process according to the invention:
  • positive working, o-quinonediazides. in particular o-naphthoquinonediazides such as naphthoquinone- (1, 2) -diazide- (2) -sulfonic acid esters or amides, which can be of low or higher molecular weight, as reproduction layers containing light-sensitive compounds, for example in DE-C-854 890, 865 109, 879 203, 894 959, 938 233, 1 109 521, 1 144 705, 1 118 606. 1 120 273, 1 124 817 and 2 331 377 and EP-A-0 021 428 and 0 055 814:
  • negative working reproduction layers with condensation products from aromatic diazonium salts and compounds with active carbonyl groups, preferably condensation products from diphenylamine diazonium salts and formaldehyde, which are described, for example, in DE-C-596 731, 1 138 399, 1 138 400, 1 138 401, 1 142 871, 1 154 123, US-A-2 679 498 and 3 050 502 and GB-A-712 606;
  • Negative-working, mixed condensation products of aromatic diazonium compounds containing reproduction layers, for example according to DE-C-20 65 732, the products with at least one unit each from a) a condensable aromatic diazonium salt compound and b) a condensable compound such as a phenol ether or an aromatic thioether by a double bonded intermediate derived from a condensable carbonyl compound such as a methylene group;
  • positive-working layers according to DE-A-26 10 842, DE-C-27 18 254 or DE-A-29 28 636, which contain a compound which splits off when irradiated, a monomeric or polymeric compound which passes through at least one Has acid-releasable COC group (z. B. an orthocarboxylic acid ester group or a carboxylic acid amidacetal group) and optionally contain a binder;
  • Negative-working layers of photopolymerizable monomers, photoinitiators, binders and, if appropriate, further additives: for example, acrylic and methacrylic acid esters or reaction products of diisocyanates with partial esters of polyhydric alcohols are used as monomers, as described, for example, in US Pat. Nos. 2,760,863 and 3,060,023 and DE-A-20 64 079 and 23 61 041 is described;
  • Negative-working layers according to DE-A-30 36 077, which contain a diazonium salt polycondensation product or an organic azido compound as the light-sensitive compound and a high molecular weight polymer with pendant alkenylsulfonyl or cycloalkenylsulfonylurethane groups as the binder.

Es können auch photohalbleitende Schichten. wie sie z. B. in den DE-C-11 17391. 15 22 497. 15 72 312, 23 22 046 und 23 22 047 beschrieben werden, auf die erfindungsgemäß hergestellten Trägermaterialien aufgebracht werden, wodurch hoch-lichtempfindliche, elektrophotographischarbeitende Druckplatten entstehen.There can also be photo-semiconducting layers. as they e.g. B. in DE-C-11 17391, 15 22 497, 15 72 312, 23 22 046 and 23 22 047 are described, to those produced according to the invention Carrier materials are applied, which creates highly light-sensitive, electrophotographic printing plates.

Die aus den erfindungsgemäß hergestellten Trägermaterialien erhaltenen beschichteten Offsetdruckplatten werden in bekannter Weise durch bildmäßiges Belichten oder Bestrahlen und Auswaschen der Nichtbildbereiche mit einem Entwickler, vorzugsweise einer wäßrigen Entwicklerlösung, in die gewünschte Druckform überführt.The 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.

Überraschenderweise zeichnen sich Offsetdruckplatten, deren Basisträgermaterialien nach dem erfindungsgemäßen zweistufigen Verfahren nachbehandelt wurden, gegenüber solchen Platten, bei denen das gleiche Basismaterial mit lediglich Alkalimetallsilikate oder Phosphor aufweisende organische Polymere enthaltenden wäßrigen Lösungen nachbehandelt wurden, durch eine verbesserte Hydrophilie der Nichtbildbereiche, eine geringere Neigung zur Farbschleierbildung und eine verbesserte Alkaliresistenz aus.Surprisingly, offset printing plates whose base support materials have been post-treated by the two-stage process according to the invention, compared to plates in which the same base material has been post-treated with aqueous solutions containing only alkali metal silicates or phosphorus-containing organic polymers, are characterized by improved hydrophilicity of the non-image areas and a lower tendency to form color fog and improved alkali resistance.

In der vorstehenden Beschreibung und den nachfolgenden Beispielen bedeuten %-Angaben, wenn nichts anderes bemerkt wird, immer Gew.- %. Gew.-Teile stehen zu Vol.-Teilen im Verhältnis von g zu cm3. Im übrigen wurden folgende Methoden zur Parameterbestimmung in den Beispielen angewandt:

  • Bei der Untersuchung, ob die Oberfläche eine Farbstoffadsorption zeigt, wird ein mit der strahlungsempfindlichen Schicht versehenes Plattenstück belichtet, entwickelt und dann eine Hälfte mit einem Korrekturmittel behandelt. Je größer die Differenz in beispielsweise den Farbwerten zwischen der unkorrigierten und der korrigierten Hälfte ist, desto mehr Farbe ist an der unkorrigierten Trägermaterialoberfläche adsorbiert. Die Werte 0 bis 5 bedeuten keine (0), eine sehr schwache (1) bis starke (5) Farbstoffadsorption, es werden nur halbe Stufen angegeben.
In the above description and the examples below,% data always mean% by weight, unless stated otherwise. Parts by weight relate to parts by volume in the ratio of g to cm 3 . The following methods for determining parameters were used in the examples:
  • When examining whether the surface shows dye adsorption, a plate piece provided with the radiation-sensitive layer is exposed, developed and then half is treated with a correction agent. The greater the difference in, for example, the color values between the uncorrected and the corrected half, the more color is adsorbed on the uncorrected substrate surface. The values 0 to 5 mean no (0), very weak (1) to strong (5) dye adsorption, only half steps are given.

Die Alkaliresistenz der Oberfläche wird durch Eintauchen eines nicht mit einer strahlungsempfindlichen Schicht versehenen Plattenstücks in eine wäßrige verdünnte NaOH-Lösung während eines bestimmten Zeitraums (z. B. 30 min) und eine sich anschließende visuelle Beurteilung der Oxidschicht ermittelt. Die Werte a bis e bedeuten keinen (a) bis starken (e) Oxidschichtangriff, es werden nur ganze Stufen angegeben.The alkali resistance of the surface is determined by immersing a piece of plate not provided with a radiation-sensitive layer in an aqueous dilute NaOH solution for a certain period of time (for example 30 minutes) and then visually assessing the oxide layer. The values a to e mean no (a) to strong (e) oxide layer attack, only whole steps are given.

Als strahlungsempfindliche Schicht wird entweder eine negativ-arbeitende mit einem Gehalt an einem Umsetzungsprodukt von Polyvinylbutyral mit Propenylsulfonylisocyanat, einem Polykondensationsprodukt aus 1 Mol 3-Methoxy- diphenylamin-4-diazoniumsulfat und 1 Mol 4,4'-Bismethoxymethyl-diphenylether ausgefällt als Mesitylensulfonat, H3P04, Viktoriareinblau FGA und Phenylazodiphenylamin oder eine positiv-arbeitende mit einem Gehalt an einem Kresol-Formaldehyd-Novolak, 4-(2-Phenylprop-2-yl)-phenylester der Naphthochinon-(1,2)-diazid-(2)-sulfonsäure-(4), Polyvinylbutyral, Naphthochinon-(1,2)-diazid-(2)-sulfonsäurechlorid-(4) und Kristallviolett auf das Trägermaterial aufgebracht. Es lassen sich so praxisgerechte Druckplatten und Druckformen daraus erstellen.As a radiation-sensitive layer, either a negative-working layer containing a reaction product of polyvinyl butyral with propenylsulfonyl isocyanate, a polycondensation product of 1 mol of 3-methoxy-diphenylamine-4-diazonium sulfate and 1 mol of 4,4'-bismethoxymethyl-diphenyl ether is precipitated as mesitylene sulfonate, H 3 P0 4 , Viktoriareinblau FGA and phenylazodiphenylamine or a positive working with a content of a cresol-formaldehyde novolak, 4- (2-phenylprop-2-yl) phenyl ester of the naphthoquinone- (1,2) -diazid- (2nd ) -sulfonic acid- (4), polyvinyl butyral, naphthoquinone- (1,2) -diazide- (2) -sulfonic acid chloride- (4) and crystal violet applied to the support material. Practical printing plates and printing forms can be created from it.

Vergleichsbeispiel V 1Comparative Example V1

Ein Aluminiumband wird in einer wäßrigen, 1,4 % an HNO3 und 6 % an Al(NO3)3 enthaltenden Lösung mit Wechselstrom (115 A/dm2 bei 35 °C) elektrochemisch aufgerauht und in einer wäßrigen H2S04 und AI3+-lonen enthaltenden Lösung mit Gleichstrom anodisch oxidiert. Die nicht nachbehandelte Oxidschicht wird in der Farbstoffadsorption mit 3 und in der Alkaliresistenz mit a bewertet.An aluminum strip is electrochemically roughened in an aqueous solution containing 1.4% of HNO 3 and 6% of Al (NO 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 untreated oxide layer is rated 3 in dye adsorption and a in alkali resistance.

Vergleichsbeispiel V 2Comparative Example V2

Es wird nach V 1 verfahren, aber in einer wäßrigen, 0,9 % an HCI enthaltenden Lösung aufgerauht; die Farbstoffadsorption wird mit 5 und die Alkaliresistenz mit a bewertet.The procedure of V 1 is followed, but roughened in an aqueous solution containing 0.9% of HCl; dye adsorption is rated 5 and alkali resistance a.

Vergleichsbeispiel V 3Comparative Example V 3

Es wird nach V 1 verfahren, Probestücke des Bandes aber in einer wäßrigen, 4 % an Na2Si03 enthaltenden Lösung während 30 sec bei 40 °C durch Tauchen nachbehandelt ; die nachbehandelte Oxidschicht wird in der Farbstoffadsorption mit 3,5 und in der Alkaliresistenz mit a bewertet.The procedure of V 1 is followed, but test pieces of the tape are after-treated in an aqueous solution containing 4% of Na 2 Si0 3 for 30 seconds at 40 ° C. by dipping; the post-treated oxide layer is rated 3.5 in dye adsorption and a in alkali resistance.

Vergleichsbeispiel V 4Comparative Example V 4

Es wird nach V 2 verfahren, Probestücke des Bandes aber in einer wäßrigen, 4 % an Na2Si03 enthaltenden Lösuhg während 30 sec bei 40 °C durch Tauchen nachbehandelt ; die nachbehandelte Oxidschicht wird in der Farbstoffadsorption mit 3 und der Alkaliresistenz mit a bewertet.The procedure according to V 2 is followed, but test pieces of the strip are after-treated in an aqueous solution containing 4% of Na 2 Si0 3 for 30 seconds at 40 ° C. by dipping; the post-treated oxide layer is rated 3 in dye adsorption and a in alkali resistance.

Vergleichsbeispiel V 5Comparative Example V 5

Es wird nach V 1 verfahren, Probestücke des Bandes aber in einer wäßrigen, 4 % an Na2Si03 enthaltenden Lösung während 30 sec bei 25 °C elektrochemisch (40 V Gleichspannung) nachbehandelt ; die nachbehandelte Oxidschicht wird in der Farbstoffadsorption mit 1 und in der Alkaliresistenz mit a bewertet.The procedure is according to V 1, but test pieces of the strip are aftertreated electrochemically (40 V DC) for 30 seconds at 25 ° C. in an aqueous solution containing 4% of Na 2 Si0 3 ; the post-treated oxide layer is rated 1 in dye adsorption and a in alkali resistance.

Vergleichsbeispiel V 6Comparative Example V 6

Es wird nach V 2 verfahren, Probestücke des Bandes aber in einer wäßrigen, 4 % an Na2Si03 enthaltenden Lösung während 30 sec bei 25 °C elektrochemisch (40 V Gleichspannung) nachbehandelt ; die nachbehandelte Oxidschicht wird in der Farbstoffadsorption mit 1,5 und in der Alkaliresistenz mit a bewertet.The procedure is V 2, but test pieces of the strip are aftertreated electrochemically (40 V DC) for 30 seconds at 25 ° C. in an aqueous solution containing 4% of Na 2 Si0 3 ; the post-treated oxide layer is rated 1.5 in dye adsorption and a in alkali resistance.

Vergleichsbeispiel V 7Comparative Example V 7

Es wird nach V 1 verfahren, Probestücke des Bandes aber in einer wäßrigen, 0,5 % an Polyvinylphosphonsäure enthaltenden Lösung während 30 sec bei 60 °C durch Tauchen nachbehandelt ; die nachbehandelte Oxidschicht wird in der Farbstoffadsorption mit 1,5 und in der Alkaliresistenz mit d bewertet.The procedure of V 1 is followed, but test pieces of the tape are after-treated by immersion at 60 ° C. for 30 seconds in an aqueous solution containing 0.5% of polyvinylphosphonic acid; the post-treated oxide layer is rated 1.5 in dye adsorption and d in alkali resistance.

Vergleichsbeispiel V 8Comparative Example V 8

Es wird nach V 2 verfahren, Probestücke des Bandes aber in einer wäßrigen, 0,5 % an Polyvinylphosphonsäure enthaltenden Lösung während 30 sec bei 60 °C durch Tauchen nachbehandelt ; die nachbehandelte Oxidschicht wird in der Farbstoffadsorption mit 2 und in der Alkaliresistenz mit e bewertet.The procedure of V 2 is followed, but test pieces of the tape are after-treated by immersion at 60 ° C. for 30 seconds in an aqueous solution containing 0.5% of polyvinylphosphonic acid; the post-treated oxide layer is rated 2 in dye adsorption and e in alkali resistance.

Vergleichsbeispiel V 9Comparative Example V 9

Es wird nach V 1 verfahren, Probestücke des Bandes aber in einer wäßrigen, 0,5 % an Polyvinylphosphonsäure enthaltenden Lösung während 30 sec bei 25 °C elektrochemisch (50 V Gleichspannung) nachbehandelt ; die nachbehandelte Oxidschicht wird in der Farbstoffadsorption mit 1 und in der Alkaliresistenz mit a bewertet.The procedure is according to V 1, but test pieces of the strip are after-treated electrochemically (50 V DC) for 30 seconds at 25 ° C. in an aqueous solution containing 0.5% polyvinylphosphonic acid; the post-treated oxide layer is rated 1 in dye adsorption and a in alkali resistance.

Vergleichsbeispiel V 10Comparative Example V 10

Es wird nach V 2 verfahren, Probestücke des Bandes aber in einer wäßrigen, 0,5 % an Polyvinylphosphonsäure enthaltenden Lösung während 30 sec bei 25 °C elektrochemisch (50 V Gleichspannung) nachbehandelt ; die nachbehandelte Oxidschicht wird in der Farbstoffadsorption mit 1 und in der Alkaliresistenz mit d bewertet.The procedure is according to V 2, but test pieces of the tape are after-treated electrochemically (50 V DC) for 30 seconds at 25 ° C. in an aqueous solution containing 0.5% of polyvinylphosphonic acid; the post-treated oxide layer is rated 1 in dye adsorption and d in alkali resistance.

Beispiel 1example 1

Es wird nach V 3 und anschließend nach V 7 verfahren ; die zweistufig nachbehandelte Oxidschicht wird in der Farbstoffadsorption mit 0,5 und in der Alkaliresistenz mit b bewertet.The procedure is V 3 and then V 7; the two-stage post-treated oxide layer is rated 0.5 in dye adsorption and b in alkali resistance.

Beispiel 2Example 2

Es wird nach V 4 und anschließend nach V 8 verfahren ; die zweistufig nachbehandelte Oxidschicht wird in der Farbstoffadsorption mit 0,5 und in der Alkaliresistenz mit b bewertet.The procedure is V 4 and then V 8; the two-stage post-treated oxide layer is rated 0.5 in dye adsorption and b in alkali resistance.

Vergleichsbeispiel V 11Comparative Example V 11

Es wird nach V 7 und anschließen nach V 3 verfahren : die zweistufig nachbehandelte Oxidschicht wird in der Farbstoffadsorption mit 1,5 und in der Alkaliresistenz mit b bewertet.The procedure is V 7 and then V 3: the two-stage aftertreated oxide layer is rated 1.5 in dye adsorption and b in alkali resistance.

Vergleichsbeispiel V 12Comparative Example V 12

Es wird nach V 8 und anschließend nach V 4 verfahren : die zweistufig nachbehandelte Oxidschicht wird in der Farbstoffadsorption mit 1,5 und in der Alkaliresistenz mit b bewertet.The procedure is V 8 and then V 4: the two-stage aftertreated oxide layer is rated 1.5 in dye adsorption and b in alkali resistance.

Beispiel 3Example 3

Es wird nach Beispiel 1 verfahren, aber in der ersten Stufe enthält die wäßrige Lösung zusätzlich noch 0,1 % an Sr2 '-lonen (in Form von Sr(N03)2) ; die zweistufig nachbehandelte Oxidschicht wird in der Farbstoffadsorption mit 0,5 und in der Alkaliresistenz mit a bewertet.The procedure of Example 1 is followed, but in the first stage the aqueous solution additionally contains 0.1% of Sr 2 ' ions (in the form of Sr (N0 3 ) 2 ); the two-stage post-treated oxide layer is rated 0.5 in dye adsorption and a in alkali resistance.

Beispiel 4Example 4

Es wird nach Beispiel 1 verfahren, aber in der ersten Stufe enthält die wäßrige Lösung zusätzlich noch 0,1 % an Sr2Y-lonen (in Form von Sr(OH)2) und 0.1 % an Lävulinsäure ; die zweistufig nachbehandelte Oxidschicht wird in der Farbstoffadsorption mit 0.5 und in der Alkaliresistenz mit a bewertet.The procedure of Example 1 is followed, but in the first stage the aqueous solution additionally contains 0.1% of Sr 2Y ions (in the form of Sr (OH) 2 ) and 0.1% of levulinic acid; the two-stage post-treated oxide layer is rated 0.5 in dye adsorption and a in alkali resistance.

Beispiele 5 und 6Examples 5 and 6

Es wird nach den Beispielen 3 und 4 verfahren, aber in der Aufrauhstufe gemäß Vergleichsbeispiel V 2 in wäßriger HCI-Lösung aufgerauht ; die zweistufig nachbehandelten Oxidschichten werden in der Farbstoffadsorption jeweils mit 0,5 und in der Alkaliresistenz mit a bewertet.The procedure of Examples 3 and 4 is followed, but roughened in the roughening stage according to Comparative Example V 2 in aqueous HCl solution; the two-stage aftertreated oxide layers are rated 0.5 in dye adsorption and a in alkali resistance.

Beispiel 7Example 7

Es wird nach V 3 und anschließend nach V 9 verfahren ; die zweistufig nachbehandelte Oxidschicht wird in der Farbstoffadsorption mit 1 und in der Alkaliresistenz mit a bewertet.The procedure is V 3 and then V 9; the two-stage post-treated oxide layer is rated 1 in dye adsorption and a in alkali resistance.

Beispiel 8Example 8

Es wird nach V 4 und anschließend nach V 10 verfahren ; die zweistufig nachbehandelte Oxidschicht wird in der Farbstoffadsorption mit 1,5 und in der Alkaliresistenz mit b bewertet.The procedure is V 4 and then V 10; the two-stage post-treated oxide layer is rated 1.5 in dye adsorption and b in alkali resistance.

Claims (11)

1. Process for manufacturing materials in the form of sheets, foils or webs, based on chemically, mechanically and/or electrochemically roughened and anodically oxidised aluminium or an alloy thereof, the aluminium oxide layers of which are post-treated with an alkali metal silicate and at least one hydrophilic, organic, phosphoruscon- taining polymer, which are each present in the form of an aqueous solution, characterised in that the post-treatment of the aluminium oxide layer is performed a) first in an aqueous solution containing an alkali metal silicate and b) then in an aqueous solution containing at least one organic polymer with vinylphosphonic acid units and/or vinylmethylphosphinic acid units.
2. Process as claimed in Claim 1, wherein the solution employed in post-treatment step a) additionally contains alkaline earth metal ions.
3. Process as claimed in Claim 2, wherein water-soluble alkaline earth metal salts, in particular nitrates or hydroxides of calcium or strontium are employed as compounds which yield alkaline earth metal ions.
4. Process as claimed in any of Claims 1 to 3, wherein the solution employed in post-treatment step b) contains polyvinylphosphonic acid.
5. Process as claimed in any of Claims 1 to 4, wherein the solution employed in post-treatment step a) contains 0.5 to 30 % by weight of alkali metal silicate and optionally 0.001 to 0.5 % by weight of alkaline earth metal ions.
6. Process as claimed in any of Claims 1 to 5, wherein the solution employed in post-treatment step b) contains 0.01 to 10% by weight of the organic polymer(s).
7. Process as claimed in Claim 2, wherein the solution employed in post-treatment step a) additionally contains at least one complex-forming substance for alkaline earth metal ions.
8. Process as claimed in any of Claims 1 to 7, wherein the post-treatment steps are performed by an electrochemical and/or by an immersion process, which are each performed over a period of 0.5 to 120 seconds and at a temperature of 15 to 80 °C.
9. Process as claimed in Claim 8, wherein at least one of the post-treatment steps is performed by an electrochemical process, at a current density of 0.1 to 10 Aldm2 and/or a voltage of 1 to 100 V.
10. Process as claimed in any of Claims 1 to 9, wherein the materials are roughened electrochemically or mechanically and · electrochemically, the aqueous electrolyte solution used in the electrochemical roughening step containing HN03 and/or HCI, and are anodically oxidised in a single-step or two-step process, using aqueous solutions containing HzS04 and/or H3P04.
11. Use of the materials manufactured as claimed in any of Claims 1 to 10 as supports for offset printing plates.
EP19850101401 1984-02-21 1985-02-09 Process for a two-step hydrophilizing aftertreatment of aluminium oxide layers with aqueous solutions, and their use in the production of supports for off-set printing plates Expired EP0154200B1 (en)

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DE19843406101 DE3406101A1 (en) 1984-02-21 1984-02-21 METHOD FOR THE TWO-STAGE HYDROPHILIZING TREATMENT OF ALUMINUM OXIDE LAYERS WITH AQUEOUS SOLUTIONS AND THE USE THEREOF IN THE PRODUCTION OF OFFSET PRINT PLATE CARRIERS
DE3406101 1984-02-21

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EP0154200A1 EP0154200A1 (en) 1985-09-11
EP0154200B1 true EP0154200B1 (en) 1987-05-27

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Families Citing this family (215)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6282089A (en) * 1985-10-04 1987-04-15 Fuji Photo Film Co Ltd Preparation of support for planographic printing plate
DE3714059C3 (en) * 1987-04-28 1995-12-07 Vaw Ver Aluminium Werke Ag Material in ribbon or plate form and process for its production and its use as a support for planographic printing forms
JPH07119151B2 (en) * 1987-12-07 1995-12-20 富士写真フイルム株式会社 Support for lithographic printing plates
US5084331A (en) * 1989-01-23 1992-01-28 International Business Machines Corporation Electroerosion recording medium of improved corrosion resistance
US5103550A (en) * 1989-12-26 1992-04-14 Aluminum Company Of America Method of making a food or beverage container
US5238715A (en) * 1989-12-26 1993-08-24 Aluminum Company Of America Food or beverage container or container panel
US5672390A (en) * 1990-11-13 1997-09-30 Dancor, Inc. Process for protecting a surface using silicate compounds
US5480762A (en) * 1990-11-28 1996-01-02 Fuji Photo Film Co., Ltd. Method for preparing lithographic printing plate
US5176947A (en) * 1990-12-07 1993-01-05 International Business Machines Corporation Electroerosion printing plates
US5254430A (en) * 1991-01-31 1993-10-19 Fuji Photo Film Co., Ltd. Presensitized plate having anodized aluminum substrate, hydrophilic layer containing phosphonic or phosphinic compound and photosensitive layer containing O-quinone diazide compound
US5230988A (en) * 1991-03-12 1993-07-27 Fuji Photo Film Co., Ltd. Method of making lithographic printing plate
DE4134143A1 (en) * 1991-10-16 1993-06-24 Hoechst Ag METHOD FOR MANUFACTURING FLAT PRESSURE FORMS AND FLAT PRINTING MAKES PRODUCED THEREOF
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
DE69426123T2 (en) * 1993-09-29 2001-06-07 Bayer Ag Process for improving the hydrophilicity of the substrate for a lithographic printing plate by treatment with polyvinylphosphonic acid solution
DE69512321T2 (en) 1994-06-16 2000-05-11 Kodak Polychrome Graphics Llc Lithographic printing plates with an oleophilic imaging layer
US5736256A (en) * 1995-05-31 1998-04-07 Howard A. Fromson Lithographic printing plate treated with organo-phosphonic acid chelating compounds and processes relating thereto
JPH09160233A (en) * 1995-11-17 1997-06-20 Hoechst Ag Radiation-sensitive recording material for manufacture of planographic printing plate
JP3506295B2 (en) 1995-12-22 2004-03-15 富士写真フイルム株式会社 Positive photosensitive lithographic printing plate
JP3830114B2 (en) * 1997-09-29 2006-10-04 富士写真フイルム株式会社 Positive photosensitive lithographic printing plate
GB9825822D0 (en) * 1998-11-16 1999-01-20 Agfa Gevaert Ltd Production of lithographic printing plate support
GB2343680A (en) * 1998-11-16 2000-05-17 Agfa Gevaert Nv Lithographic printing plate support
DE60042764D1 (en) 1999-05-21 2009-09-24 Fujifilm Corp Photosensitive composition and planographic printing plate base therewith
US6255042B1 (en) 1999-11-24 2001-07-03 Kodak Polychrome Graphics, Llc Developing system for alkaline-developable lithographic printing plates with different interlayers
US6358616B1 (en) 2000-02-18 2002-03-19 Dancor, Inc. Protective coating for metals
DE60137398D1 (en) 2000-11-30 2009-03-05 Fujifilm Corp Lithographic printing plate precursors
JP4268345B2 (en) * 2001-04-20 2009-05-27 富士フイルム株式会社 Support for lithographic printing plate
ES2195765B1 (en) * 2002-01-29 2005-02-01 Planchas Y Productos Para Offset Lithoplate, S.A. IRON FOR OFFSET PRINTING AND PROCEDURE FOR MANUFACTURING.
US20040067435A1 (en) 2002-09-17 2004-04-08 Fuji Photo Film Co., Ltd. Image forming material
EP2354854B2 (en) 2002-09-20 2016-04-06 FUJIFILM Corporation Method of making lithographic printing plate
EP1464486B1 (en) 2003-03-26 2009-06-17 FUJIFILM Corporation Lithographic printing method and presensitized plate
JP2005105366A (en) 2003-09-30 2005-04-21 Fuji Photo Film Co Ltd Method for manufacturing support for planographic printing plate
US20050153239A1 (en) 2004-01-09 2005-07-14 Fuji Photo Film Co., Ltd. Lithographic printing plate precursor and lithographic printing method using the same
JP2005234118A (en) 2004-02-18 2005-09-02 Fuji Photo Film Co Ltd Photosensitive lithographic printing plate
WO2005111717A2 (en) 2004-05-19 2005-11-24 Fujifilm Corporation Image recording method
US20050263021A1 (en) 2004-05-31 2005-12-01 Fuji Photo Film Co., Ltd. Platemaking method for lithographic printing plate precursor and planographic printing method
JP2006021396A (en) 2004-07-07 2006-01-26 Fuji Photo Film Co Ltd Original lithographic printing plate and lithographic printing method
ATE398298T1 (en) 2004-07-20 2008-07-15 Fujifilm Corp IMAGE-PRODUCING MATERIAL
US7425406B2 (en) 2004-07-27 2008-09-16 Fujifilm Corporation Lithographic printing plate precursor and lithographic printing method
US20060032390A1 (en) 2004-07-30 2006-02-16 Fuji Photo Film Co., Ltd. Lithographic printing plate precursor and lithographic printing method
US20060032756A1 (en) * 2004-08-13 2006-02-16 Justus William D Method for producing anodized and coated expanded aluminum foil material in a continuous process
JP2006058430A (en) 2004-08-18 2006-03-02 Fuji Photo Film Co Ltd Lithography original plate
US7416831B2 (en) * 2004-08-20 2008-08-26 Eastman Kodak Company Substrate for lithographic printing plate precursor
ATE389900T1 (en) 2004-08-24 2008-04-15 Fujifilm Corp METHOD FOR PRODUCING A LITHOGRAPHIC PRINTING PLATE
JP2006062188A (en) 2004-08-26 2006-03-09 Fuji Photo Film Co Ltd Color image forming material and original plate of lithographic printing plate
US7049048B2 (en) * 2004-08-27 2006-05-23 Eastman Kodak Company Alkali resistant polymeric interlayers for lithoplates
DE102004041609B3 (en) 2004-08-27 2006-07-13 Kodak Polychrome Graphics Gmbh Interlayer for lithographic printing plates
JP2006062322A (en) 2004-08-30 2006-03-09 Fuji Photo Film Co Ltd Original plate for planographic printing plate, stacked body thereof, and plate making method
JP5089866B2 (en) 2004-09-10 2012-12-05 富士フイルム株式会社 Planographic printing method
JP4404734B2 (en) 2004-09-27 2010-01-27 富士フイルム株式会社 Planographic printing plate precursor
US20060150846A1 (en) 2004-12-13 2006-07-13 Fuji Photo Film Co. Ltd Lithographic printing method
EP1685957B1 (en) 2005-01-26 2013-12-11 FUJIFILM Corporation Packaged body of lithographic printing plate precursors
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US20060204732A1 (en) 2005-03-08 2006-09-14 Fuji Photo Film Co., Ltd. Ink composition, inkjet recording method, printed material, method of producing planographic printing plate, and planographic printing plate
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Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE540601A (en) * 1950-12-06
US2882153A (en) * 1954-02-04 1959-04-14 Polychrome Corp Planographic printing plate
BE606888A (en) * 1960-08-05 1900-01-01
US3181461A (en) * 1963-05-23 1965-05-04 Howard A Fromson Photographic plate
US3280734A (en) * 1963-10-29 1966-10-25 Howard A Fromson Photographic plate
ZA6807938B (en) * 1967-12-04
AT309942B (en) * 1971-05-18 1973-09-10 Isovolta Process for anodic oxidation of objects made of aluminum or its alloys
US3902976A (en) * 1974-10-01 1975-09-02 S O Litho Corp Corrosion and abrasion resistant aluminum and aluminum alloy plates particularly useful as support members for photolithographic plates and the like
CA1112600A (en) * 1975-11-13 1981-11-17 Shyoichi Anada Electrolytically treating aluminium surface in bath of hydroxide or salt with acid
US4383897A (en) * 1980-09-26 1983-05-17 American Hoechst Corporation Electrochemically treated metal plates
DE3126627A1 (en) * 1981-07-06 1983-01-20 Hoechst Ag, 6000 Frankfurt POLYVINYLMETHYLPHOSPHINIC ACID, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE
DE3126636A1 (en) * 1981-07-06 1983-01-27 Hoechst Ag, 6000 Frankfurt HYDROPHILIZED CARRIER MATERIALS FOR OFFSET PRINTING PLATES, A METHOD FOR THEIR PRODUCTION AND THEIR USE
US4376814A (en) * 1982-03-18 1983-03-15 American Hoechst Corporation Ceramic deposition on aluminum
DE3219922A1 (en) * 1982-05-27 1983-12-01 Hoechst Ag, 6230 Frankfurt METHOD FOR TREATING ALUMINUM OXIDE LAYERS WITH AQUEOUS SOLUTIONS CONTAINING ALKALISILICATE AND THE USE THEREOF IN THE PRODUCTION OF OFFSET PRINT PLATE CARRIERS
DE3232485A1 (en) * 1982-09-01 1984-03-01 Hoechst Ag, 6230 Frankfurt METHOD FOR TREATING ALUMINUM OXIDE LAYERS WITH AQUEOUS SOLUTIONS CONTAINING ALKALISILICATE AND THE USE THEREOF IN THE PRODUCTION OF OFFSET PRINT PLATE CARRIERS
JPS59101651A (en) * 1982-12-02 1984-06-12 Fuji Photo Film Co Ltd Photosensitive lithographic printing plate

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US4689272A (en) 1987-08-25
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CA1236045A (en) 1988-05-03

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