EP0154200B1 - Procédé pour le traitement postérieur hydrophilisant en deux étapes de couches d'oxyde d'aluminium avec solutions aqueuses et leur utilisation pour la fabrication de supports pour plaques d'impression offset - Google Patents

Procédé pour le traitement postérieur hydrophilisant en deux étapes de couches d'oxyde d'aluminium avec solutions aqueuses et leur utilisation pour la fabrication de supports pour plaques d'impression offset 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
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP19850101401
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German (de)
English (en)
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EP0154200A1 (fr
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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Publication of EP0154200A1 publication Critical patent/EP0154200A1/fr
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Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • 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.

Claims (11)

1. Procédé pour la fabrication de matériaux en forme de plaques, de feuilles ou de bandes, à base d'aluminium ou d'un de ses alliages, grainé chimiquement, mécaniquement et/ou électrochimiquement, et oxydé par anodisation, dont les couches d'oxyde d'aluminium sont post-traitées avec un silicate de métal alcalin et au moins un polymère organique hydrophile, contenant du phosphore, chacun d'eux en solution aqueuse, caractérisé en ce que le post-traitement de la couche d'oxyde d'aluminium est effectué a) en premier lieu dans une solution aqueuse contenant un silicate de métal alcalin et b) ensuite dans une solution aqueuse contenant au moins un polymère organique comportant des motifs acide vinylphosphonique et/ou acide vinylméthylphos- phinique.
2. Procédé selon la revendication 1, caractérisé en ce que la solution utilisée dans l'étape de post-traitement a) contient en plus des ions alcalino-terreux.
3. Procédé selon la revendication 2, caractérisé en ce que l'on utilise en tant que composés donnant des ions alcalino-terreux des sels de métaux alcalino-terreux solubles dans l'eau, en particulier des nitrates ou des hydroxydes de calcium ou de strontium.
4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que la solution utilisée dans l'étape de post-traitement b) contient de l'acide polyvinylphosphonique.
5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que la solution utilisée dans l'étape de post-traitement a) contient 0,5 à 30 % en poids d'un silicate de métal alcalin et éventuellement 0,001 à 0,5 % en poids d'ions alcalino-terreux.
6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que la solution utilisée dans l'étape de post-traitement b) contient 0,01 à 10 % en poids du ou des polymères organiques.
7. Procédé selon la revendication 2. caractérisé en ce que la solution utilisée dans l'étape de post-traitement a) contient en outre au moins un complexant d'ions alcalino-terreux.
8. Procédé selon l'une des revendications 1 à 7, caractérisé en ce que les étapes de post-traitement sont effectuées par un traitement électrochimique et/ou par un traitement par immersion, qui sont effectués chacun pendant une durée de 0,5 à 120 secondes, et à une température de 15 à 80 °C.
9. Procédé selon la revendication 8, caractérisé en ce que au moins une des étapes de post-traitement est effectuée par voie électrochimique, avec une densité de courant de 0.1 à 10 A/dm2 et/ou une tension de 1 à 100 V.
10. Procédé selon l'une des revendications 1 à 9, caractérisé en ce que les matériaux sont grainés électrochimiquement ou mécaniquement et électrochimiquement, la solution électrolytique aqueuse utilisée dans l'étape de grainage électrochimique contenant HN03 et/ou HCI, et sont oxydés par anodisation en une ou deux étapes dans des solutions aqueuses contenant HzS04 et/ou H3P04.
11. Utilisation des matériaux produits selon l'une des revendications 1 à 10 en tant que supports pour plaques d'impression offset.
EP19850101401 1984-02-21 1985-02-09 Procédé pour le traitement postérieur hydrophilisant en deux étapes de couches d'oxyde d'aluminium avec solutions aqueuses et leur utilisation pour la fabrication de supports pour plaques d'impression offset Expired EP0154200B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3406101 1984-02-21
DE19843406101 DE3406101A1 (de) 1984-02-21 1984-02-21 Verfahren zur zweistufigen hydrophilierenden nachbehandlung von aluminiumoxidschichten mit waessrigen loesungen und deren verwendung bei der herstellung von offsetdruckplattentraegern

Publications (2)

Publication Number Publication Date
EP0154200A1 EP0154200A1 (fr) 1985-09-11
EP0154200B1 true EP0154200B1 (fr) 1987-05-27

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EP19850101401 Expired EP0154200B1 (fr) 1984-02-21 1985-02-09 Procédé pour le traitement postérieur hydrophilisant en deux étapes de couches d'oxyde d'aluminium avec solutions aqueuses et leur utilisation pour la fabrication de supports pour plaques d'impression offset

Country Status (7)

Country Link
US (1) US4689272A (fr)
EP (1) EP0154200B1 (fr)
JP (1) JPS60194096A (fr)
BR (1) BR8500701A (fr)
CA (2) CA1236045A (fr)
DE (2) DE3406101A1 (fr)
ZA (1) ZA851216B (fr)

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JPS60194096A (ja) 1985-10-02
DE3560202D1 (en) 1987-07-02
CA1239612A (fr) 1988-07-26
CA1236045A (fr) 1988-05-03
ZA851216B (en) 1985-10-30
DE3406101A1 (de) 1985-08-22
US4689272A (en) 1987-08-25
BR8500701A (pt) 1985-10-08
EP0154200A1 (fr) 1985-09-11

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