EP1046497B1 - Méthode pour la fabrication des planches d'impression lithographiques utilisant une résine novolaque - Google Patents

Méthode pour la fabrication des planches d'impression lithographiques utilisant une résine novolaque Download PDF

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Publication number
EP1046497B1
EP1046497B1 EP19990201217 EP99201217A EP1046497B1 EP 1046497 B1 EP1046497 B1 EP 1046497B1 EP 19990201217 EP19990201217 EP 19990201217 EP 99201217 A EP99201217 A EP 99201217A EP 1046497 B1 EP1046497 B1 EP 1046497B1
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EP
European Patent Office
Prior art keywords
novolac
ink
resin
printing
lithographic
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
EP19990201217
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German (de)
English (en)
Other versions
EP1046497A1 (fr
Inventor
Leo c/o Agfa-Gevaert N.V. Oelbrandt
Augustin c/o Agfa-Gevaert N.V. Meisters
Huub c/o Agfa-Gevaert N.V. Van Aert
Luc C/O Agfa-Gevaert N.V. Leenders
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.)
Agfa Gevaert NV
Original Assignee
Agfa Gevaert NV
Agfa Gevaert AG
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Publication date
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Priority to DE69912740T priority Critical patent/DE69912740T2/de
Priority to EP19990201217 priority patent/EP1046497B1/fr
Priority to JP2000116194A priority patent/JP2000313178A/ja
Publication of EP1046497A1 publication Critical patent/EP1046497A1/fr
Application granted granted Critical
Publication of EP1046497B1 publication Critical patent/EP1046497B1/fr
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Classifications

    • 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
    • B41C1/1066—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by spraying with powders, by using a nozzle, e.g. an ink jet system, by fusing a previously coated powder, e.g. with a laser

Definitions

  • the present invention relates to methods for making lithographic printing plates.
  • it relates to a method for directly making the lithographic printing plates by using hydrophobic novolac resins, which makes it possible to produce the lithographic plates directly from digital data output from computers, facsimiles, or the like without using any intermediate films having negative or positive images.
  • the direct plate-making method a method wherein an image or non-image portion is directly formed on a substrate by ink-jet printing is known to the art.
  • the ink-jet printing system is a relatively rapid image output system and has a simple construction because it does not require any complex optical system. Therefore, the printing system makes an apparatus for making printing plates simple and the cost for making printing plates can be reduced since the maintenance labor is largely reduced.
  • Japanese Kokai Publication 113456/1981 proposes the methods for preparing printing plates wherein ink-repelling materials (e.g. curable silicone) are printed on a printing plate by ink-jet printing.
  • the printing plate obtained by this method is an intaglio printing plate in which the ink-repelling material formed on the surface of the substrate serves as a non-image part.
  • the resolution of the printed images at shadow area or reversed lines is not so good.
  • a large amount of ink is needed in this method because the ink-repelling material must be deposited on the whole non-image part which occupies most of the surface of the printing plate, thereby delaying the printing process.
  • US-P- 5 511 477 discloses a method for the production of photopolymeric relief-type printing plates comprising: forming a positive or a negative image on a substrate by ink-jet printing with a photopolymeric ink composition, optionally preheated to a temperature of about 30°-260°C; and subjecting the resulting printed substrate to UV radiation, thereby curing said ink composition forming said image.
  • This is an obnoxious method due to the sometimes high vapour pressure and toxicity of said inks.
  • US-P- 5 312 654 discloses a method for making lithographic printing plates comprising: forming an image on a substrate having an ink absorbing layer and a hydrophilized layer between the substrate and absorbing layer by ink-jet printing using a photopolymerizable ink composition, and exposing it to an active light in the wavelength region with which said ink composition is sensitized to cure the image.
  • the printing endurance of said printing plates is low.
  • Japanese Kokai Publication 69244/1992 discloses a method for making printing plates comprising the steps of forming a printed image on a recording material subjected to a hydrophilic treatment by ink-jet printing using a hydrophobic ink containing photocurable components; and exposing the whole surface to an active light.
  • the surface of the substrate to be used for the lithographic plate is usually subjected to various treatments such as a mechanical graining, an anodizing or a hydrophilic treatment to obtain good hydrophilic property and water retention property. Therefore, even the use of an ink composition having a very high surface tension results in a poor image on the surface of the substrate because of ink spreading and low printing endurance.
  • EP-A- 533 168 discloses a method for avoiding said ink spreading by coating the lithographic base with an ink absorbing layer which is removed after ink printing. This is an uneconomical and cumbersome method.
  • Research Disclosure 289118 of May 1988 discloses a method for making printing plates with the use of an ink jet wherein the ink is a hydrophobic polymer latex.
  • said printing plates have a bad ink acceptance and a low printing endurance.
  • EP-A- 776 763 discloses a method for producing a lithographic printing plate containing a printable resinous image comprising: depositing a liquid comprising at least one reactant of a resin producing reaction mixture onto said plate employing at least one printer head in a predetermined image-reproducing manner, said liquid deposited onto said plate in contact with remaining reactants necessary to complete said mixture on the surface of said plate; and polymerizing said complete mixture on said plate under resin polymerization conditions whereby said lithographic plate containing a printable resinous image is produced.
  • This is a cumbersome manner for producing a printing plate by ink jet.
  • a method for making a lithographic printing plate comprising the step of dispensing in a predetermined pattern a novolac resin onto a hydrophilic surface of a lithographic base.
  • a novolac is any of the phenol-formaldehyde resins made with an excess of phenol in the reaction.
  • Said phenol can be phenol, cresol etc.
  • Preferred novolac resins are poly (cresol-xylenol-formaldehyde) resins and poly (phenol-xylenol-formaldehyde) resins.
  • the novolac resin is dispersed in an aqueous medium or dissolved in an organic solvent. Suitable organic solvents are e.g. 1-methoxy-2-propanol, ethyl acetate, methyl ethylketone and isopropanol.
  • the concentration of the resin in solution ranges from 5 to 50 % by weight, more preferably from 10 to 30 % by weight.
  • the concentration of novolac resins in an aqueous dispersion ranges from 5 % to 80 % by weight, more preferably from 20 to 60 % by weight.
  • the novolac resins according to the invention have a molecular weight of at least 1000, more preferably of at least 5000, most preferably of at least 10000. Said novolacs could comprise an epoxy group.
  • the novolac resin is a hydrophobic, oleophilic resin.
  • a hydrophobic oleophilic compound is a compound that, when brought in a mixture of water and oil, is wetted by oil while a hydrophilic compound, when brought in a mixture of water and oil, is wetted with water.
  • the lithographic base with a hydrophilic surface is preferably heated after spraying said hydrophilic surface with droplets of the hydrophobic polymer in the predetermined pattern at a temperature of preferably at least 45°C, more preferably at least 55°C.
  • said heating is carried out in an oven.
  • the lithographic base having a hydrophilic surface after being sprayed with droplets of the hydrophobic polymer in the predetermined pattern is heated preferably for at least one minute, more preferably for at least 5 minutes.
  • said heating is carried out by contacting to a hot body.
  • said heating is carried out with an IR-heater or laser.
  • the time of heating is then the time of the laser 5 dwell time, i.e. from 0.005 to 2 us.
  • This mode of heating requires that the lithographic base or the novolac resin solution or dispersion comprises a compound capable of converting laser-light to heat.
  • an infrared pigment or dye for that purpose.
  • Particularly desirable in this invention is an infrared dye.
  • pigments can be used as well such as e.g.carbon black, a conductive polymer particle, metal carbides, borides, nitrides, carbonitrides, bronze-structured oxides and oxides structurally related to the bronze family but lacking the A component e.g. WO2.9.
  • curing agents In order to improve the abrasion resistance, there can be added curing agents to the solution or more preferably to the dispersion of said novolac resin.
  • Suitable curing agents are amines such as Jeffamine TM, trade name of Texaco Chemical Co and Euredur TB03345 TM, trade name of Witco Chemical Cob but also mercaptans or alcohol groups containing components can be used. Said curing agents are preferably used in an amount of 5 to 80 % by weight of the novolac.
  • coupling agents can be added to the solution or dispersion of a novolac in order to improve the adhesion between said novolac and the hydrophilic surface of the lithographic support.
  • Suitable coupling agents are alkoxysilanes with a amino- or an epoxy function, but other adhesion improving functions are also possible.
  • Said coupling agents are preferably used in an amount of 2 to 10 % by weight.
  • the lithographic base may be an anodised aluminum support.
  • a particularly preferred lithographic base is an electrochemically grained and anodised aluminum support.
  • the anodised aluminum support may be treated to improve the hydrophilic properties of its surface.
  • the aluminum support may be silicated by treating its surface with sodium silicate solution at elevated temperature, e.g. 95°C.
  • a phosphate treatment may be applied which involves treating the aluminum oxide surface with a phosphate solution that may further contain an inorganic fluoride.
  • the aluminum oxide surface may be rinsed with a citric acid or citrate solution. This treatment may be carried out at room temperature or may be carried out at a slightly elevated temperature of about 30 to 50°C.
  • a further interesting treatment involves rinsing the aluminum oxide surface with a bicarbonate solution.
  • the aluminum oxide surface may be treated with polyvinylphosphonic acid, polyvinylmethylphosphonic acid, phosphoric acid esters of polyvinyl alcohol, polyvinylsulphonic acid, polyvinylbenzenesulphonic acid, sulphuric acid esters of polyvinyl alcohol, and acetals of polyvinyl alcohols formed by reaction with a sulphonated aliphatic aldehyde It is further evident that one or more of these post treatments may be carried out alone or in combination.
  • the lithographic base with a hydrophilic surface comprises a flexible support, such as e.g. paper or plastic film, provided with a cross-linked hydrophilic layer.
  • a particularly suitable cross-linked hydrophilic layer may be obtained from a hydrophilic binder cross-linked with a cross-linking agent such as formaldehyde, glyoxal, polyisocyanate or a hydrolysed tetraalkylorthosilicate. The latter is particularly preferred.
  • hydrophilic binder there may be used hydrophilic (co)polymers such as for example, homopolymers and copolymers of vinyl alcohol, acrylamide, methylol acrylamide, methylol methacrylamide, acrylate acid, methacrylate acid, hydroxyethyl acrylate, hydroxyethyl methacrylate or maleic anhydride/vinylmethylether copolymers.
  • the hydrophilicity of the (co)polymer or (co)polymer mixture used is preferably the same as or higher than the hydrophilicity of polyvinyl acetate hydrolyzed to at least an extent of 60 percent by weight, preferably 80 percent by weight.
  • the amount of crosslinking agent, in particular of tetraalkyl orthosilicate, is preferably at least 0.2 parts by weight per part by weight of hydrophilic binder, more preferably between 0.5 and 5 parts by weight, most preferably between 1.0 parts by weight and 3 parts by weight.
  • a cross-linked hydrophilic layer in a lithographic base used in accordance with the present embodiment preferably also contains substances that increase the mechanical strength and the porosity of the layer.
  • colloidal silica may be used.
  • the colloidal silica employed may be in the form of any commercially available water-dispersion of colloidal silica for example having an average particle size up to 40 nm, e.g. 20 nm.
  • inert particles of larger size than the colloidal silica may be added e.g. silica prepared according to Stöber as described in J. Colloid and Interface Sci., Vol.
  • alumina particles or particles having an average diameter of at least 100 nm which are particles of titanium dioxide or other heavy metal oxides.
  • the thickness of a cross-linked hydrophilic layer in a lithographic base in accordance with this embodiment may vary in the range of 0.2 to 25 ⁇ m and is preferably 1 to 10 ⁇ m.
  • plastic film e.g. substrated polyethylene terephthalate film, substrated polyethylene naphthalate film, cellulose acetate film, polystyrene film, polycarbonate film etc.
  • the plastic film support may be opaque or transparent.
  • glass with a thickness less than 1.2 mm and a failure stress (under tensile stress) equal or higher than 5 x 10 7 .
  • the amount of silica in the adhesion improving layer is between 200 mg per m 2 and 750 mg per m 2 .
  • the ratio of silica to hydrophilic binder is preferably more than 1 and the surface area of the colloidal silica is preferably at least 300 m 2 per gram, more preferably at least 500 m 2 per gram.
  • the novolac dispersion is defined as a stable colloidal dispersion of a novolac substance in an aqueous medium.
  • the novolac particles are usually approximately spherical and of typical colloidal dimensions: particle diameters range from about 20 to 1000 nm.
  • the dispersion medium is usually a dilute aqueous solution containing substances such as electrolytes, surfactants, hydrophilic polymers and initiator residues
  • hydrophobic novolac resins can be used.
  • carbon black or dyes or pigments can be mixed with a novolac resin.
  • the novolac resin can be dispensed onto the lithographic base having a hydrophilic surface preferably by an ink jet printer.
  • a volatilization preventive agent is added to the ink according to the present invention, if necessary, to suppress evaporation of the liquid in the ink-jet nozzle and to prevent clogging due to precipitation of the dissolved or dispersed components.
  • a surfactant is preferably added to the the ink according to the present invention to adjust the size of droplets of the dispersion blowing out from the ink jet nozzle, to adjust the surface tension of the ink so that images can be formed in high resolution.
  • heat polymerisation inhibitors desinfectants, anticontamination agents and anti-fungal agents can be also added.
  • buffers and solubilizers is effective to improve the solubility or dispersibility of the polymer.
  • Addition of defoaming agents and foam suppressing agents are also possible to suppress foaming of the ink in the ink-jet nozzle.
  • the image forming requires the following steps. On demand, microdots of the hydrophobic novolac resin are sprayed onto the lithographic base in a predetermined pattern as the plate passes through the printer or by a printhead shutteling over the plate. 5 According to one embodiment of the invention, the microdots have a diameter of about 30 ⁇ m.
  • the lithographic base sprayed with hydrophobic novolac resin can be heated. This can be done by irradiation, by convection or by contact with a hot surface e.g.in an oven, by flash exposure, by IR-heaters or by laser irradiation.
  • the image forming can also be carried out with the lithographic base already on the printing cylinder.
  • the optional heating of the novolac resin can be effected by using a heated printing cylinder.
  • the printing plate of the present invention can also be used in the printing process as a seamless sleeve printing plate.
  • This cylindrical printing plate has such a diameter that it can be slided on the print cylinder. More details on sleeves are given in "Grafisch Nieuws" ed. Keesing, 15, 1995, page 4 to 6.
  • KIESELSOL 300 F (tradename for 30 % aqueous dispersion of colloidal silica - surface area of 300 m 2 per g).
  • Anionic wetting agents ( 0.6 g ) and biocides (1 g ) were added.
  • a 0.30 mm thick aluminum foil was degreased by immersing the foil in an aqueous solution containing 5 g/l of sodium hydroxide at 50°C and rinsed with demineralized water.
  • the foil was then electrochemically grained using an alternating current in an aqueous solution containing 4 g/l of hydrochloric acid, 4 g/l of hydroboric acid and 5 g/l of aluminum ions at a temperature of 35°C and a current density of 1200 A/m 2 to form a surface topography with an average center-line roughness Ra of 0.5 ⁇ m.
  • the aluminum foil was then etched with an aqueous solution containing 300 g/l of sulfuric acid at 60°C for 180 seconds and rinsed with demineralized water at 25°C for 30 seconds.
  • the foil was subsequently subjected to anodic oxidation in an aqueous solution containing 200 g/l of sulfuric acid at a temperature of 45°C, a voltage of about 10 V and a current density of 150 A/m 2 for about 300 seconds to form an anodic oxidation film of 3.00 g/m 2 of Al 2 O 3 then washed with demineralized water, posttreated with a solution containing polyvinylphosphonic acid and subsequently with a solution containing aluminum trichloride, rinsed with demineralized water at 20°C during 120 seconds and dried.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacture Or Reproduction Of Printing Formes (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Ink Jet (AREA)

Claims (9)

  1. Procédé pour fabriquer un cliché d'impression lithographique comprenant les étapes consistant à disperser en un modèle prédéterminé une résine novolaque sur une surface hydrophile d'une base lithographique.
  2. Procédé pour fabriquer un cliché d'impression lithographique selon la revendication 1, dans lequel ladite résine novolaque est une résine de poly-(crésol-xylénol-formaldéhyde) ou une résine de poly-(phénol-xylénol-formaldéhyde).
  3. Procédé selon la revendication 1 ou 2, dans lequel ladite résine novolaque est dissoute dans un solvant organique.
  4. Procédé selon la revendication 3, dans lequel la concentration de la résine en solution s'élève de 5 à 50 % en poids.
  5. Procédé selon la revendication 1 ou 2, dans lequel ladite résine novolaque est dispersée dans un milieu aqueux.
  6. Procédé selon la revendication 5, dans lequel la concentration de la résine en dispersion s'élève de 5 à 80 %.
  7. Procédé selon l'une quelconque des revendications 1 à 6, dans lequel ladite résine novolaque comprend un agent de durcissement.
  8. Procédé selon l'une quelconque des revendications 1 à 7, dans lequel ladite résine novolaque comprend un agent de couplage.
  9. Procédé selon l'une quelconque des revendications 1 à 8, dans lequel ladite étape de mise en dispersion est mis en oeuvre via un appareil d'impression par jet d'encre.
EP19990201217 1999-04-19 1999-04-19 Méthode pour la fabrication des planches d'impression lithographiques utilisant une résine novolaque Expired - Lifetime EP1046497B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE69912740T DE69912740T2 (de) 1999-04-19 1999-04-19 Verfahren zur Herstellung von lithographischen Druckplatten, das ein Novolakharz verwendet
EP19990201217 EP1046497B1 (fr) 1999-04-19 1999-04-19 Méthode pour la fabrication des planches d'impression lithographiques utilisant une résine novolaque
JP2000116194A JP2000313178A (ja) 1999-04-19 2000-04-18 ノボラック溶液又は分散液からのポジティブ作用性印刷版の作製方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19990201217 EP1046497B1 (fr) 1999-04-19 1999-04-19 Méthode pour la fabrication des planches d'impression lithographiques utilisant une résine novolaque

Publications (2)

Publication Number Publication Date
EP1046497A1 EP1046497A1 (fr) 2000-10-25
EP1046497B1 true EP1046497B1 (fr) 2003-11-12

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JP (1) JP2000313178A (fr)
DE (1) DE69912740T2 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10136068A1 (de) * 2001-07-25 2003-02-13 Heidelberger Druckmasch Ag Verfahren und Vorrichtung zur Strukturierung einer Oberfläche in hydrophile und hydrophobe Bereiche
US6969541B2 (en) 2001-07-25 2005-11-29 Heidelberger Druckmaschinen Ag Method and device for structuring a surface to form hydrophilic and hydrophobic regions
DE102011052991B4 (de) * 2011-08-25 2013-12-24 Gert Sieger Verfahren zur Herstellung einer Druckform für den wasserlosen Offsetdruck

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2078361A1 (fr) * 1991-09-17 1993-03-18 Seiji Arimatsu Methode de fabrication directe de plaques d'impression pour systeme a jet d'encre
US5820932A (en) * 1995-11-30 1998-10-13 Sun Chemical Corporation Process for the production of lithographic printing plates

Also Published As

Publication number Publication date
JP2000313178A (ja) 2000-11-14
EP1046497A1 (fr) 2000-10-25
DE69912740D1 (de) 2003-12-18
DE69912740T2 (de) 2004-09-23

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