EP0095581B1 - Procédé de post traitement de couches d'oxyde d'aluminium avec des solutions aqueuses contenant silicate alcalin et son application dans la fabrication de supports de plaques d'impression offset - Google Patents

Procédé de post traitement de couches d'oxyde d'aluminium avec des solutions aqueuses contenant silicate alcalin et son application dans la fabrication de supports de plaques d'impression offset Download PDF

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Publication number
EP0095581B1
EP0095581B1 EP83104145A EP83104145A EP0095581B1 EP 0095581 B1 EP0095581 B1 EP 0095581B1 EP 83104145 A EP83104145 A EP 83104145A EP 83104145 A EP83104145 A EP 83104145A EP 0095581 B1 EP0095581 B1 EP 0095581B1
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EP
European Patent Office
Prior art keywords
aqueous
aluminum
acid
und
der
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Expired
Application number
EP83104145A
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German (de)
English (en)
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EP0095581A3 (en
EP0095581A2 (fr
Inventor
Gerhard Dr. Dipl.-Chem. Usbeck
Hans Block
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Hoechst AG
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Hoechst AG
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Publication of EP0095581A2 publication Critical patent/EP0095581A2/fr
Publication of EP0095581A3 publication Critical patent/EP0095581A3/de
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Publication of EP0095581B1 publication Critical patent/EP0095581B1/fr
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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
    • B41N3/034—Chemical or electrical pretreatment characterised by the electrochemical treatment of the aluminum support, e.g. anodisation, electro-graining; Sealing of the anodised layer; Treatment of the anodic layer with inorganic compounds; Colouring of the anodic layer
    • 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
    • C25D11/246—Chemical after-treatment for sealing layers

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 silicate.
  • Carrier materials for offset printing plates are provided either directly by the consumer or by the manufacturer of precoated printing plates on one or both sides with a radiation-sensitive layer (reproduction layer), with the aid of which a printing image of a template is generated in a photomechanical way.
  • the layer support carries the image areas which will guide the color during later printing and at the same time forms the hydrophilic image background for the lithographic printing process at the areas which are later free of image (non-image areas).
  • Aluminum, steel, copper, brass or zinc, but also plastic films or paper can be used as the base material for such layers. These raw materials are processed by suitable operations such as. B. grain, matt chrome plating, surface oxidation and / or application of an intermediate layer in layer support for offset printing plates.
  • the suitable aqueous solutions should contain at a pH of 5 to 6 citric acid, tartaric acid, gallic acid, sugar acid or their alkali, ammonium or alkaline earth salts; an application in the printing plate field is not mentioned.
  • the complexing agents include amines, amino acids and sulfonic acids.
  • Phenols and glycols also salts of organic carboxylic acids such as maleic acid, fumaric acid, citric acid or tartaric acid.
  • This anodic oxidation reaction is generated directly on the aluminum, ie without the formation of an aluminum oxide layer in the meantime by anodic oxidation in H 2 SO 4 or H 3 PO 4 .
  • the electrolyte concentrations should preferably be between 0.1 and 15% by weight for the silicate and between 1 and 12% by weight for the complexing agent.
  • the preferred process parameters are: the temperature between 15 and 40 ° C, the coating time between 0.5 and 5 min, the current density between 0.5 and 3 A / dm 2 .
  • a printing plate support material was in Example 9 in an electrolyte containing 9.2% by weight of sodium silicate, 6.3% by weight of monoethanolamine and 0.9% by weight of sodium potassium tartrate at a current density of 3 A / dm2 for 15 min and anodized at 45 to 50 ° C.
  • the process for the production of grain-like or grained surfaces on aluminum according to DE-AS 26 51 346 is carried out directly on aluminum with alternating current in an electrolyte which is 0.01 to 0.5 mol / l in aqueous solution contains an alkali or alkaline earth metal hydroxide or salt and optionally 0.01 to 0.5 mol / 1 of a barrier layer former.
  • a coloring treatment is carried out, optionally after previous anodic oxidation.
  • To the barrier layer formers u. a. also include citric acid, tartaric acid, succinic acid, lactic acid, malic acid or their salts.
  • Example 5 No anodic oxidation of the aluminum is carried out before the grain-like or grained surface is produced.
  • the aluminum substrate to be treated is hung vertically in the electrolytic bath in order to achieve the desired grain.
  • an aqueous electrolyte with a content of 10 g / l of Na orthosilicate and 30 g / l of Na tartrate was used at a current density of 3 A / dm 2 for 15 minutes.
  • the products produced in this way are said to be suitable for the production of window frames, wall panels (paneling) and decorative moldings for vehicles or household articles.
  • 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.
  • the invention is based on the known process for the production of plate, sheet or strip materials based on chemically, mechanically and / or electrochemically roughened and anodically oxidized aluminum or one of its alloys, the aluminum oxide layers of which are post-treated with an aqueous alkali silicate solution.
  • the process according to the invention is then characterized in that the aftertreatment with an aqueous alkali silicate Solution is carried out, which additionally contains at least one aliphatic hydroxy mono-, di- or tricarboxylic acid, an aliphatic dicarboxylic acid or a water-soluble salt of these acids. Materials treated in this way are used in particular as supports for offset printing plates.
  • the aliphatic carboxylic acids which can be used in the process according to the invention include, in particular, hydroxytricarboxylic acids such as citric acid, hydroxydicarboxylic acids such as tartaric or malic acid, hydroxymonocarboxylic acids such as glycolic, lactic or gluconic acid or dicarboxylic acids such as oxalic, malonic, maleic or succinic acid.
  • hydroxytricarboxylic acids such as citric acid
  • hydroxydicarboxylic acids such as tartaric or malic acid
  • hydroxymonocarboxylic acids such as glycolic, lactic or gluconic acid or dicarboxylic acids
  • oxalic, malonic, maleic or succinic acid oxalic, malonic, maleic or succinic acid.
  • the corresponding water-soluble salts such as alkali or ammonium salts are preferably used, since they only slightly change the pH of the aqueous alkali silicate solution; this should suit
  • the treatment can be carried out as an immersion treatment or electrochemically, the latter procedure often bringing an increase in the resistance to alkali.
  • 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 .
  • the treatment of the materials can be carried out batchwise or continuously in modern conveyor systems, the treatment times are expediently in the range of 5 to '120 seconds and the treatment temperature at 15 to 80 ° C, especially at 40 to 75 ° C.
  • the aqueous solution generally contains 1 to 50 g / l, in particular 5 to 30 g / l, of an alkali silicate (such as sodium metasilicate or the sodium and silicate contained in the "water glass") and 3 to 50 g / l I, in particular 5 to 20 g / I, one of the acids and / or salts mentioned above.
  • the weight ratio of silicate to acid / salt is preferably in the range from 1: 1 to 4: 1.
  • the aluminum support materials for printing plates encountered in practice are mechanically (e.g. by brushing and / or with abrasive treatments), chemically (e.g. by etching agents) or electrochemically (e.g. by AC treatment in aqueous HCI and / or HN0 3 before applying the light-sensitive layer Solutions) roughened.
  • Aluminum printing plates with electrochemical roughening are used in particular for the present invention.
  • the process parameters in the roughening stage are in the following ranges: the temperature of the electrolyte between 20 and 60 ° C, the active substance (acid, salt) concentration between 5 and 100 g / I, the current density between 15 and 130 A / dm 2 , the residence time between 10 and 100 sec and the electrolyte flow rate in continuous processes on the surface of the workpiece to be treated between 5 and 100 cm / sec; AC is usually used as the type of current, but modified types of current such as AC with different amplitudes of the current strength are also possible for the anode and cathode currents.
  • the average roughness depth R z of the roughened surface is in the range from about 1 to 15 ⁇ m, in particular in the range from 2 to 8 ⁇ m.
  • the roughness depth is determined in accordance with DIN 4768 in the version from October 1970, the roughness depth R z is then the arithmetic mean of the individual roughness depths of five adjacent individual measuring sections.
  • Direct current is preferably used for the anodic oxidation, however alternating current or a combination of these types of current (eg direct current with superimposed alternating current) can also be used; the electrolyte is in particular an aqueous solution containing H 3 PO 4 .
  • the layer weights of aluminum oxide range from 1 to 10 g / m 2 , corresponding to a layer thickness of approximately 0.3 to 3.0 ⁇ m.
  • all layers are suitable as light-sensitive layers which, after exposure, optionally with subsequent development and / or fixation, provide an imagewise surface from which printing can take place. They are either applied to the substrate by the manufacturer of presensitized printing plates or directly by the consumer.
  • photoconductive layers such as z. B. in DE-PSen 11 17391, 15 22 497, 1572312, 2322046 and 2322047 are described, to those produced according to the invention Carrier materials are applied, which creates highly light-sensitive, electrophotographic printing plates.
  • offset printing plates obtained from the carrier materials provided according to the invention are converted into the desired printing form in a known manner by imagewise exposure or irradiation and washing out the non-image areas with a developer, preferably an aqueous developer solution.
  • a developer preferably an aqueous developer solution.
  • offset printing plates the base support materials of which have been post-treated by the processes according to the invention, are distinguished from such plates in which the same base material has been post-treated with aqueous solutions containing only silicates, by improved hydrophilicity of the non-image areas, a lower tendency to color fog binding, improved alkali resistance and Achieve a steeper gradation (measured with a halftone step part).
  • the hydrophilicity of the carrier materials produced according to the invention is checked using wetting angle measurements in relation to a drop of water placed on it, the angle between the carrier surface and a tangent through the point of contact of the drop being determined, it is generally between 0 and 90 °. The smaller the angle, the better the wetting.
  • Zinc certificate (according to US Pat. No. 3,940,321, columns 3 and 4, lines 29 to 68 and lines 1 to 8):
  • the rate at which the layer dissolves in an alkaline zincate solution is used as a measure of the alkali resistance of an aluminum oxide layer.
  • the layer is more alkali-resistant the longer it takes to dissolve it.
  • the layer thicknesses should be roughly comparable, since of course they also represent a parameter for the dissolution rate.
  • a drop of a solution of 500 ml of distilled H 2 O, 480 g of KOH and 80 g of zinc oxide is placed on the surface to be examined and the period of time until the appearance of metallic zinc is determined, which can be seen from the darkening of the examination site.
  • the sample of a defined size protected on the back by a layer of lacquer is moved in a bath containing an aqueous solution of 6 g / l of NaOH.
  • the weight loss experienced in this bath is determined gravimetrically and is given in g / m 2 . Times of 1, 2, 4 or 8 minutes are selected as the treatment time in the alkaline bath.
  • An aluminum foil is electrochemically roughened in dilute aqueous HN0 3 solution with alternating current and anodically oxidized in dilute aqueous H 3 SO 4 solution with direct current.
  • the subsequent treatment is carried out either only with Na 2 SiO 3 . 5H 2 0 (comparative examples V2, V3), carried out only with KN tartrate (comparative example V4) or with a mixture of the two components (examples 1 to 3) and compared with a film without any aftertreatment (comparative example V1).
  • the test conditions and results can be found in the table below.
  • An aluminum foil is roughened electrochemically in a dilute aqueous HCl or NHO 3 solution using alternating current and anodically oxidized in a dilute aqueous H 2 S0 4 or H 3 P0 4 solution.
  • the subsequent treatment is carried out either only with Na 2 SiO 3 . 5 H 2 0 (V5 to V16) or with a mixture of silicate and KN-tartrate (Examples 4 to 15) and compared with foils without any aftertreatment (V1 and V17).
  • the test conditions and results can be found in the table below, the effective temperatures and sometimes the effective times being varied.
  • the electrochemical type of treatment usually improves the resistance to alkali compared to a pure immersion treatment under otherwise identical conditions.
  • Oxide layers produced in H 2 S0 4 solutions are attacked more strongly by silicate solutions at higher temperatures than oxide layers produced in H 3 PO 4 solutions, so that - without using the mixture according to the invention - the treatment times and temperatures are severely restricted.
  • An aluminum foil is in dilute aqueous HCI or HN0 3 solution. electrochemically roughened with alternating current and anodized in dilute aqueous H 2 SO 4 solution.
  • Which subsequent treatment with an aqueous solution of a content of 40 g / I of Na 3 SiO 3 ⁇ 5 H 2 0 and 20 g / I of KNa-tartrate (Examples 16 and 17) performed with foils without any post-treatment (V18 and V20) or with polyvinylphosphonic acid (PVPS) aftertreatment (V19 and V21).
  • the test conditions and results can be found in the table below.
  • the oxide layers aftertreated with aqueous polyvinylphosphonic acid solutions do show good hydrophilicity and a good reduction in the color fog sensitivity, but they are not yet satisfactory in all cases.
  • An aluminum foil is roughened in dilute aqueous HCI or HN0 3 solution with alternating electrochemically and in dilute aqueous H z S0 4 solution anodically oxidized.
  • the subsequent treatment is carried out with an aqueous solution of Na 3 SiO 3 .5 H 2 O (comparative examples) or a mixture of silicate / organic carboxylic acid or carboxylic acid salt - as can be seen from the table.
  • Hydroxycarbon or dicarboxylic acids are used as carboxylic acids, ie carboxylic acids with one or more carboxyl groups and at least one hydroxyl group or carboxylic acids with two carboxyl groups.
  • the pH of the resulting aqueous solutions drops by about 1.5 to 2.5 values, which in some cases leads to a reduction in the alkali resistance (measured by the gravimetric method).
  • This effect can be compensated for by increasing the temperature or extending the treatment time, including use the electrochemical process variant brings improvements.
  • a significant improvement in the alkali resistance to pure silicate solutions can be achieved by adjusting the pH values of the aqueous solutions to values which are in the range of the pH value of pure silicate solutions. This setting can be brought about by the direct use of salts (alkali or ammonium salts) of the CaArbonic acids mentioned, or by adding bases such as aqueous NaOH solution to the aqueous silicate / acid mixtures. It is also possible to use alternating current instead of direct current in the electrochemical process variant.
  • An aluminum foil is electrochemically roughened in a dilute aqueous HCl or HN0 3 solution with alternating current and anodically oxidized in a dilute aqueous H 2 S0 4 solution.
  • the subsequent treatment is no longer carried out with Na 2 SiO 3 ' 5 H 2 0 (sodium metasilicate) with a ratio of Na 2 0: Si0 2 such as 1: 1, which, without addition, has a relatively aggressive influence on the aluminum oxide layer, but with water glass DAB VI with a solids content of about 33%, ie usually a mixture of sodium tri- and tetrasilicates with an approximate ratio of Na 2 O: Si0 2 such as 3: 1.
  • KN tartrate is added as the second component.
  • Examples 73 to 76 and Comparative Examples V37 to V40 The procedure of the example groups 1 to 3 and V1 to V4 is followed, but with aluminum foil which is anodically oxidized in an aqueous electrolyte containing H 2 S0 4 and H 3 P0 4 (according to Teaching of DE-OS 28 36 803).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Electrochemical Coating By Surface Reaction (AREA)

Claims (8)

1. Procédé pour la fabrication de matériaux en forme de plaque, feuille ou bande, à base d'aluminium ou d'un de ses alliages, grainé mécaniquement et/ou électrochimiquement, et oxydé par anodisation, dont les couches d'oxyde d'aluminium sont post-traitées avec une solution aqueuse d'un silicate alcalin, caractérisé en ce que l'on effectue le post-traitement avec une solution aqueuse d'un silicate alcalin, qui contient en outre au moins un acide hydroxy-mono-, -di- ou -tricarboxylique aliphatique, un acide dicarboxylique aliphatique ou un sel de ces acides, soluble dans l'eau.
2. Procédé selon la revendication 1, caractérisé en ce que la solution aqueuse présente un pH de 11,5 à 13,5.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la solution aqueuse présente un pH de 12,0 à 13,0.
4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que l'on effectue le post-traitement par voie électrochimique, avec une densité de courant de 0,1 à 10 A/dm2.
5. Procédé selon l'une revendications 1 à 4, caractérisé en ce que l'on effectue le post-traitement pendant une durée de 5 à 120 secondes, et à une température de 15 à 80°C.
6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que la solution aqueuse contient de 1 à 50g/litre de silicate alcalin et de 3 à 50 g/litre d'au moins un acide carboxylique ou un de ses sels.
7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que l'on soumet les matériaux à un grainage électrochimique dans une solution aqueuse contenant HCI et/ou HN03, et à une oxydation anodique dans une solution aqueuse contenant H3PO4.
8. Utilisation du procédé selon l'une des revendications 1 à 7, pour la production de matériaux en tant que supports pour plaques d'immpression offset.
EP83104145A 1982-05-27 1983-04-28 Procédé de post traitement de couches d'oxyde d'aluminium avec des solutions aqueuses contenant silicate alcalin et son application dans la fabrication de supports de plaques d'impression offset Expired EP0095581B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3219922 1982-05-27
DE19823219922 DE3219922A1 (de) 1982-05-27 1982-05-27 Verfahren zur nachbehandlung von aluminiumoxidschichten mit alkalisilikat enthaltenden waessrigen loesungen und dessen verwendung bei der herstellung von offsetdruckplattentraegern

Publications (3)

Publication Number Publication Date
EP0095581A2 EP0095581A2 (fr) 1983-12-07
EP0095581A3 EP0095581A3 (en) 1986-08-06
EP0095581B1 true EP0095581B1 (fr) 1988-06-15

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP83104145A Expired EP0095581B1 (fr) 1982-05-27 1983-04-28 Procédé de post traitement de couches d'oxyde d'aluminium avec des solutions aqueuses contenant silicate alcalin et son application dans la fabrication de supports de plaques d'impression offset

Country Status (4)

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EP (1) EP0095581B1 (fr)
JP (1) JPS58213894A (fr)
CA (1) CA1225613A (fr)
DE (2) DE3219922A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8309571D0 (en) * 1983-04-08 1983-05-11 Albright & Wilson Accelerated sealing of anodised aluminium
DE3406101A1 (de) * 1984-02-21 1985-08-22 Hoechst Ag, 6230 Frankfurt Verfahren zur zweistufigen hydrophilierenden nachbehandlung von aluminiumoxidschichten mit waessrigen loesungen und deren verwendung bei der herstellung von offsetdruckplattentraegern
DE3406102A1 (de) * 1984-02-21 1985-08-22 Hoechst Ag, 6230 Frankfurt Verfahren zur nachbehandlung von aluminiumoxidschichten mit alkalimetallsilikat enthaltenden waessrigen loesungen und deren verwendung bei der herstellung von offsetdruckplattentraegern
JP2520712B2 (ja) * 1988-10-17 1996-07-31 富士写真フイルム株式会社 平版印刷版用アルミニウム支持体の製造方法
CN103276431B (zh) * 2013-05-21 2015-08-26 昆山乙盛机械工业有限公司 铝制品高光阳极工艺
CN106191962A (zh) * 2016-08-30 2016-12-07 无锡库帕油品有限公司 一种铝及铝合金常温环保封闭剂及其制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3376205A (en) * 1964-07-15 1968-04-02 Samuel L Cohn Method of reviving silicate sealing solutions
BE792852A (fr) * 1971-12-17 1973-06-15 Henkel & Cie Gmbh Procede de traitement de surfaces d'aluminium par oxydation suivie d'une densification
JPS4928577A (fr) * 1972-07-14 1974-03-14

Also Published As

Publication number Publication date
DE3219922A1 (de) 1983-12-01
EP0095581A3 (en) 1986-08-06
EP0095581A2 (fr) 1983-12-07
CA1225613A (fr) 1987-08-18
DE3377069D1 (en) 1988-07-21
JPS58213894A (ja) 1983-12-12
JPH0365440B2 (fr) 1991-10-11

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