EP0154201B1 - Procédé pour le traitement postérieur de couches d'oxyde d'aluminium avec solutions aqueuses contenant du silicate de métal alcalin et leur utilisation pour la fabrication de supports pour plaques d'impression offset - Google Patents

Procédé pour le traitement postérieur de couches d'oxyde d'aluminium avec solutions aqueuses contenant du silicate de métal alcalin et leur utilisation pour la fabrication de supports pour plaques d'impression offset Download PDF

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Publication number
EP0154201B1
EP0154201B1 EP85101402A EP85101402A EP0154201B1 EP 0154201 B1 EP0154201 B1 EP 0154201B1 EP 85101402 A EP85101402 A EP 85101402A EP 85101402 A EP85101402 A EP 85101402A EP 0154201 B1 EP0154201 B1 EP 0154201B1
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EP
European Patent Office
Prior art keywords
aqueous solution
post
alkaline earth
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
EP85101402A
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German (de)
English (en)
Other versions
EP0154201A1 (fr
Inventor
Ulrich Dr. Dipl.-Chem. Simon
Reiner Beutel
Gerhard Dr. Dipl.-Chem. Sprintschnik
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0154201A1 publication Critical patent/EP0154201A1/fr
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Publication of EP0154201B1 publication Critical patent/EP0154201B1/fr
Expired legal-status Critical Current

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Classifications

    • 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
    • C25D11/20—Electrolytic after-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment

Definitions

  • the invention relates to an aftertreatment process for roughened and anodically oxidized aluminum, in particular of support materials for offset printing plates with aqueous solutions containing alkali metal silicate.
  • 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 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 in order to produce the hydrophilic non-image areas.
  • 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 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:
  • EP-A 0 095 581 describes an aftertreatment process for aluminum oxide layers, aftertreatment being carried out with an alkali silicate solution which additionally contains at least one aliphatic hydroxymono-, di- or tricarboxylic acid, an aliphatic dicarboxylic acid or a water-soluble salt of these acids.
  • 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 Silikalmaschinesclar improved in effect.
  • the invention is based on the known process for the production of plate, foil or tape-shaped materials based on electrochemically in an aqueous solution containing nitric acid or mechanically and electrochemically roughened and anodically oxidized aluminum or one of its alloys containing nitric acid.
  • the aluminum oxide layers are aftertreated with an aqueous solution containing alkali metal silicate.
  • the invention is then characterized in that the aftertreatment is carried out with an aqueous solution containing alkali metal silicate and alkaline earth metal cations.
  • 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 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 tetrasilicates contained in the water glass) and 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, aminocarboxylic acids, nitrogen or hydroxy compounds containing hydroxyl or carboxyl groups (for example levulinic acid, ethylenediaminetetraacetic acid or salts thereof).
  • at least one complexing agent for alkaline earth metal ions such as hydroxycarboxylic acids, aminocarboxylic acids, nitrogen or hydroxy compounds containing hydroxyl or carboxyl groups (for example levulinic acid, ethylenediaminetetraacetic acid or salts thereof).
  • the aftertreatment can be carried out as an immersion treatment or also 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 A / dm 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 materials in which the retention of this topography plays a major role, for example for printing plate support materials.
  • Suitable base materials for the material to be treated according to the invention include those made of aluminum or one of its alloys, which have, for example, a content of more than 98.5% by weight of Al and proportions of Si, Fe, Ti, Cu and Zn.
  • These aluminum carrier materials can also be roughened mechanically (for example by brushing with wire or nylon brushes and / or with abrasive treatments), if necessary after pre-cleaning, before the electrochemical stage will. 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 continuous process control, in the electrochemical roughening stage are in the following ranges: the temperature of the aqueous electrolyte, in particular 0.3 to 3.0% by weight of nitric acid (HNO 3 ), between 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 sec and the electrolyte flow rate at 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.
  • HNO 3 nitric acid
  • alternating current of a frequency of 50 to 80 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.
  • aluminum ions in the form of aluminum salts in particular Al (NO 3 ) 3
  • Al (NO 3 ) 3 can also be added to the aqueous electrolyte; the addition of certain other acids and salts such as boric acid or borates or of corrosion inhibitors such as amines is also known.
  • the aftertreatment according to the invention is surprisingly effective only after roughening in aqueous electrolytes based on HNO 3 , but not, for example, after roughening in an electrolyte based on HCl.
  • 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 (up to 5 g / m 2 between the stages);
  • aqueous solutions of alkali metal hydroxide or aqueous solutions of alkaline salts or aqueous acid solutions based on HN0 3 , H 2 SO 4 or H 3 PO 4 are used as abrasive solutions.
  • non-electrochemical treatments which essentially have only a rinsing and / or cleaning effect and for example to remove deposits formed during roughening (“Schmant •) or simply serve to remove electrolyte residues; For example, dilute aqueous alkali hydroxide solutions or water are used for these purposes.
  • anodic oxidation of the aluminum follows in a further process step, for example to improve the abrasion and adhesion properties of the surface of the carrier material.
  • the usual electrolytes such as H 2 S0 4 , H 3 P0 4 , H 2 C 2 0 4 , amidosulfonic acid, sulfosuccinic acid, sulfosalicylic acid or mixtures thereof can be used for anodic oxidation; in particular, H 2 S0 4 and H 3 P0 4 are used alone, in a mixture and / or in a multi-stage anodizing process.
  • 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 image-like area from which printing can take place.
  • photoconductive layers such as z. B. in DE-C 11 17 391, 15 22 497, 15 72 312, 23 22 046 and 23 22 047 are described, applied to the carrier materials produced according to the invention, whereby highly light-sensitive, electrophotographic printing plates are formed.
  • coated offset printing plates obtained from the carrier materials produced according to the invention are converted into the desired printing form in a known manner by imagewise exposure or irradiation and washing out of the non-image areas with a developer, preferably an aqueous developer solution.
  • offset printing plates the base support materials of which have been post-treated by the process according to the invention, are distinguished from those in which the same base material has been post-treated with aqueous solutions containing only alkali metal silicates, by improved hydrophilicity of the non-image areas, 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.
  • An aluminum strip is electrochemically roughened in an aqueous solution containing 1.4% of HN0 3 and 6% of Al (N0 3 ) 3 using alternating current (115 A / dm 2 at 35 ° C.) and in an aqueous H 2 S0 4 and Al 3+ ion containing solution anodized with direct current.
  • the 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 strip are after-treated in an aqueous solution containing 4% of Na 2 SiO 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 after-treated electrochemically (40 V DC) for 30 seconds at 25 ° C. in an aqueous solution containing 4% of Na 2 SiO 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.
  • test pieces of the tape are in an aqueous solution containing 4% of Na z Si0 3 for 30 seconds at 40 ° C. in the first stage and in a 0.1% Sr 2 + ion [in the form after-treatment of Sr (NO 3 ) 2 ] in aqueous solution in the second stage for 10 seconds at 25 ° C. by immersion; the two-stage post-treated oxide layer is rated 2.5 in dye adsorption and a in alkali resistance.
  • Example 1 The procedure of Example 1 is followed, but after-treated electrochemically (25 V DC) for 30 seconds at 25 ° C .; the oxide layer aftertreated according to the invention is rated 0.5 in dye adsorption and a in alkali resistance.
  • Example 1 The procedure of Example 1 is followed, but the electrochemical roughening step is carried out in aqueous HCl solution; the post-treated oxide layer is rated 4 in dye adsorption and a in alkali resistance.

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

Claims (11)

1. Procédé pour la production de matériaux en forme de plaques, feuilles ou bandes, à base d'aluminium ou d'un de ses alliages, grainé électrochimiquement dans une solution aqueuse contenant de l'acide nitrique, ou mécaniquement et électrochimiquement dans une solution contenant de l'acide nitrique, et oxydé par anodisation, dont les couches d'oxyde d'aluminium sont post- traitées avec une solution aqueuse contenant un silicate d'un métal alcalin, caractérisé en ce que l'on effectue le post-traitement avec une solution aqueuse contenant un silicate d'un métal alcalin et des cations de métaux alcalino-terreux.
2. Procédé selon la revendication 1, 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.
3. Procédé selon la revendication 2, caractérisé en ce que l'on utilise en tant que sels de métaux alcalino-terreux des sels, 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, dans le post-traitement, la solution aqueuse contient 0,5 à 30 % en poids de silicate de métal alcalin et 0,001 à 0,5 % en poids d'ions alcalino-terreux.
5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que, dans le post-traitement, la solution aqueuse contient 1 à 15 % en poids de silicate de métal alcalin et 0,005 à 0,3 % en poids d'ions alcalinoaterreux.
6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que, dans le post-traitement, la solution aqueuse contient en outre au moins un agent complexant d'ions alcalino-terreux.
7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que l'on effectue le post-traitement électrochimiquement ou par un traitement par immersion, pendant une durée de 0,5 à 120 secondes et à une température de 15 à 80 °C.
8. Procédé selon la revendication 7, caractérisé en ce que l'on effectue le post-traitement électrochimiquement à une densité de courant de 0,1 à 10 A/dm2 et/ou à une tension de 1 à 100 V.
9. Procédé selon l'une des revendications 1 à 8, caractérisé en ce que les matériaux sont grainés électrochimiquement dans une solution aqueuse contenant 0,3 à 3,0 % en poids d'acide nitrique.
10. Procédé selon l'une des revendications 1 à 9, caractérisé en ce que les matériaux sont oxydés par anodisation en une ou deux étapes dans des solutions aqueuses contenant H2S04 et/ou H3PO4.
11. Utilisation du procédé selon l'une des revendications 1 à 10, pour la production d'un matériau de support pour plaques d'impression offset.
EP85101402A 1984-02-21 1985-02-09 Procédé pour le traitement postérieur de couches d'oxyde d'aluminium avec solutions aqueuses contenant du silicate de métal alcalin et leur utilisation pour la fabrication de supports pour plaques d'impression offset Expired EP0154201B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3406102 1984-02-21
DE19843406102 DE3406102A1 (de) 1984-02-21 1984-02-21 Verfahren zur nachbehandlung von aluminiumoxidschichten mit alkalimetallsilikat enthaltenden waessrigen loesungen und deren verwendung bei der herstellung von offsetdruckplattentraegern

Publications (2)

Publication Number Publication Date
EP0154201A1 EP0154201A1 (fr) 1985-09-11
EP0154201B1 true EP0154201B1 (fr) 1987-08-19

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EP85101402A Expired EP0154201B1 (fr) 1984-02-21 1985-02-09 Procédé pour le traitement postérieur de couches d'oxyde d'aluminium avec solutions aqueuses contenant du silicate de métal alcalin et leur utilisation pour la fabrication de supports pour plaques d'impression offset

Country Status (5)

Country Link
EP (1) EP0154201B1 (fr)
JP (1) JPS60194095A (fr)
BR (1) BR8500702A (fr)
DE (2) DE3406102A1 (fr)
ZA (1) ZA851217B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0514312A1 (fr) * 1991-05-16 1992-11-19 Sers, S.A. Plaque d'impression offset et son procédé de fabrication
EP0683248A1 (fr) 1994-05-21 1995-11-22 Hoechst Aktiengesellschaft Procédé de post-traitement de plaques, feuilles ou bandes et son application comme support pour plaques d'impression

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3717757A1 (de) * 1986-05-26 1987-12-03 Fuji Photo Film Co Ltd Verfahren zur herstellung eines traegers fuer die verwendung in der herstellung einer lithografischen druckplatte
JP2639693B2 (ja) * 1988-06-17 1997-08-13 富士写真フイルム株式会社 感光性平版印刷版の現像処理方法
JP2538793B2 (ja) * 1988-07-29 1996-10-02 富士写真フイルム株式会社 感光性平版印刷版の現像液
JP2004106200A (ja) * 2002-09-13 2004-04-08 Fuji Photo Film Co Ltd 平版印刷版用支持体、その製造方法および平版印刷版原版

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2882153A (en) * 1954-02-04 1959-04-14 Polychrome Corp Planographic printing plate
DE3219922A1 (de) * 1982-05-27 1983-12-01 Hoechst Ag, 6230 Frankfurt Verfahren zur nachbehandlung von aluminiumoxidschichten mit alkalisilikat enthaltenden waessrigen loesungen und dessen verwendung bei der herstellung von offsetdruckplattentraegern
DE3232485A1 (de) * 1982-09-01 1984-03-01 Hoechst Ag, 6230 Frankfurt Verfahren zur nachbehandlung von aluminiumoxidschichten mit alkalisilikat enthaltenden waessrigen loesungen und dessen verwendung bei der herstellung von offsetdruckplattentraegern

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0514312A1 (fr) * 1991-05-16 1992-11-19 Sers, S.A. Plaque d'impression offset et son procédé de fabrication
EP0683248A1 (fr) 1994-05-21 1995-11-22 Hoechst Aktiengesellschaft Procédé de post-traitement de plaques, feuilles ou bandes et son application comme support pour plaques d'impression
US5556531A (en) * 1994-05-21 1996-09-17 Agfa-Gevaert Ag Process for the aftertreatment of aluminum materials substrates of such materials and their use for offset printing plates
US5770315A (en) * 1994-05-21 1998-06-23 Agfa-Gevaert Ag Process for the aftertreatment of aluminum materials, substrates of such materials, and their use for offset printing plates

Also Published As

Publication number Publication date
DE3406102A1 (de) 1985-08-22
DE3560489D1 (en) 1987-09-24
ZA851217B (en) 1985-10-30
BR8500702A (pt) 1985-10-08
EP0154201A1 (fr) 1985-09-11
JPS60194095A (ja) 1985-10-02

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