EP0069319B1 - Matériaux de support pour plaques lithographiques, aux propriétés hydrophiles améliorées, procédés pour leur fabrication, et leur utilisation - Google Patents

Matériaux de support pour plaques lithographiques, aux propriétés hydrophiles améliorées, procédés pour leur fabrication, et leur utilisation Download PDF

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Publication number
EP0069319B1
EP0069319B1 EP82105717A EP82105717A EP0069319B1 EP 0069319 B1 EP0069319 B1 EP 0069319B1 EP 82105717 A EP82105717 A EP 82105717A EP 82105717 A EP82105717 A EP 82105717A EP 0069319 B1 EP0069319 B1 EP 0069319B1
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EP
European Patent Office
Prior art keywords
support material
printing plates
offset printing
weight
acid
Prior art date
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Expired
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EP82105717A
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German (de)
English (en)
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EP0069319A1 (fr
Inventor
Dieter Dr. Mohr
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Hoechst AG
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Hoechst AG
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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
    • B41N3/036—Chemical or electrical pretreatment characterised by the presence of a polymeric hydrophilic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • B41C1/1016—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials characterised by structural details, e.g. protective layers, backcoat layers or several imaging layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/04—Intermediate layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/02—Positive working, i.e. the exposed (imaged) areas are removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/04—Negative working, i.e. the non-exposed (non-imaged) areas are removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/06—Developable by an alkaline solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers

Definitions

  • Hydrophilized substrates for offset printing plates a process for their production and their use.
  • the invention relates to plate, film or ribbon-shaped support materials for offset printing plates based on aluminum with a hydrophilic coating, a process for the production of these materials and the use of the materials in the production of offset printing plates.
  • 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 light-sensitive layer (copying layer), with the aid of which a printing image is generated photomechanically.
  • the support carries the printing image areas and at the same time forms the hydrophilic background for the lithographic printing process in the non-image areas (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 carrier materials in particular anodically oxidized carrier materials based on aluminum, are subjected to a further treatment step to improve the layer adhesion, to increase the hydrophilicity and / or to facilitate the developability of the light-sensitive layers before the application of a light-sensitive layer for example the following methods.
  • DE-PS907147 US-PS 2 714 066
  • DE-AS 14 71 707 US-PS 3 181 461 and US-PS 3 280 73
  • DE-OS 25 32 769 US- PS 3 902 976
  • processes for the hydrophilization of 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.
  • the use of salts of these compounds is also mentioned, but is not specified in detail.
  • DE-AS 10 56 931 describes the use of water-soluble, linear copolymers based on alkyl vinyl ethers and maleic anhydrides in light-sensitive layers for printing plates.
  • these copolymers those in which the maleic anhydride component has not been reacted with, or more or less completely, with ammonia, an alkali metal hydroxide or an alcohol are particularly hydrophilic.
  • DE-AS 10 91 433 discloses the hydrophilization of printing plate support materials based on metals with film-forming organic polymers such as polymethacrylic acid or sodium carboxymethyl cellulose or hydroxyethyl cellulose in the case of aluminum supports or a mixed polymer of methyl vinyl ether and maleic anhydride in the case of magnesium supports.
  • film-forming organic polymers such as polymethacrylic acid or sodium carboxymethyl cellulose or hydroxyethyl cellulose in the case of aluminum supports or a mixed polymer of methyl vinyl ether and maleic anhydride in the case of magnesium supports.
  • water-soluble polyfunctional amino-urea-aldehyde synthetic resins or sulfonated urea-aldehyde synthetic resins are first used, which are in a water-insoluble state on the metal support be cured.
  • the hydrophilic layer on a printing plate support material according to DE-PS 21 07 901 is formed from a water-insoluble hydrophilic acrylate or methacrylate homopolymer or copolymer with a water absorption of at least 20% by weight.
  • a process is used to compact anodized aluminum surfaces in which a solution is used at a temperature of at least 90 ° C. and a pH of 5 to 6.5 is applied which contains water-soluble phosphonic acids which form complexes with divalent metals or their salts (such as 1-hydroxyethane-1,1-diphosphonic acid or aminotrimethylenephosphonic acid) and Ca 2 + ions; these solutions can also contain dextrins.
  • a solution is used at a temperature of at least 90 ° C. and a pH of 5 to 6.5 is applied which contains water-soluble phosphonic acids which form complexes with divalent metals or their salts (such as 1-hydroxyethane-1,1-diphosphonic acid or aminotrimethylenephosphonic acid) and Ca 2 + ions; these solutions can also contain dextrins.
  • the layer weight of the hydrophilic adhesive layer on cellulose ether is 0.2 to 1.1 mg / dm 2 , and the same layer weight is also given for the water-soluble salts.
  • the mixture of cellulose ether and salt is applied to the support in aqueous solution, optionally with the addition of an organic solvent and / or a surfactant.
  • hydrophilizing agents for printing plate support materials according to US Pat. No. 4,049,746 contain salt-like reaction products from water-soluble polyacrylic resins with carboxyl groups and polyalkyleneimine-urea-aldehyde resins.
  • GB-PS 1 246696 describes hydrophilic colloids such as hydroxyethyl cellulose, polyacrylamide, polyethylene oxide, polyvinyl pyrrolidone, starch or gum arabic as hydrophilizing agents for anodized aluminum printing plate supports.
  • the object of the invention is therefore to modify the hydrophilicity of support materials for offset printing plates in such a way that they are equally suitable as supports for positive, negative or electrophotographic light-sensitive layers without the aforementioned disadvantages of known modification methods occurring.
  • the invention is based on the known plate, foil or tape-shaped carrier materials for offset printing plates based on chemically, mechanically and / or electrochemically roughened aluminum, optionally having an aluminum oxide layer produced by anodic oxidation, or one of its alloys with a hydrophilic coating of at least one hydrophilic organic polymers on at least one surface of the carrier material.
  • the carrier materials according to the invention are then characterized in that the hydrophilic organic polymer is a complex reaction product of a) a water-soluble organic polymer with carboxylate, carboxamide and / or carboximide substituents as functional groups and b) a salt of an at least divalent metal cation and the amount of complex-type reaction product is less than 0.1 mg per dm2 of substrate surface.
  • the complex reaction products 1 to 3, preferably 2, coordination sites of the metal cation are occupied by the functional groups of the polymer, which probably functions as a chelating ligand.
  • the water-soluble polymers used to prepare the complex reaction products are, in particular, polyacrylic acid, a copolymer based on polyacrylic acid, polyacrylamide, a copolymer based on polyacrylamide, a hydrolyzed or partially or completely subjected to ammonolysis with NH 3 based on ethylene or vinyl methyl ether and maleic anhydride or carboxyalkyl cellulose (with alkyl groups from C 1 to C 3 , in particular carboxymethyl cellulose) or their mixed ethers such as carboxymethyl hydroxyethyl cellulose.
  • the metal cations are generally used in the form of their salts with mineral acid anions or as acetates; the divalent, trivalent or tetravalent, in particular the divalent, are preferred.
  • the cations are in particular V5 + -Bi3 + - , Al 3 + - , Fe 3 + - , Zr 4 + - , Sn 4 + - , Ca 2 + - , Ba2 + - , Sr 2 + - , Ti 3 + - , Co 2+ -, Fe 2 + - , Mn 2 + - , Ni 2 + - , C u 2 + - , Zn 2 + - or Mg 2 + - ions.
  • the metal cation is usually present both in aqueous solution and in the solid state as an octahedral complex, preferably two of the six coordination sites being occupied by the functional groups of the polymer and the four remaining coordination sites by anions of the salt used, Hydroxyl ions, amine ligands and predominantly water or completely filled with water.
  • these products are soluble in more or less acidic media and are precipitated quantitatively when the acidic solution is neutralized with alkali hydroxide or ammonia; they are insoluble in neutral or alkaline aqueous and in the usual organic solvents.
  • the isolated and dried complex reaction products are preferably in 0.1 to 10%, in particular 0.5 to 3%, mineral acids, preferably phosphoric acid, in Concentrations of 0.05 to 5%, especially in concentrations of 0.1 to 1%, dissolved.
  • the treatment of these substrates with the solutions of the complex reaction products is expediently carried out by dipping formats or by passing the substrate tape through a bath of these solutions. Temperatures of 20 ° to 95 ° C., preferably of 25 ° to 60 ° C. and residence times of 2 seconds to 10 minutes, preferably of 10 seconds to 3 minutes, have proven to be the most favorable for practical use. An increase in the bath temperature favors the chemisorption of the polymer-metal complexes on the substrate. This makes it possible to reduce the dwell times considerably, particularly in the case of continuous strip treatment.
  • the immersion treatment is then expediently followed by a rinsing step with water, primarily with tap water.
  • This rinsing process can serve on the one hand to remove excess treatment solution from the support, on the other hand the acidic treatment solution on the support is shifted so strongly towards the neutral point by dilution with water that the dissolved complexes can precipitate in the pores of the substrate and thus on the substrate Carriers are firmly fixed.
  • the substrate treated in this way is then expediently dried at temperatures of 110 ° to 130 ° C.
  • the treatment of the aluminum substrate can also be carried out as a two-step process.
  • the substrate is immersed, for example, in a 0.2 to 10%, preferably 0.5 to 5%, aqueous solution of the starting polymer.
  • the substrate can then be transferred to a second bath without prior rinsing or drying, which contains a 0.1% to saturated, preferably 0.5 to 10% aqueous salt solution with the polyvalent metal ions listed above.
  • the rinsing and drying is carried out as in the one-step process.
  • the complex reaction products described above are formed on the substrate during the treatment. This variant of the method allows complex reaction products which are difficult to dissolve even in strongly acidic media to be applied to the substrate.
  • an aluminum foil e.g. made of electrochemically roughened and anodized aluminum with a thickness of 0.03 mm
  • weight increases in the range of approximately 4 to 8 mg / m 2 (0.04 to 0.08 mg / dm 2 ) are then determined, depending on the type of complex reaction product.
  • the support materials according to the invention thus produced can then be coated with various light-sensitive layers for the production of offset printing plates.
  • the aluminum support materials for printing plates which are very common in practice, are generally mechanically (e.g. by brushing and / or with abrasive treatments), chemically (e.g. by etching agents) or electrochemically (e.g. B. by 'AC treatment in aqueous HCI or HN0 3 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 / l, the current density between 15 and 130 A / dm 2 , the residence time between 10 and 100 sec and the electrolyte flow rate 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 4 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.
  • the individual roughness depth is defined as the distance between two parallels to the middle line, which touch the roughness profile at the highest or lowest point within the Elnzel measurement sections.
  • the individual measuring section is the fifth part of the length of the part of the roughness profile which is used directly for evaluation and is projected perpendicularly onto the middle line.
  • the middle line is the line parallel to the general direction of the roughness profile from the shape of the geometrically ideal profile, which divides the roughness profile so that the sum of the material-filled areas above it and the material-free ones Areas under it are the same.
  • 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 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 by the manufacturer of presensitized printing plates or directly by the consumer on one of the usual carrier materials.
  • Suitable layers also include the electrophotographic layers, i.e. H. those containing 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 photosensitive compositions or compounds can be used in the coating of the carrier materials produced by the process according to the invention.
  • Positive-working o-quinonediazide preferably o-naphthoquinonediazide compounds, which are described, for example, in DE-PS 854 890, 865 109, 879 203, 894 959, 938 233, 1 109 521, 1 144 705, 1 118 606, 1 120 273 and 1 124 817.
  • Negative-working 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-PS 596 731, 1 138 399, 1 138 400, 1 138 401, 1 142 871, 1 154 123 U.S. Patents 2,679,498 and 3,050,502 and British Patent 712,606.
  • Negative mixed condensation products of aromatic diazonium compounds for example according to DE-OS 2 024 244, which each have at least one unit of the general types A (-D) n and B connected by a double-bonded intermediate member derived from a condensable carbonyl compound.
  • A is the remainder of a compound containing at least two aromatic carbocyclic and / or heterocyclic nuclei, which is capable of condensation with an active carbonyl compound in at least one position in an acid medium.
  • D is a diazonium salt group attached to an aromatic carbon atom of A; n is an integer from 1 to 10; and B the remainder of a compound free of diazonium groups, which in acid Medium at at least one position of the molecule is capable of condensation with an active cabonyl compound.
  • Positive-working layers according to DE-OS 26 10 842 which contain a compound which splits off acid when irradiated, a compound which has at least one C-O-C group which can be split off by acid (e.g. an orthocarboxylic acid ester group or a carboxylic acid amide acetal group) and, if appropriate, a binder.
  • acid e.g. an orthocarboxylic acid ester group or a carboxylic acid amide acetal group
  • the monomers used here are, for example, acrylic and methacrylic acid esters or reaction products of diisocyanates with partial esters of polyhydric alcohols, as described, for example, in US Pat. Nos. 2760863 and 3060023 and DE-OSes 20 64 079 and 23 61 041.
  • photoinitiators are u. a. Benzoin, benzoin ethers, multinuclear quinones, acridine derivatives, phenazine derivatives, quinoxaline derivatives, quinazoline derivatives or synergistic mixtures of different ketones.
  • soluble organic polymers can be used as binders, e.g. B. polyamides, polyesters, alkyd resins, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin or cellulose ether.
  • Negative working layers according to DE-OS 3 036 077 which contain a diazonium salt polycondensation product or an organic azido compound as a photosensitive compound and a high molecular weight polymer with pendant alkenylsulfonyl or cycloalkenylsulfonylurethane groups as a binder.
  • photoconductive layers such as z. B. in DE-PSen 11 17 391, 15 22 497, 15 72 312, 2322046 and 23 22 047 are described, applied to the support materials produced according to the invention, whereby highly light-sensitive, electrophotographic printing plates are formed.
  • offset printing plates obtained from the carrier materials 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.
  • a developer preferably an aqueous developer solution.
  • offset printing plates, the base support materials of which were treated according to the invention with the complex reaction products are distinguished from those plates in which the same base material was treated with the corresponding polymers without a reaction with metal cations, by considerably improved hydrophilicity of the non-image areas and by an increased practical sensitivity to light ( better layer adhesion).
  • % 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 also used in the examples.
  • the hydrophilicity of the carrier materials produced according to the invention is tested 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 degrees. The smaller the angle, the better the wetting.
  • 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 the more alkali-resistant the longer it is used Resolution needs.
  • 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 recognized by the blackening of the examination site.
  • Example 1 To produce further polymer-metal complexes, the copolymer used in Example 1 is dissolved in dilute aqueous NH 3 solution, the maleic anhydride functions being hydrolyzed to amide or half-amide groups. The further reaction with the metal cation is carried out according to Example 1.
  • Example 1 To prepare the polymer-metal complexes of polyacrylic acid or polyacrylamide, the procedure according to Example 1 is followed, with only the first hydrolysis step being omitted; H. working at 25 ° C.
  • a bright rolled aluminum strip with a thickness of 0.3 mm is degreased with an aqueous alkaline 2% pickling solution at an elevated temperature of around 50 ° to 70 ° C.
  • the electrochemical roughening of the aluminum surface is carried out with alternating current and in an electrolyte containing HN0 3 , a surface roughness having an R z value of 6 ⁇ m being obtained.
  • the subsequent anodic oxidation is carried out in accordance with the process described in DE-OS 2811 396 in an electrolyte containing sulfuric acid; the oxide weight is 3.0 g / m 2 .
  • the aluminum strip prepared in this way is then passed through a bath heated to 60 ° C. from a 0.5% solution (in 2% H 3 PO 4 ) of the polymer-metal complex composed of the copolymer of vinyl methyl ether and maleic anhydride and Al 3 + - ion guided.
  • the residence time in the bath is 20 seconds.
  • the excess solution is then removed with tap water in a rinsing step and the strip is dried with hot air at temperatures between 100 ° and 130 ° C.
  • the printing plate produced in this way can be developed quickly and free of fog.
  • the non-image areas are characterized by a very good ink-repelling effect.
  • the contact angle measurement compared to a drop of water gave a value of 18 ° for the stripped material, the print run was 200,000.
  • the coated tape is dried in the drying tunnel at temperatures up to 120 ° C.
  • the printing plates thus produced are exposed under a positive template and developed with a developer of the following composition:
  • the printing forms received are free of copying and printing technology.
  • the non-image areas have a very good ink-repellent effect, which manifests itself in the fast free running of the printing form in the printing press.
  • the print run is 120,000.
  • the printing plates produced in this way are distinguished by the same advantages as indicated in Example 13.
  • An aluminum support which is roughened by brushing with an aqueous abrasive suspension, is after-treated according to Example 23 and coated with the following solution:
  • the layer is negatively charged to about 400 V in the dark by means of a corona.
  • the charged plate is exposed imagewise in a repro camera and then developed with an electrophotographic suspension developer which is obtained by dispersing 3.0 parts by weight of magnesium sulfate in a solution of 7.5 parts by weight of pentaerythritol resin ester in 1200 parts by volume of an isoparaffin mixture with a boiling range of 185 to 2.10 ° C was obtained.
  • the plate is poured out into a solution for 60 seconds submerged.
  • the plate is then rinsed off with a powerful jet of water, removing the areas of the photoconductor layer not covered with toner.
  • the plate is then ready for printing.
  • the planographic printing plate thus produced has a very good ink-repellent effect in the non-image areas.
  • the light-sensitive layer is exposed under a negative original for 35 seconds using a metal halide lamp with a power of 5 kW.
  • the exposed layer is made using a plush pad with a developer solution of the following composition. treated, the non-image areas are removed.
  • the exposed carrier surfaces have a very good ink-repellent effect, which is manifested in the fast free running of the printing plate in the printing press.
  • the circulation of the plate in a sheetfed offset press is 170,000 sheets.
  • An aluminum sheet which had been electrochemically roughened and anodically oxidized according to Example 4 was immersed for 30 seconds at 65 ° C. in a 1% strength aqueous solution of the copolymer of ethylene and maleic anhydride hydrolyzed at 80 ° C. When the substrate is removed from the bath, the excess solution is scraped off the surface. Subsequently, the still moist substrate is immersed in a 2% aqueous solution of Al (NO 3 ) 3 .9H 2 0 for 30 seconds at room temperature, it is rinsed with tap water and dried with hot air (100 to 130 ° C.). The substrate treated in this way is then coated with the light-sensitive solution described in Example 5, exposed and developed. The properties of the printing plate produced in this way correspond to that of a material produced according to Example 5.

Claims (13)

1. Matériau de support en forme de plaques, de feuilles ou de bandes, pour plaques pour impression offset, à base d'aluminium rendu rugueux par voie chimique mécanique, et/ou électrochimique, portant éventuellement une couche d'oxyde d'aluminium obtenue par oxydation anodique, ou d'un alliage d'aluminium, avec un revêtement hydrophile constitué d'au moins un polymère organique hydrophile sur au moins une surface du matériau de support, le polymère organique hydrophile étant un produit de réaction complexe de a) un polymère organique soluble dans l'eau - à l'exception des éthers de cellulose - avec des substituants carboxylate, amide d'acide carboxylique et/ou imide d'acide carboxylique comme groupes fonctionnels et b) un sel d'un cation métallique au moins divalent, et la quantité de produit de réaction complexe étant inférieure à 0,1 mg/dm2 de surface du matériau de support.
2. Matériaux de support pour plaques pour impression offset selon la revendication 1, caractérisés en ce que de un à trois sites de coordination du cation métallique sont occupés par les groupes fonctionnels du polymère.
3. Matériaux de support pour plaques pour impression offset selon la revendication 1 ou 2, caractérisés en ce que le polymère organique soluble dans l'eau est un acide poly-acrylique, un copolymère à base d'acide polyacrylique, un polyacrylamide, un copolymère à base de polyacrylamide, un copolymère hydrolysable à base d'éthylène ou d'éther vinylméthylique et d'anhydride maléique, un copolymère à base d'éthylène ou d'éther vinylméthylique et d'anhydride maléique soumis à une ammonolyse partielle ou totale avec NH3, ou un des sels de ces polymères avec un cation monovalent.
4. Matériaux de support pour plaques pour impression offset selon l'une quelconque des revendications 1 à 3, caractérisés en ce que le cation métallique est di-, tri- ou tétravalent.
5. Matériaux de support pour plaques pour impression offset selon l'une quelconque des revendications 1 à 4, caractérisés en ce que le cation métallique est un ion Bi3+-, AI3+-, Fe3+-, Zr4+-, Sn4+-, Ca2+-, Ba2+-, Sr2+-, Ti3+-, C0 2+_, Fe2+-, Mn2+-, Ni2+-, Cu2+-, Zn2+- ou Mg2+.
6. Procédé de préparation du matériau de support pour plaques pour impression offset selon l'une quelconque des revendications 1 à 5, dans lequel le produit de réaction complexe dissous dans un milieu acide aqueux est appliqué sur au moins une surface du matériau de support, puis rincé avec de l'eau et le matériau de support ainsi modifié est séché.
7. Procédé selon la revendication 6, caractérisé en ce que le produit de réaction complexe est dissous en une concentration de 0,05 à 5 % en poids dans des acides aqueux à 0,1 à 10 % en poids.
8. Procédé selon la revendication 6 ou 7, caractérisé en ce que le produit de réaction complexe est dissous en une concentration de 0,1 à 1 % en poids dans des acides aqueux à 0,5 à 3 % en poids.
9. Procédé selon l'une quelconque des revendications 6 à 8, caractérisé en ce que, comme acide, on utilise l'acide phosphorique.
10. Procédé de préparation du matériau de support pour des plaques pour impression offset selon l'une quelconque des revendications 1 à 5, dans lequel le produit de réaction complexe est produit à partir des constituants a) + b) sur le matériau de support, puis rincé avec de l'eau.
11. Procédé selon la revendication 10, caractérisé en ce que le matériau de support est immergé successivement dans une solution aqueuse de constituant a) et dans une solution aqueuse du constituant b).
12. Procédé selon la revendication 11, caractérisé en ce que la première solution aqueuse contient de 0,2 à 10 % en poids du constituant a) et la seconde solution aqueuse contient de 0,1 % en poids jusqu'à la saturation de constituant b).
13. Utilisation du matériau de support selon l'une quelconque des revendications 1 à 5 pour la préparation de plaques pour impression offset présentant une couche photosensible.
EP82105717A 1981-07-06 1982-06-28 Matériaux de support pour plaques lithographiques, aux propriétés hydrophiles améliorées, procédés pour leur fabrication, et leur utilisation Expired EP0069319B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3126626 1981-07-06
DE19813126626 DE3126626A1 (de) 1981-07-06 1981-07-06 Hydrophilierte traegermaterialien fuer offsetdruckplatten, ein verfahren zu ihrer herstellung und ihre verwendung

Publications (2)

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EP0069319A1 EP0069319A1 (fr) 1983-01-12
EP0069319B1 true EP0069319B1 (fr) 1986-11-12

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EP82105717A Expired EP0069319B1 (fr) 1981-07-06 1982-06-28 Matériaux de support pour plaques lithographiques, aux propriétés hydrophiles améliorées, procédés pour leur fabrication, et leur utilisation

Country Status (6)

Country Link
US (1) US4427766A (fr)
EP (1) EP0069319B1 (fr)
JP (1) JPS5818291A (fr)
BR (1) BR8203903A (fr)
CA (1) CA1184448A (fr)
DE (2) DE3126626A1 (fr)

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EP0689096B1 (fr) 1994-06-16 1999-09-22 Kodak Polychrome Graphics LLC Plaques d'impression lithographiques utilisant une couche oléophile à formation d'image
JP4469927B2 (ja) 2000-05-23 2010-06-02 Ｄｉｃ株式会社 感光性組成物およびこれを用いた平版印刷版原版、画像形成方法
JP2002341536A (ja) 2001-05-21 2002-11-27 Kodak Polychrome Graphics Japan Ltd ネガ型感光性組成物およびネガ型感光性平版印刷版
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JP4410714B2 (ja) 2004-08-13 2010-02-03 富士フイルム株式会社 平版印刷版用支持体の製造方法
US7083895B2 (en) * 2004-09-01 2006-08-01 Kodak Polychrome Graphics Llc Adhesion promoting ingredients for on-press developable lithographic printing plate precursors
EP1712368B1 (fr) 2005-04-13 2008-05-14 FUJIFILM Corporation Procédé de fabrication d'un substrat pour plaque lithographique
JP2009208140A (ja) 2008-03-06 2009-09-17 Fujifilm Corp 平版印刷版用アルミニウム合金板の製造方法、ならびに該製造方法により得られる平版印刷版用アルミニウム合金板および平版印刷版用支持体
EP2110261B1 (fr) 2008-04-18 2018-03-28 FUJIFILM Corporation Plaque d'alliage en aluminium pour plaque d'impression lithographique, support de plaque d'impression lithographique, plaque présensibilisée, procédé de fabrication d'une plaque en alliage d'aluminium et procédé de fabrication du support de plaque d'impression lithographique
JP5296434B2 (ja) 2008-07-16 2013-09-25 富士フイルム株式会社 平版印刷版用原版
CN102548769B (zh) 2009-09-24 2015-08-12 富士胶片株式会社 平版印刷版原版

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Also Published As

Publication number Publication date
EP0069319A1 (fr) 1983-01-12
CA1184448A (fr) 1985-03-26
JPH0249239B2 (fr) 1990-10-29
DE3274221D1 (en) 1987-01-02
JPS5818291A (ja) 1983-02-02
DE3126626A1 (de) 1983-01-20
BR8203903A (pt) 1983-06-28
US4427766A (en) 1984-01-24

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