EP0468313B1 - Plaques, feuilles ou matériel en forme de bandes comme support pour des plaques d'impression offset, procédé pour sa préparation et son utilisation - Google Patents

Plaques, feuilles ou matériel en forme de bandes comme support pour des plaques d'impression offset, procédé pour sa préparation et son utilisation Download PDF

Info

Publication number
EP0468313B1
EP0468313B1 EP91111643A EP91111643A EP0468313B1 EP 0468313 B1 EP0468313 B1 EP 0468313B1 EP 91111643 A EP91111643 A EP 91111643A EP 91111643 A EP91111643 A EP 91111643A EP 0468313 B1 EP0468313 B1 EP 0468313B1
Authority
EP
European Patent Office
Prior art keywords
support material
acidic
groups
monomer
aluminum
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 - Lifetime
Application number
EP91111643A
Other languages
German (de)
English (en)
Other versions
EP0468313A1 (fr
Inventor
Engelbert Dr. Dipl.-Chem. Pliefke
Raimund-Josef Dr. Dipl.-Chem. Faust
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 EP0468313A1 publication Critical patent/EP0468313A1/fr
Application granted granted Critical
Publication of EP0468313B1 publication Critical patent/EP0468313B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • 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
    • B41N1/00—Printing plates or foils; Materials therefor
    • 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
    • Y10T428/31—Surface property or characteristic of web, sheet or block
    • 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]
    • Y10T428/31678—Of metal
    • Y10T428/31692—Next to addition polymer from unsaturated monomers
    • 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]
    • Y10T428/31678—Of metal
    • Y10T428/31692—Next to addition polymer from unsaturated monomers
    • Y10T428/31696—Including polyene monomers [e.g., butadiene, etc.]

Definitions

  • the invention relates to plate, film or tape-shaped carrier material for offset printing plates, consisting of pretreated aluminum or one of its alloys, which has a hydrophilic coating of a polymer containing acid side groups on at least one side, a process for producing a carrier material and the use of a carrier material .
  • 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 layer support carries the printing image areas and at the same time forms the hydrophilic image 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 layer supports. These raw materials are processed through suitable processing measures, e.g. Grain, matt chrome plating, surface oxidation and / or application of an intermediate layer, transferred into layer supports for offset printing plates.
  • Aluminum, which is probably the most frequently used base material for offset printing plates today is roughened on the surface by known methods such as dry brushing, wet brushing, sandblasting, chemical and / or electrochemical treatment or a combination thereof.
  • the roughened substrate can also be subjected to an anodization step to build up a thin oxide layer.
  • DE-B 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.
  • a) an aqueous dispersion of a modified one is first of all carried out on the support Urea-formaldehyde resin, an alkylated methylol-melamine resin or a melamine-formaldehyde-polyalkylene polyamine resin applied, b) an aqueous dispersion of a polyhydroxy or polycarboxy compound, such as sodium carboxymethyl cellulose, and finally the thus coated base c) with a treated aqueous solution of a Zr, Hf, Ti or Th salt.
  • the hydrophilic layer on a printing plate support material according to DE-C 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.
  • the layer weight of the hydrophilic adhesive layer on cellulose ether is 0.2 to 1.1 mg / dm2, 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 agent for printing plate support materials Contain the hydrophilizing agent for printing plate support materials according to US-A 4,049,746 salt-like reaction products from water-soluble polyacrylic resins with carboxyl groups and polyalkyleneimine-urea-aldehyde resins.
  • GB-A 1,246,696 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.
  • EP-B 0 149 490 describes compounds for hydrophilization which, in addition to amino groups, additionally contain carboxyl or carboxylate groups, sulfo groups or hydroxyl groups, is based on monomers and describes a molecular weight of 1000 as the upper limit.
  • SU-A 647 142 uses a copolymer of acrylamide and vinyl monomers for the hydrophilization of offset printing plates.
  • DE-C 10 91 433 describes a process for the aftertreatment of offset printing plate supports with polymers of methacrylic acid, methyl vinyl ether and maleic anhydride.
  • DE-A 29 47 708 describes u.a. Ni salt solutions of acrylamide and acrylic acid as well as acrylamide and vinyl pyrrolidone.
  • a carrier material for offset printing plates is known, the surface of which is hydrophilized with a high molecular weight, cationic polymer containing numerous amino groups, which additionally improves esterified (non-acidic) carboxy groups, hydroxy groups to improve the hydrophilic properties. or may contain amino groups.
  • the object of the invention is therefore to produce support materials for offset printing plates with good hydrophilization properties, which are suitable as supports for positive, negative or electrophotographic light-sensitive layers, without reducing their shelf life, reactions between the hydrophilizing agent and the photosensitive layer or reducing the layer adhesion.
  • the invention is based on a plate, film or tape-shaped carrier material for offset printing plates, consisting of mechanically, chemically or electrochemically roughened and optionally anodized aluminum or one of its alloys, which has a hydrophilic coating of a polymer containing acid side groups on at least one side has an average molecular weight of at least 1000.
  • hydrophilic polymer with repeating units also contains basic groups capable of protonation in addition to the acid side groups.
  • the mixed polymer consists of at least 2 mol% of units with a basic side group, optionally nonionic units, and at least 2 mol% of units with an acidic side group capable of salt formation - preferably with a divalent or higher-valent metal cation.
  • Suitable monomer units with basic side groups are compounds which contain aliphatic or aromatic amino groups, in particular tertiary amino groups, for example dimethylaminoethyl acrylate, Dimethylaminoethyl methacrylate and vinyl pyridine.
  • Vinyl compounds can be used as non-ionic components, e.g. Acrylic acid esters, such as ethyl, propyl, butyl, hexyl and decyl acrylate as well as the corresponding methacrylic acid esters and styrene, isoprene and butadiene.
  • Acrylic acid esters such as ethyl, propyl, butyl, hexyl and decyl acrylate as well as the corresponding methacrylic acid esters and styrene, isoprene and butadiene.
  • the acidic components include Carboxylic, sulfonic and phosphonic acids, e.g. Acrylic, methacrylic, vinylphosphonic, vinylsulfonic, maleic, itaconic, vinylbenzoic, vinylnaphthoeic, vinylphenylsulfonic, vinylphenylphosphonic and cinnamic acids.
  • Carboxylic, sulfonic and phosphonic acids e.g. Acrylic, methacrylic, vinylphosphonic, vinylsulfonic, maleic, itaconic, vinylbenzoic, vinylnaphthoeic, vinylphenylsulfonic, vinylphenylphosphonic and cinnamic acids.
  • the ratio of the monomer units can be varied within a wide range.
  • the molar ratios of the acidic to the basic monomer units can be varied from 2:98 to 98: 2.
  • a ratio of about 1: 1 (equimolar) is particularly preferred.
  • non-ionic, neutral groups can still be used in the copolymer to adjust solubility.
  • the acidic groups ensure good adhesion to the (anodized) aluminum substrate;
  • the basic groups effect an additional hydrophilization of the non-image areas and an improvement in adhesion through interaction with layer components in the image areas in the acidic wash water. Because the groups are anchored to a polymer backbone, there are numerous anchoring points to the layer and to the support, and the risk of loss of effectiveness during the printing process is reduced very strong.
  • the average molecular weight is at least 1,000, preferably between 5,000 and 50,000, but polymers with an even higher average molecular weight than 50,000 can also be used with technical advantage.
  • the copolymers are preferably dissolved in water with the addition of acids or alkalis so that a pH between 1 and 13, preferably between 3 and 10, is set.
  • the compounds described can also be used in the form of their metal or ammonium salts, the salts of divalent and higher-valent metals being particularly preferred.
  • 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 of the coating are in particular V5+-, Bi3+-, Al3+-, Fe3+-, Zr4+-, Sn4+-, Ca2+-, Ba2+-, Sr2+-, Ti3+-, Co2+-, Fe2+, Mn2+, Ni2+, Cu2+, Ce4+, Zn2+ or Mg2+ ions.
  • reaction products can be prepared in a simple manner in aqueous solution at temperatures from 20 to 100 ° C., preferably at 25 to 40 ° C.
  • the metal salt dissolved in water or, if necessary, dissolved in dilute mineral acid, is slowly added dropwise to the aqueous polymer solution. This leads to the immediate conversion of the reaction components to the previously described products.
  • the rapid onset of reaction can - depending on the metal cation used - in show immediately occurring color change of the solution or through precipitation.
  • the products can be precipitated by neutralizing the reaction solution with dilute alkali hydroxide or ammonia solutions, the unreacted starting products remaining in the solution.
  • the yields of these reactions are over 90%.
  • the salt forms with a monovalent cation, such as sodium or ammonium salt instead of the acid forms of the polymers described.
  • the aqueous solutions of the copolymers are used in concentrations of 0.001 to 10%, preferably in concentrations of 0.1 to 1%.
  • the treatment of these substrates with the solutions is expediently carried out by dipping formats or by passing the substrate tape through a bath of these solutions. Temperatures from 20 to 95 ° C., preferably from 40 to 80 ° C., and residence times from 1 s to 10 min, preferably from 2 s to 1 min, are found to be the most favorable for practical use. An increase in the bath temperature accelerates the chemisorption of the copolymers and 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 advantageously followed by a rinsing step with water.
  • the substrate treated in this way is then expediently dried at temperatures of 110 to 130.degree.
  • the pH is adjusted between 1 to 13, preferably to a pH of 3 to 10, and in particular to a value of 4 to 8.
  • the treatment of the aluminum substrate with the salts of the copolymers can also be carried out as a two-stage process.
  • the substrate is immersed, for example, in a 0.01 to 10%, preferably 0.1 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 reaction products described above are formed on the substrate during the treatment.
  • This variant of the process can also be used to apply the reaction products of trivalent metal ions, which are sparingly soluble in strongly acidic media, to the substrate.
  • 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 method according to the invention can also be applied to other aluminum alloys.
  • 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. by AC treatment in aqueous HCl or HNO3 solutions) roughened.
  • chemically e.g. by etching agents
  • electrochemically e.g. by AC treatment in aqueous HCl or HNO3 solutions
  • 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 / dm2, the residence time between 10 and 100 s and the electrolyte flow rate on the surface of the workpiece to be treated between 5 and 100 cm / s; 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 mean 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 7» m.
  • the roughness depth is determined in accordance with DIN 4768 (as of 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 individual 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 areas below it are the same.
  • Direct current is preferably used for the anodic oxidation, however alternating current or a combination of these types of current (for example direct current with superimposed alternating current) can also be used.
  • the layer weights of aluminum oxide range from 1 to 10 g / m2, 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 applied either by the manufacturer of presensitized printing plates or directly by the consumer on one of the usual carrier materials.
  • the suitable layers also include the electrophotographic layers, ie those which contain an inorganic or organic photoconductor.
  • these layers can of course also contain other constituents, such as resins, dyes or plasticizers.
  • the following photosensitive compositions or compounds can be used in the coating of the Carrier materials produced by the process according to the invention are used: positive working, o-quinonediazide, preferably o-naphthoquinonediazide compounds, which are described, for example, in DE-C 854 890, 865 109, 879 203, 894 959, 938 233, 1 109 521, 1 144 705, 1 118 606, 1 120 273 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-C 596 731, 1 138 399, 1
  • A is the remainder of a compound containing at least two aromatic carbocyclic and / or heterocyclic nuclei, which is capable of condensing with an active carbonyl compound in an acidic medium at at least one position.
  • D is a diazonium salt group attached to an aromatic carbon atom of A;
  • n is an integer from 1 to 10 and
  • B is the remainder of a compound free of diazonium groups which is present in an acidic medium on at least one Position of the molecule is capable of condensation with an active carbonyl compound; positive working layers which contain a compound which releases acid upon irradiation, a compound which has at least one COC group which can be removed by acid (for example an orthocarboxylic acid ester group, a carboxamide amide acetal group or an acetal group) and optionally a binder; Negative working layers made of photopolymerizable monomers, photoinitiators, binders and optionally other additives.
  • the monomers used here are, for example, acrylic and methacrylic acid esters or reaction products of di-isocyanates with partial esters of polyhydric alcohols, as described, for example, in US Pat. Nos. 2,670,863 and 3,060,023 and DE-A 20 64 079 and 23 61 041.
  • Suitable photoinitiators include benzoin, benzoin ethers, multinuclear quinones, acridine derivatives, phenazine derivatives, quinoxaline derivatives, quinazoline derivatives or synergistic mixtures of various ketones.
  • a large number of soluble organic polymers can be used as binders, for example polyamides, polyesters, alkyd resins, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, gelatin or cellulose ether; Negative working layers according to DE-A 30 36 077, which as a photosensitive compound is a diazonium salt polycondensation product or an organic azido compound and as a binder a high molecular weight polymer with pendant alkenylsulfonyl or Contain cycloalkenylsulfonyl urethane groups.
  • photo-semiconducting layers such as e.g. in DE-C 11 17 391, 15 22 497, 15 72 312, 23 22 046 and 23 22 047 are described, to which carrier materials are applied, which results in highly light-sensitive, electrophotographic layers.
  • the coated 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 carrier materials of which have been treated according to the invention show a significantly lower color haze and improved hydrophilicity compared to plates which have been treated with high polymer acrylic acid, with polymeric vinylphosphonic acid or only with hot water.
  • the adhesion of the light-sensitive layer to the surface of the support was also better in the samples treated according to the invention than in the comparison samples.
  • a carrier produced in this way is designated in Table 2 with the number 3.
  • the thus prepared carriers are immersed in a 60 ° C warm bath of an aqueous solution of 0.4% of one of the aftertreatment agents listed in Table 1 under A to N, which was adjusted to a pH between 5 and 6 with H3PO4 or NaOH .
  • the dwell time in the bath is 60 s.
  • the excess solution is then removed with deionized water in a rinsing step and the carrier is air-dried.
  • Carriers from Example A2 are immersed in a 0.2% solution of preparations A to N (Table 1) at 40 ° C.
  • the carriers are switched as an anode and treated with 10 volt direct current for 20 s.
  • the excess solution is then removed with deionized water in a rinsing step, and the carriers are on air dried.
  • Table 3 shows the supports thus produced and the results of the measurements described below.
  • the rate of dissolution of the layer in an alkaline zincate solution in seconds is 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 H2O, 480 g of KOH and 80 g of zinc oxide is brought to the surface to be examined and the period of time until the appearance of metallic zinc is determined, which can be recognized by a blackening of the examination site.
  • This "zinc certificate” is mentioned in column 4 of Table 2. This method is described, for example, in US Pat. No. 3,940,321, columns 3 and 4, lines 29 to 68 and lines 1 to 8.
  • the test is carried out using wetting angle measurements against a drop of water.
  • the angle is determined between the carrier surface under the drop and a tangent placed through the point of contact of the drop; it is generally between 0 ° and 90 °. The smaller the angle, the better the wetting.
  • the carriers are dried as described under point D1.
  • the dry layer weight is 0.75 g / m2.
  • the reproduction layer is exposed under a negative original for 35 s with a metal halide lamp with a power of 5 kW.
  • the exposed layer is covered with a plush pad with a developer solution of the following composition 5 parts by weight of sodium lauryl sulfate 1 part by weight of sodium metasilicate x 5 H2O 94 parts by volume of water developed.
  • the carriers are dried as described under point D1.
  • Table 2 shows that the products according to the invention are better than the prior art in many properties, but none worse than this in none.
  • Table 3 Example No. carrier Post-treatment agent Zincate test time (s) Contact angle Color veil 1) * Layer remnants 2) * 40 2nd D + + + + 41 2nd F + + + + 42 2nd E + O + + 43 2nd G + O + + 44 2nd L + O + + 45 2nd H + O + O 46 2nd K + O + + 47 2nd M + O + + 48 2nd I. + O + + 49 2nd N + O + O 50 2nd B - - + - 51 2nd A O O O O O 1 *) for positive layers 2 *) for negative layers
  • Table 3 shows that the electrochemically aftertreated supports give correspondingly good values as in Table 2, the values for the zincate test in particular being still improved.

Landscapes

  • Printing Plates And Materials Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Claims (18)

  1. Matériau de support en forme de plaque, pellicule ou ruban, pour plaques d'impression offset, constitué d'aluminium ou d'un de ses alliages, grainé mécaniquement, chimiquement ou électrochimiquement et eventuellement anodisé, qui porte sur au moins une face un revêtement hydrophile à base d'un polymère ayant une masse moléculaire moyenne d'au moins 1 000 et contenant des groupes latéraux acides, caractérisé en ce que le polymère hydrophile contient au moins 2 % en moles de motifs à groupes latéraux acides et, en plus des groupes latéraux acides, encore au moins 2 % en moles de motifs à groupes basiques, aptes à une protonation.
  2. Matériau de support selon la revendication 1, caractérisé en ce que le polymère hydrophile est un copolymère à base d'un motif monomère pourvu de groupes basiques et d'un motif monomère portant des groupes acides.
  3. Matériau de support selon la revendication 2, caractérisé en ce que le monomère portant des groupes basiques contient un groupe amino.
  4. Matériau de support selon la revendication 3, caractérisé en ce que le groupe amino contient au moins un radical alkyle ou aryle.
  5. Matériau de support selon la revendication 2, caractérisé en ce que le monomère portant des groupes acides contient un groupe carboxy.
  6. Matériau de support selon la revendication 2, caractérisé en ce que le monomère portant des groupes acides contient un groupe acide sulfonique.
  7. Matériau de support selon la revendication 2, caractérisé en ce que le monomère portant des groupes acides contient un groupe acide phosphonique.
  8. Matériau de support selon la revendication 1, caractérisé en ce que, en plus des groupes latéraux acides et des groupes latéraux basiques, le copolymère contient encore des motifs dépourvus d'activité acide/base.
  9. Matériau de support selon la revendication 1, caractérisé en ce que le copolymère a une masse moléculaire moyenne de 5 000 à 50 000.
  10. Matériau de support selon la revendication 1, caractérisé en ce que le copolymère a une masse moléculaire de plus de 50 000.
  11. Matériau de support selon la revendication 1, caractérisé en ce que le rapport de monomères des motifs monomères basiques présents dans le copolymère aux motifs monomères acides se situe dans la plage allant de 2:98 à 98:2.
  12. Matériau de support selon la revendication 11, caractérisé en ce que le rapport molaire des motifs monomères basiques aux motifs monomères acides est équimolaire.
  13. Matériau de support selon la revendication 12, caractérisé en ce que le rapport molaire des motifs monomères ioniques aux motifs monomères non ioniques va de 4:96 à 100 : 0.
  14. Matériau de support selon la revendication 1, caractérisé en ce que les groupes latéraux acides se présentent sous forme de sels métalliques avec des cations métalliques.
  15. Matériau de support selon la revendication 14, caractérisé en ce que le cation métallique du revêtement est union V⁵⁺, Bi³⁺, Al³⁺, Fe³⁺, Zr⁴⁺, Sn⁴⁺, Ca²⁺, Ba²⁺, Sr²⁺, Ti³⁺, Co²⁺, Fe²⁺, Ce⁴⁺, Mn²⁺, Ni²⁺, Cu²⁺, Zn²⁺ ou Mg²⁺.
  16. Procédé pour la fabrication d'un matériau de support pour plaques d'impression offset, selon l'une des revendications 1 à 15, caractérisé en ce que l'aluminium ou l'un de ses alliages est revêtu, par traitement par immersion ou électrochimique, avec le copolymère dissous, à une concentration de 0,02 à 5,0 % en poids, en solution aqueuse, éventuellement acide, et la couche est ensuite séchée.
  17. Procédé pour la fabrication d'un matériau de support selon la revendication 16, caractérisé en ce que l'aluminium ou l'un de ses alliages est d'abord traité par une solution à 0,01-10,0 % des polymères selon l'invention, et ensuite par une solution de préférence aqueuse d'un sel avec les cations V⁵⁺, Bi³⁺, Al³⁺, Fe³⁺, Zr⁴⁺, Sn⁴⁺, Ca²⁺, Ba²⁺, Sr²⁺, Ti³⁺, Co²⁺, Fe²⁺, Mn²⁺, Ni²⁺, Cu²⁺, Ce⁴⁺, Zn²⁺ ou Mg²⁺, à une concentration allant de 1,0 % à la saturation, et la couche formée à partir des produits de réaction est séchée.
  18. Utilisation d'un matériau de support selon l'une des revendications 1 à 15, pour le revêtement avec des substances photosensibles.
EP91111643A 1990-07-21 1991-07-12 Plaques, feuilles ou matériel en forme de bandes comme support pour des plaques d'impression offset, procédé pour sa préparation et son utilisation Expired - Lifetime EP0468313B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4023267A DE4023267A1 (de) 1990-07-21 1990-07-21 Platten-, folien- oder bandfoermiges traegermaterial fuer offsetdruckplatten, verfahren zu seiner herstellung und seine verwendung
DE4023267 1990-07-21

Publications (2)

Publication Number Publication Date
EP0468313A1 EP0468313A1 (fr) 1992-01-29
EP0468313B1 true EP0468313B1 (fr) 1995-06-14

Family

ID=6410773

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91111643A Expired - Lifetime EP0468313B1 (fr) 1990-07-21 1991-07-12 Plaques, feuilles ou matériel en forme de bandes comme support pour des plaques d'impression offset, procédé pour sa préparation et son utilisation

Country Status (7)

Country Link
US (1) US5302460A (fr)
EP (1) EP0468313B1 (fr)
JP (1) JP2529041B2 (fr)
KR (1) KR920002368A (fr)
BR (1) BR9103111A (fr)
CA (1) CA2047464A1 (fr)
DE (2) DE4023267A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5316831A (en) * 1991-05-08 1994-05-31 Fuji Electric Co., Ltd. Metallic printed board
DE69603102T2 (de) * 1995-03-01 2000-03-02 Agfa Gevaert Nv Verfahren zur Herstellung einer Aluminiumfolie zur Verwendung als Träger in lithographischen Druckplatten
US5888695A (en) * 1995-11-20 1999-03-30 Aluminum Company Of America Lithographic sheet material including a metal substrate, thermoplastic adhesive layer and mineral or metal particles
JPH09231821A (ja) * 1995-12-22 1997-09-05 Toto Ltd 照明器具及び照度維持方法
GB9825822D0 (en) * 1998-11-16 1999-01-20 Agfa Gevaert Ltd Production of lithographic printing plate support
JP4056682B2 (ja) * 2000-07-11 2008-03-05 富士フイルム株式会社 平版印刷版用支持体
US7063935B2 (en) * 2002-03-26 2006-06-20 Fuji Photo Film Co., Ltd. Support for lithographic printing plate and presensitized plate and method of producing lithographic printing plate
US6854391B2 (en) * 2002-06-10 2005-02-15 Flint Ink Corporation Lithographic printing method and materials
JP2005305740A (ja) * 2004-04-20 2005-11-04 Konica Minolta Medical & Graphic Inc 感光性平版印刷版材料用アルミニウム板支持体、その製造方法及び感光性平版印刷版材料

Family Cites Families (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE540601A (fr) * 1950-12-06
GB864033A (en) * 1956-08-21 1961-03-29 Harris Intertype Corp Photo-lithographic plates and coating compositions therefor
US2991204A (en) * 1957-06-19 1961-07-04 Harris Intertype Corp Hydrophilic surface
GB907718A (en) * 1957-11-01 1962-10-10 Lithoplate Inc Hydrophilic base plates for diazo presensitized lithographic printing plates
US3073723A (en) * 1958-10-03 1963-01-15 Lithoplate Inc Resinous coatings adapted to receive a light-sensitive layer in the production of lithographic printing plates
BE606888A (fr) * 1960-08-05 1900-01-01
US3298852A (en) * 1963-02-07 1967-01-17 Dick Co Ab Metal offset plate and method for manufacture
US3280734A (en) * 1963-10-29 1966-10-25 Howard A Fromson Photographic plate
US3181461A (en) * 1963-05-23 1965-05-04 Howard A Fromson Photographic plate
US3258339A (en) * 1964-05-28 1966-06-28 Harris Intertype Corp Lithographic plate and method of preparing same
US3440050A (en) * 1965-02-05 1969-04-22 Polychrome Corp Lithographic plate
NL6809658A (fr) * 1967-07-12 1969-01-14
ZA6807938B (fr) * 1967-12-04
GB1246696A (en) * 1969-01-29 1971-09-15 Hawthorn Baker Ltd Improvements in anodised aluminium photolithographic printing plates
DE1938039C3 (de) * 1969-07-26 1978-04-06 Henkel Kgaa, 4000 Duesseldorf Verfahren zur Behandlung von anodisch oxydierten Aluminiumoberflächen
JPS492286B1 (fr) * 1970-02-19 1974-01-19
US4049746A (en) * 1970-12-11 1977-09-20 The Richardson Company Intermediate coating compositions and long running planographic plates prepared therewith
US3769043A (en) * 1971-05-20 1973-10-30 Ricoh Kk Treating solution for planographic printing plates
BE794939A (fr) * 1972-02-03 1973-08-02 Eastman Kodak Co Produit propre a l'utilisation en lithographie
US3861917A (en) * 1972-02-22 1975-01-21 Grace W R & Co Continuous tone lithographic plate and method of making
US3860426A (en) * 1972-12-22 1975-01-14 Eastman Kodak Co Subbed lithographic printing plate
US4116695A (en) * 1974-09-12 1978-09-26 Fuji Photo Film Co., Ltd. Method of producing a support for a printing plate
US3902976A (en) * 1974-10-01 1975-09-02 S O Litho Corp Corrosion and abrasion resistant aluminum and aluminum alloy plates particularly useful as support members for photolithographic plates and the like
NL7603530A (nl) * 1975-04-07 1976-10-11 Dow Chemical Co Werkwijze, samenstelling en emulsie voor de be- handeling van beeld-dragende lithografische druk- platen, alsmede als zodanig verkregen beklede platen.
JPS53104301A (en) * 1977-02-22 1978-09-11 Ricoh Kk Treating solution for lithographic printing
SU647142A1 (ru) * 1977-05-23 1979-02-15 Львовский политехнический институт Офсетна печатна форма
JPS5573591A (en) * 1978-11-29 1980-06-03 Fuji Photo Film Co Ltd Photosensitive planographic printing plate
DE3126636A1 (de) * 1981-07-06 1983-01-27 Hoechst Ag, 6000 Frankfurt Hydrophilierte traegermaterialien fuer offsetdruckplatten, ein verfahren zu ihrer herstellung und ihre verwendung
DE3126626A1 (de) * 1981-07-06 1983-01-20 Hoechst Ag, 6000 Frankfurt Hydrophilierte traegermaterialien fuer offsetdruckplatten, ein verfahren zu ihrer herstellung und ihre verwendung
US4420549A (en) * 1981-09-08 1983-12-13 Minnesota Mining And Manufacturing Company Lithographic substrate and its process of manufacture
JPS59101651A (ja) * 1982-12-02 1984-06-12 Fuji Photo Film Co Ltd 感光性平版印刷版
US4483913A (en) * 1983-07-18 1984-11-20 Polychrome Corporation Planographic printing plate
DE3569703D1 (en) * 1984-01-17 1989-06-01 Fuji Photo Film Co Ltd Presensitized plate having an anodized aluminum base with an improved hydrophilic layer
JPS63112193A (ja) * 1986-10-31 1988-05-17 Nippon Parkerizing Co Ltd 平版印刷用アルミニウム基板の製造方法
JPH062434B2 (ja) * 1986-11-20 1994-01-12 富士写真フイルム株式会社 平版印刷版用支持体
JPH02125789A (ja) * 1988-11-04 1990-05-14 Fuji Photo Film Co Ltd 平版印刷版用アルミニウム支持体の製造方法
DE4023269A1 (de) * 1990-07-21 1992-01-23 Hoechst Ag Hydrophile mischpolymere sowie deren verwendung in der reprographie
DE4023271A1 (de) * 1990-07-21 1992-01-23 Hoechst Ag Thermisch vernetzbare hydrophile mischpolymere sowie deren verwendung in der reprographie

Also Published As

Publication number Publication date
KR920002368A (ko) 1992-02-28
BR9103111A (pt) 1992-02-11
JPH05139067A (ja) 1993-06-08
EP0468313A1 (fr) 1992-01-29
DE59105689D1 (de) 1995-07-20
DE4023267A1 (de) 1992-01-23
CA2047464A1 (fr) 1992-01-22
US5302460A (en) 1994-04-12
JP2529041B2 (ja) 1996-08-28

Similar Documents

Publication Publication Date Title
EP0069320B1 (fr) Matériaux de support pour plaques lithographiques, aux propriétés hydrophiles améliorées, procédés pour leur fabrication, et leur utilisation
EP0105170B1 (fr) Procédé de posttraitement de couches d'oxyde d'aluminium avec des solutions aqueuses contenant du silicate alcalin et son application dans la fabrication des supports pour plaques d'impression
EP0069319B1 (fr) Matériaux de support pour plaques lithographiques, aux propriétés hydrophiles améliorées, procédés pour leur fabrication, et leur utilisation
EP0008440B1 (fr) Procédé d'oxydation anodique d'aluminium et son application comme support de plaque d'impression
EP0121880B1 (fr) Procédé en deux pas pour la préparation de matériaux anodisés d'aluminium en forme plane et leur utilisation dans la fabrication de planches à imprimer offset
EP0154200A1 (fr) 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
EP0268790B1 (fr) Procédé pour la modification par enlèvement de supports en aluminium ou en alliage de l'aluminium décapés en plusieurs étapes et utilisation de ceux-ci pour la fabrication de plaques offset
EP0004569A1 (fr) Procédé d'oxydation anodique de l'aluminium et son utilisation comme matériau porteur pour plaques d'impression
EP0097301B1 (fr) Procédé pour la modification par l'enlèvement de supports en aluminium décapés par voie électrochimique et l'utilisation de ceux-ci pour la fabrication des plaques offset
EP0468313B1 (fr) Plaques, feuilles ou matériel en forme de bandes comme support pour des plaques d'impression offset, procédé pour sa préparation et son utilisation
EP0190643B1 (fr) Matériau de supports hydrophilisés pour plaques d'impression offset, procédé de fabrication et leur emploi
EP0086956B1 (fr) Procédé pour la production de matériaux de support pour des plaques d'impression offset
EP0095581B1 (fr) 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
EP0161461B1 (fr) Procédé d'oxydation anodique d'aluminium et son application comme matériau de support pour plaques d'impression offset
EP0170045B1 (fr) Procédé pour le décapage et le chromage simultanés de plaques d'acier comme supports pour des utilisations lithographiques
DE3637764A1 (de) Traegermaterial auf der basis von aluminium oder dessen legierungen fuer offsetdruckplatten sowie verfahren zu dessen herstellung
EP0154201B1 (fr) 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
EP0167087B1 (fr) Procédé pour le décapage électrochimique de plaques d'acier pour l'utilisation comme supports pour plaques d'impression offset ainsi qu'une solution électrolytique appropriée à ce procédé
EP0035730A2 (fr) Procédé pour la modification de la surface de matériaux supports de plaques d'impression en aluminium et procédé pour la production de plaques d'impression en ces matériaux

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB IT NL

17P Request for examination filed

Effective date: 19920217

17Q First examination report despatched

Effective date: 19931215

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB IT NL

REF Corresponds to:

Ref document number: 59105689

Country of ref document: DE

Date of ref document: 19950720

ET Fr: translation filed
ITF It: translation for a ep patent filed

Owner name: SOCIETA' ITALIANA BREVETTI S.P.A.

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19950814

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20000705

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20000706

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20000710

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20000720

Year of fee payment: 10

REG Reference to a national code

Ref country code: GB

Ref legal event code: 746

Effective date: 20000821

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010712

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020201

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20010712

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020329

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20020201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020501

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050712