EP0773112A1 - Heat sensitive imaging element and method for making a printing plate therewith - Google Patents

Heat sensitive imaging element and method for making a printing plate therewith Download PDF

Info

Publication number
EP0773112A1
EP0773112A1 EP96202950A EP96202950A EP0773112A1 EP 0773112 A1 EP0773112 A1 EP 0773112A1 EP 96202950 A EP96202950 A EP 96202950A EP 96202950 A EP96202950 A EP 96202950A EP 0773112 A1 EP0773112 A1 EP 0773112A1
Authority
EP
European Patent Office
Prior art keywords
imaging element
image forming
image
forming layer
cross
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.)
Granted
Application number
EP96202950A
Other languages
German (de)
French (fr)
Other versions
EP0773112B1 (en
Inventor
Joan Agfa-Gevaert N.V. IIE 3800 Vermeersch
Marc Agfa-Gevaert N.V. IIE 3800 Van Damme
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
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 Agfa Gevaert NV filed Critical Agfa Gevaert NV
Priority to EP19960202950 priority Critical patent/EP0773112B1/en
Publication of EP0773112A1 publication Critical patent/EP0773112A1/en
Application granted granted Critical
Publication of EP0773112B1 publication Critical patent/EP0773112B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41CPROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00Forme preparation
    • B41C1/10Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008Forme 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
    • B41C1/1025Forme 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 using materials comprising a polymeric matrix containing a polymeric particulate material, e.g. hydrophobic heat coalescing particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/36Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties
    • B41M5/366Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties using materials comprising a polymeric matrix containing a polymeric particulate material, e.g. hydrophobic heat coalescing particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41CPROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/04Negative working, i.e. the non-exposed (non-imaged) areas are removed
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41CPROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/08Developable by water or the fountain solution
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41CPROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/24Preparation 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

  • the present invention relates to a method for making a printing plate involving the use of a heat sensitive imaging element and that can be developed by means of plain water or an aqueous liquid.
  • Lithography is the process of printing from specially prepared surfaces, some areas of which are capable of accepting lithographic ink, whereas other areas, when moistened with water, will not accept the ink.
  • the areas which accept ink form the printing image areas and the ink-rejecting areas form the background areas.
  • a photographic material is made imagewise receptive to oily or greasy inks in the photo-exposed (negative-working) or in the non-exposed areas (positive-working) on a hydrophilic background.
  • lithographic printing plates also called surface litho plates or planographic printing plates
  • a support that has affinity to water or obtains such affinity by chemical treatment is coated with a thin layer of a photosensitive composition.
  • Coatings for that purpose include light-sensitive polymer layers containing diazo compounds, dichromate-sensitized hydrophilic colloids and a large variety of synthetic photopolymers. Particularly diazo-sensitized systems are widely used.
  • the exposed image areas become insoluble and the unexposed areas remain soluble.
  • the plate is then developed with a suitable liquid to remove the diazonium salt or diazo resin in the unexposed areas.
  • diazo based printing plates most commonly use an anodized and roughened aluminium as a support having a hydrophilic surface since they offer the advantage of a high printing endurance.
  • a particular disadvantage of such type of printing plates is that they require special developing liquids for development which is costly and inconvenient.
  • EP-A 601240 discloses a diazo based printing plate that uses a polyester film provided with a cross-linked hydrophilic layer as a lithographic base on which a photosensitive diazo layer is provided. Such a diazo based printing plate can be developed by rinsing it with plain water subsequent to image-wise exposure.
  • Lithocraft 10008 FOTOPLATETM is a diazo based printing plate that comprises on a paper support a hydrophilic layer on top of which is provided a diazo based photosensitive layer.
  • a plate can be prepared by image-wise exposure of the lithographic printing plate precursor or imaging element, mounting the exposed imaging element on the press and wiping its surface with Lithocraft® 10008 Developer Desensitizer.
  • the plate instructions also contemplate a method wherein no developer desensitizer is used. However, such method most often results in poor lithographic preformance so that in practice a Developer Desensitizer is almost always needed.
  • diazo-based printing plates carry in common irrespective of the type of lithographic base used, is that they have to be shielded from the light. Moreover, diazo's are insufficiently sensitive to be exposed by means of a commercial and economical laser.
  • FR-A-1,561,957 describes a recording material comprising at least a recording layer containing a hydrophilic binder and an hydrophobic compound dispersed in said hydrophylic binder. Upon irradiation and development said recording material can be used as a planographic printing plate.
  • US-A-3,476,937 describes also a recording material comprising at least a recording layer containing a hydrophilic binder and an hydrophobic compound dispersed in said hydrophylic binder. Upon irradiation and development said recording material can be used as a planographic printing plate.
  • US-A- 3,580,719 describes an imaging element containing a recording layer containing at least about 80 % by weight of a normally water-soluble polymer which, when heated, undergoes a loss in its normal solubility in aqueous solvent.
  • the three last imaging elements all have the disadvantage that the corresponding printing plates have low printing endurances.
  • EP 514.145 describes a method for making a printing plate wherein a heat-sensitive imaging element is used that comprises on a lithographic base such as an anodised aluminium an image forming layer comprising core-shell particles and a light to heat converting substance.
  • the shell of these particles is hydrophilic in nature and renders the particles developable.
  • the core is hydrophobic in nature and flows out when heated.
  • the image-forming layer can be rendered insoluble at the exposed areas.
  • the image forming layer can be removed by means of an aqueous developer containing ethanolamine. Subsequent the material is baked.
  • the present invention provides an imaging element comprising (i) on a hydrophilic surface of a lithographic base an image forming layer comprising hydrophobic thermoplastic polymer particles dispersed in a hydrophilic binder and (ii) a compound capable of converting light to heat, said compound being comprised in said image forming layer or a layer adjacent thereto, characterised in that said image forming layer further comprises a cross-linking agent capable of cross-linking said hydrophilic binder upon heating in a ratio between 1 :100 and 200:1 by weight versus the hydrophilic binder.
  • this invention provides a method for making a lithographic printing plate comprising the steps of:
  • An imaging element for use in accordance with the present invention comprises on a hydrophilic surface of a lithographic base an image forming layer comprising hydrophobic thermoplastic polymer particles dispersed in a hydrophilic binder and a cross-linking agent capable of cross-linking the hydrophilic binder upon heating.
  • the hydrophilic binder used in connection with the present invention is perferably not cross-linked or only slightly cross-linked.
  • the imaging element further includes a compound capable of converting light to heat. This compound is preferably comprised in the image forming layer but can also be provided in a layer adjacent to the image forming layer.
  • the lithographic base can be an anodised aluminium.
  • a particularly preferred lithographic base is an electrochemically grained and anodised aluminium support.
  • an anodised aluminium support may be treated to improve the hydrophilic properties of its surface.
  • the aluminium 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 aluminium oxide surface with a phosphate solution that may further contain an inorganic fluoride.
  • the aluminium oxide surface may be rinsed with a citric acid or citrate solution.
  • This treatment may be carried out at room temperature or can be carried out at a slightly elevated temperature of about 30 to 50°C.
  • a further interesting treatment involves rinsing the aluminium oxide surface with a bicarbonate solution. It is further evident that one or more of these post treatments may be carried out alone or in combination.
  • the lithographic base 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 tetra-alkylorthosilicate. 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, acrylic acid, methacrylic 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, preferably between 0.5 and 5 parts by weight, more 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 can 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. a polyester such as a substrated polyethylene terephthalate film or polyethylene naphthalate film, cellulose acetate film, polystyrene film, polycarbonate film etc.
  • the plastic film support may be opaque or transparent.
  • the amount of silica in the adhesion improving layer is 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 a surface area of 500 m 2 per gram.
  • an image forming layer on top of a hydrophilic surface there is provided an image forming layer.
  • an image forming layer in connection with the present invention comprises thermoplastic polymer particles dispersed in a hydrophilic binder and a cross-linking agent that can be activated by heat.
  • Suitable hydrophilic binders for use in an image forming layer in connection with this invention are preferably those that contain reactive groups e.g. hydroxy, amine or carboxyl groups.
  • hydrophilic binders are synthetic homo or copolymers such as a polyvinylalcohol, dimethylhydantoine-formaldehyde resin, a poly(meth)acrylic acid, a poly(meth)acrylamide, a polyhydroxyethyl(meth)acrylate, a polyvinylmethylether or natural binders such as gelatin, a polysacharide such as e.g. dextran, pullulan, cellulose, arabic gum, alginic acid.
  • Hydrophobic thermoplastic polymer particles used in connection with the present invention have a preferably a glass transition temperature of at least 90 °C, more preferably of at least 100 °C.
  • Hydrophobic thermoplastic polymer particles used in connection with the present invention preferably have a coagulation temperature above 50°C and more preferably above 70°C. Coagulation may result from softening or melting of the thermoplastic polymer particles under the influence of heat. There is no specific upper limit to the coagulation temperature of the thermoplastic hydrophobic polymer particles, however the temperature should be sufficiently below the decomposition of the polymer particles. Preferably the coagulation temperature is at least 10°C below the temperature at which the decomposition of the polymer particles occurs.
  • said polymer particles When said polymer particles are subjected to a temperature above coagulation temperature they coagulate to form a hydrophobic agglomerate in the hydrophilic layer so that at these parts the hydrophilic layer becomes insoluble in plain water or an aqueous liquid.
  • hydrophobic polymer particles for use in connection with the present invention are e.g. polystyrene, polyvinyl chloride, polymethyl methacrylate, polyvinylidene chloride, polyacrylonitrile, polyvinyl carbazole etc. or copolymers and/or mixtures thereof. Most preferably used is polymethyl methacrylate.
  • the weight average molecular weight of the polymers may range from 5,000 to 1,000,000g/mol.
  • the hydrophobic particles may have a particle size from 0.01 ⁇ m to 50 ⁇ m, more preferably between 0.05 ⁇ m and 10 ⁇ m and most preferably between 0.05 ⁇ m and 0.5 ⁇ m.
  • the polymer particles are present as a dispersion in the aqueous coating liquid of the image forming layer and may be prepared by the methods disclosed in US-P-3.476.937. Another method especially suitable for preparing an aqueous dispersion of the thermoplastic polymer particles comprises:
  • the amount of hydrophobic thermoplastic polymer particles contained in the image forming layer is preferably above 35% by weight and more preferably above 50% by weight and most preferably above 65% by weight.
  • Suitable compounds capable of converting light into heat are preferably infrared absorbing components although the wavelength of absorption is not of particular importance as long as the absorption of the compound used is in the wavelength range of the light source used for image-wise exposure.
  • Particularly useful compounds are for example dyes and in particular infrared dyes, carbon black, metal carbides, borides, nitrides, carbonitrides, bronze-structured oxides and oxides structurally related to the bronze family but lacking the A component e.g. WO 2.9 .
  • conductive polymer dispersion such as polypyrrole or polyaniline-based conductive polymer dispersions.
  • the lithographic performance and in particular the print endurance obtained depends on the heat-sensitivity of the imaging element. In this respect it has been found that carbon black yields very good and favorable results.
  • a light to heat converting compound in connection with the present invention is most preferably added to the image forming layer but at least part of the light to heat converting compound may also be comprised in a neighbouring layer.
  • Such layer can be for example the cross-linked hydrophilic layer of a lithographic base according to the second embodiment of lithographic bases explained above.
  • Suitable heat-activatable cross-linking agents for use in the image forming layer in connection with the present invention are used in a ratio between 1:100 to 200:1 by weight versus the hydrophilic binder, more preferably in a ratio between 1:50 to 50:1, most preferably in a ratio betxeen 1:10 to 10:1.
  • Suitable heat-activatable cross-linking agents for use in the image forming layer in connection with the present invention are preferably compounds that have two or more groups that can react with the hydrophilic binder, e.g. with one of the reactive groups listed above.
  • a cross-linking agent in connection with the present invention may be a low molecular weight compound or may be an oligomer or polymer.
  • suitable cross-linking agents for use in an image forming layer in accordance with the present invention are e.g. aldehydes such as formaldehyde, hexamethoxymethyl melamine, amine-formaldehyde resins such as e.g.
  • melamine-formaldehyde resin or guanamine-formaldehyde resin dimethylolurea-formaldehyde resins, phenol-formaldehyde resins, compounds having two or more expoxy groups e.g. a polymer having epoxy groups etc...
  • a catalyst to an image forming layer in connection with the present invention.
  • Such catalyst will speed-up the cross-linking reaction and accordingly total plate making time can be reduced while maintaining a high level of cross-linking needed to obtain a high printing endurance.
  • Particularly suitable catalysts for use in this context are acid catalysts. It may furthermore be advantageous to use a precursor of a catalyst so as to improve the selectivity of the process and to obtain the best lithographic performance. Such a precursor will convert to the actual catalyst upon heating i.e. the catalyst will be formed at least partially during the image-wise exposure.
  • Suitable precursors of a catalyst are for example precursors that release an acid upon heating.
  • suitable acid releasing catalyst precursors are sulfonium compounds, in particular benzylsulfonium compounds, as disclosed in e.g. EP 612065, EP 615233, and US 5.326.677, inorganic nitrates such as e.g. Mg(NO 3 ) 2 .6H 2 O or organic nitrates such as guanidinium nitrate, ammonium nitrate, pyridinium nitrate etc... as disclosed in EP 462763, WO 81/1755, US 4.370.401, compounds that release a sulfonic acid such as 3-sulfolenes, e.g.
  • thermolytic compounds disclosed in GB 1.204.495 2,5-dihydrothio-thiophene-1,1-dioxides as disclosed in US 5.312.721, thermolytic compounds disclosed in GB 1.204.495, co-cristalin adducts of an amine and an volatile organic acid as disclosed in US 3.669.747, aralkylcyanoforms as disclosed in US 3.166.583, thermo-acids disclosed in EP 159725 and DE 3515176, squaric acid generating compounds as disclosed in US 5.278.031, acid generating compounds disclosed in US 5.225.314 and US 5.227.277 and RD 11511 of November 1973.
  • an imaging element in accordance with the present invention is image-wise exposed to light and subsequently developed preferably by rinsing it with plain water.
  • the obtained imaged imaging element is then preferably overall heated to obtain the highest printing endurance.
  • the compound capable of converting light into heat absorbs the light used for image-exposure and converts this in heat so as to generate an image-wise pattern of heat in the image-forming layer.
  • the hydrophobic thermoplastic polymer particles coagulate and render the image forming layer insoluble for plain water or an aqueous liquid while the non-exposed parts remain soluble in plain water or an aqueous liquid.
  • the imaged imaging element is preferably overall heated which will cause substantial cross-linking of the image-forming layer and accordingly will improve the wear resistance of the printing areas during printing. Nevertheless, even without the additional overall heating, a printing endurance can be obtained that is suitable for a number of print jobs.
  • a gum before subjecting the imaged imaging element to the overall heat treatment. This will secure the hydrophilic properties at the non-printing areas in particular when an anodised aluminium is used as a lithographic base.
  • Suitable gums for this purpose are well-known and commercially available e.g. Polychrome PC965TM (Polychrome).
  • Image-wise exposure in connection with the present invention is preferably an image-wise scanning exposure involving the use of a laser or L.E.D.. It is highly preferred in connection with the present invention to use a laser emitting in the infrared (IR) and/or near-infrared, i.e. emitting in the wavelength range 700-1500nm. Particularly preferred for use in connection with the present invention are laser diodes emitting in the near-infrared.
  • IR infrared
  • near-infrared i.e. emitting in the wavelength range 700-1500nm.
  • laser diodes emitting in the near-infrared are particularly preferred for use in connection with the present invention.
  • a preferred imaging apparatus suitable for image-wise scanning exposure in accordance with the present invention preferably includes a laser output that can be provided directly to the imaging elements surface via lenses or other beam-guiding components, or transmitted to the surface of a blank imaging element from a remotely sited laser using a fiber-optic cable.
  • a controller and associated positioning hardware maintains the beam output at a precise orientation with respect to the imaging elements surface, scans the output over the surface, and activates the laser at positions adjacent selected points or areas of the imaging element.
  • the controller responds to incoming image signals corresponding to the original document and/or picture being copied onto the imaging element to produce a precise negative or positive image of that original.
  • the image signals are stored as a bitmap data file on a computer.
  • Such files may be generated by a raster image processor (RIP) or other suitable means.
  • a RIP can accept Input data in page-description language, which defines all of the features required to be transferred onto the imaging element, or as a combination of page-description language and one or more image data files.
  • the bitmaps are constructed to define the hue of the color as well as screen frequencies and angles in case of amplitude modulation screening.
  • the present invention is particularly suitable for use in combination with frequency modulation screening as disclosed in e.g. EP-A 571010, EP-A 620677 and EP-A 620674.
  • the imaging apparatus can be configured as a flatbed recorder or as a drum recorder, with the imaging element mounted to the interior or exterior cylindrical surface of the drum.
  • the requisite relative motion between the laser beam and the imaging element is achieved by rotating the drum(and the imaging element mounted thereon) about its axis and moving the beam parallel to the rotation axis, thereby scanning the imaging element circumferentially so the image "grows" in the axial direction.
  • the beam can move parallel to the drum axis and, after each pass across the imaging element, increment angularly so that the image on the imaging element "grows" circumferentially.
  • the beam is drawn across either axis of the imaging element, and is indexed along the other axis after each pass.
  • the requisite relative motion between the beam and the imaging element may be produced by movement of the imaging element rather than (or in addition to) movement of the beam.
  • the beam is scanned, it is generally preferable (for reasons of speed) to employ a plurality of lasers and guide their outputs to a single writing array.
  • the writing array is then indexed, after completion of each pass across or along the imaging element, a distance determined by the number of beams emanating from the array, and by the desired resolution (i.e. the number of image points per unit length.
  • a 0.2mm thick aluminium foil was degreased by immersing the foil in an aqueous solution containing 5g/l of sodium hydroxide at 50°C and rinsed with demineralised water.
  • the foil was then electrochemically grained using an alternating current in an aqueous solution containing 4g/l of hydrochloric acid, 4 g/l of hydroboric acid and 0.5g/l of aluminium 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 R a of 0.5 ⁇ m.
  • the aluminium foil was then etched with an aqueous solution containing 300g/l of sulfuric acid ate 60°C for 180 seconds and rinsed with demineralised 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 at temperature of 45°c, a voltage of about 10V and a current density of 150 A/m 2 for about 300 seconds to form an anodic oxidation film of 3g/m 2 Al 2 O 3 , then washed with demineralised water, post treated with a solution containing 20 g/l of sodium bicarbonated at 40°C for 30s, subsequently rinsed with demineralised water of 20°C during 120s and dried.
  • the obtained lithographic base was submersed in an aqueous solution containing 5% by weight of citric at 50°C for 60s, rinsed with demineralised water and dried at 40°C.
  • An imaging element according to the invention was produced by preparing the following coating composition and coating it to the above described lithographic base in an amount of 30g/m 2 (wet coating amount) and drying it at 35°C.
  • the obtained imaging element was subjected to an image-wise scanning exposure using an infrared laser diode emitting at 830 nm.
  • the scanspeed was 1 m/s, spot size 10 ⁇ m and 120 mW power on the plate surface.
  • the imaging element was subsequent developed in a Polychrome PC28ETM processor filled with water in the developing section and a gum (Polychrome PC965TM) in the gumming section.
  • the obtained printing plate was then mounted on a Heidelberg GTO46 offset press equipped with K + E 125 ink and as dampening liquid Rotamatic. 15000 clear copies were obtained with no ink-acceptance in the non-image areas. Even after printing 15000 copies, no damage to the image areas could be seen.
  • Printing plates were prepared as described in example 1 but with the modification that hexamethoxymethylmelamine (cross-linker) was not used in the coating composition. Printing was carried out as in example 1 and only 6000 copies could be printed due to damage to the image areas.

Abstract

The present invention discloses an imaging element comprising on a hydrophilic surface of a lithographic base an image forming layer comprising hydrophobic thermoplastic polymer particles dispersed in a hydrophilic binder and (ii) a compound capable of converting light to heat, said compound being comprised in said image forming layer or a layer adjacent thereto, characterised in that said image forming layer further comprises a cross-linking agent capable of cross-linking said hydrophilic binder upon heating in a ratio between 1 :100 and 200:1 by weight versus the hydrophilic binder.
The present invention further provides a method for making a printing plate therewith. According to this method, the above imaging element is preferably exposed by means of a laser and is subsequently developed with plain water or an aqueous liquid.

Description

    1. Field of the invention.
  • The present invention relates to a method for making a printing plate involving the use of a heat sensitive imaging element and that can be developed by means of plain water or an aqueous liquid.
  • 2. Background of the invention
  • Lithography is the process of printing from specially prepared surfaces, some areas of which are capable of accepting lithographic ink, whereas other areas, when moistened with water, will not accept the ink. The areas which accept ink form the printing image areas and the ink-rejecting areas form the background areas.
  • In the art of photolithography, a photographic material is made imagewise receptive to oily or greasy inks in the photo-exposed (negative-working) or in the non-exposed areas (positive-working) on a hydrophilic background.
  • In the production of common lithographic printing plates, also called surface litho plates or planographic printing plates, a support that has affinity to water or obtains such affinity by chemical treatment is coated with a thin layer of a photosensitive composition. Coatings for that purpose include light-sensitive polymer layers containing diazo compounds, dichromate-sensitized hydrophilic colloids and a large variety of synthetic photopolymers. Particularly diazo-sensitized systems are widely used.
  • Upon image-wise exposure of the light-sensitive layer the exposed image areas become insoluble and the unexposed areas remain soluble. The plate is then developed with a suitable liquid to remove the diazonium salt or diazo resin in the unexposed areas.
  • Commercially available diazo based printing plates most commonly use an anodized and roughened aluminium as a support having a hydrophilic surface since they offer the advantage of a high printing endurance. A particular disadvantage of such type of printing plates is that they require special developing liquids for development which is costly and inconvenient.
  • EP-A 601240 discloses a diazo based printing plate that uses a polyester film provided with a cross-linked hydrophilic layer as a lithographic base on which a photosensitive diazo layer is provided. Such a diazo based printing plate can be developed by rinsing it with plain water subsequent to image-wise exposure.
  • Commercial plates are also available that use a flexible support such as paper provided with a hydrophilic layer. For example, Lithocraft 10008 FOTOPLATE™ is a diazo based printing plate that comprises on a paper support a hydrophilic layer on top of which is provided a diazo based photosensitive layer. According to plate instructions of the supplier, a plate can be prepared by image-wise exposure of the lithographic printing plate precursor or imaging element, mounting the exposed imaging element on the press and wiping its surface with Lithocraft® 10008 Developer Desensitizer. The plate instructions also contemplate a method wherein no developer desensitizer is used. However, such method most often results in poor lithographic preformance so that in practice a Developer Desensitizer is almost always needed.
  • A particular disadvantage that the above diazo-based printing plates carry in common irrespective of the type of lithographic base used, is that they have to be shielded from the light. Moreover, diazo's are insufficiently sensitive to be exposed by means of a commercial and economical laser.
  • On the other hand, methods are known for making printing plates involving the use of imaging elements that are heat sensitive rather than photosensitive. For example, Research Disclosure no. 33303 of January 1992 discloses a heat sensitive imaging element comprising on a support a cross-linked hydrophilic layer containing thermoplastic polymer particles and an infrared absorbing pigment such as e.g. carbon black. By image-wise exposure to an Infrared laser, the thermoplastic polymer particles are image-wise coagulated thereby rendering the surface of the imaging element and these areas ink acceptant without any further development. A disadvantage of this method is that the printing plate obtained is easily damaged since the non-printing areas may become ink accepting when some pressure is applied thereto. Moreover, under critical conditions, the lithographic performance of such a printing plate may be poor and accordingly such printing plate has little lithographic printing latitude.
  • FR-A-1,561,957 describes a recording material comprising at least a recording layer containing a hydrophilic binder and an hydrophobic compound dispersed in said hydrophylic binder. Upon irradiation and development said recording material can be used as a planographic printing plate.
  • US-A-3,476,937 describes also a recording material comprising at least a recording layer containing a hydrophilic binder and an hydrophobic compound dispersed in said hydrophylic binder. Upon irradiation and development said recording material can be used as a planographic printing plate.
  • US-A- 3,580,719 describes an imaging element containing a recording layer containing at least about 80 % by weight of a normally water-soluble polymer which, when heated, undergoes a loss in its normal solubility in aqueous solvent.
  • The three last imaging elements all have the disadvantage that the corresponding printing plates have low printing endurances.
  • EP 514.145 describes a method for making a printing plate wherein a heat-sensitive imaging element is used that comprises on a lithographic base such as an anodised aluminium an image forming layer comprising core-shell particles and a light to heat converting substance. The shell of these particles is hydrophilic in nature and renders the particles developable. The core is hydrophobic in nature and flows out when heated. Thus upon image-wise exposure with an infrared laser diode, the image-forming layer can be rendered insoluble at the exposed areas. At the non-exposed areas, the image forming layer can be removed by means of an aqueous developer containing ethanolamine. Subsequent the material is baked. Although such printing plates can yield a high printing endurance, their development puts a burden on the environment because of the use of an alkanol amine.
  • 3. Summary of the invention
  • Accordingly, it is an object of the present invention to provide a heat-sensitive imaging element for making a printing plate that can be developed in a convenient and environmental friendly way and that preferably can be exposed by means of a commercially available laser.
  • It is a further object of the present invention to provide a heat-sensitive imaging element that can be used to obtain printing plates having a high printing endurance.
  • Further objects of the invention will become clear from the description hereinafter.
  • The present invention provides an imaging element comprising (i) on a hydrophilic surface of a lithographic base an image forming layer comprising hydrophobic thermoplastic polymer particles dispersed in a hydrophilic binder and (ii) a compound capable of converting light to heat, said compound being comprised in said image forming layer or a layer adjacent thereto, characterised in that said image forming layer further comprises a cross-linking agent capable of cross-linking said hydrophilic binder upon heating in a ratio between 1 :100 and 200:1 by weight versus the hydrophilic binder.
  • Further, this invention provides a method for making a lithographic printing plate comprising the steps of:
    • (1) image-wise exposing an imaging element as defined above to light;
    • (2) developing a thus obtained image-wise exposed imaging element it with plain water or an aqueous liquid;
    • (3) and optionally overall heating a thus obtained imaged imaging element.
    4. Detailed description of the invention
  • An imaging element for use in accordance with the present invention comprises on a hydrophilic surface of a lithographic base an image forming layer comprising hydrophobic thermoplastic polymer particles dispersed in a hydrophilic binder and a cross-linking agent capable of cross-linking the hydrophilic binder upon heating. The hydrophilic binder used in connection with the present invention is perferably not cross-linked or only slightly cross-linked. The imaging element further includes a compound capable of converting light to heat. This compound is preferably comprised in the image forming layer but can also be provided in a layer adjacent to the image forming layer.
  • According to one embodiment of the present invention, the lithographic base can be an anodised aluminium. A particularly preferred lithographic base is an electrochemically grained and anodised aluminium support. According to the present invention, an anodised aluminium support may be treated to improve the hydrophilic properties of its surface. For example, the aluminium support may be silicated by treating its surface with sodium silicate solution at elevated temperature, e.g. 95°C. Alternatively, a phosphate treatment may be applied which involves treating the aluminium oxide surface with a phosphate solution that may further contain an inorganic fluoride. Further, the aluminium oxide surface may be rinsed with a citric acid or citrate solution. This treatment may be carried out at room temperature or can be carried out at a slightly elevated temperature of about 30 to 50°C. A further interesting treatment involves rinsing the aluminium oxide surface with a bicarbonate solution. It is further evident that one or more of these post treatments may be carried out alone or in combination.
  • According to another embodiment in connection with the present invention, the lithographic base 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 tetra-alkylorthosilicate. The latter is particularly preferred.
  • As hydrophilic binder there may be used hydrophilic (co)polymers such as for example, homopolymers and copolymers of vinyl alcohol, acrylamide, methylol acrylamide, methylol methacrylamide, acrylic acid, methacrylic 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, preferably between 0.5 and 5 parts by weight, more 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. For this purpose 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. In addition inert particles of larger size than the colloidal silica can be added e.g. silica prepared according to Stöber as described in J. Colloid and Interface Sci., Vol. 26, 1968, pages 62 to 69 or alumina particles or particles having an average diameter of at least 100 nm which are particles of titanium dioxide or other heavy metal oxides. By incorporating these particles the surface of the cross-linked hydrophilic layer is given a uniform rough texture consisting of microscopic hills and valleys, which serve as storage places for water in background areas.
  • 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 µm and is preferably 1 to 10 µm.
  • Particular examples of suitable cross-linked hydrophilic layers for use in accordance with the present embodiment are disclosed in EP-A 601240, GB-P-1419512, FR-P-2300354, US-P-3971660, US-P-4284705 and EP-A 514490.
  • As flexible support of a lithographic base in connection with the present embodiment it is particularly preferred to use a plastic film e.g. a polyester such as a substrated polyethylene terephthalate film or polyethylene naphthalate film, cellulose acetate film, polystyrene film, polycarbonate film etc... The plastic film support may be opaque or transparent.
  • It is particularly preferred to use a polyester film support to which an adhesion improving layer has been provided. Particularly suitable adhesion improving layers for use in accordance with the present invention comprise a hydrophilic binder and colloidal silica as disclosed in EP-A 619524, EP-A 620502 and EP-A 619525. Preferably, the amount of silica in the adhesion improving layer is 200 mg per m2 and 750 mg per m2. Further, 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 m2 per gram, more preferably a surface area of 500 m2 per gram.
  • In accordance with the present invention, on top of a hydrophilic surface there is provided an image forming layer. Optionally, there may be provided one or more intermediate layers between the lithographic base and the image forming layer. An image forming layer in connection with the present invention comprises thermoplastic polymer particles dispersed in a hydrophilic binder and a cross-linking agent that can be activated by heat.
  • Suitable hydrophilic binders for use in an image forming layer in connection with this invention are preferably those that contain reactive groups e.g. hydroxy, amine or carboxyl groups. Specific examples of hydrophilic binders are synthetic homo or copolymers such as a polyvinylalcohol, dimethylhydantoine-formaldehyde resin, a poly(meth)acrylic acid, a poly(meth)acrylamide, a polyhydroxyethyl(meth)acrylate, a polyvinylmethylether or natural binders such as gelatin, a polysacharide such as e.g. dextran, pullulan, cellulose, arabic gum, alginic acid.
  • Hydrophobic thermoplastic polymer particles used in connection with the present invention have a preferably a glass transition temperature of at least 90 °C, more preferably of at least 100 °C.
  • Hydrophobic thermoplastic polymer particles used in connection with the present invention preferably have a coagulation temperature above 50°C and more preferably above 70°C. Coagulation may result from softening or melting of the thermoplastic polymer particles under the influence of heat. There is no specific upper limit to the coagulation temperature of the thermoplastic hydrophobic polymer particles, however the temperature should be sufficiently below the decomposition of the polymer particles. Preferably the coagulation temperature is at least 10°C below the temperature at which the decomposition of the polymer particles occurs. When said polymer particles are subjected to a temperature above coagulation temperature they coagulate to form a hydrophobic agglomerate in the hydrophilic layer so that at these parts the hydrophilic layer becomes insoluble in plain water or an aqueous liquid.
  • Specific examples of hydrophobic polymer particles for use in connection with the present invention are e.g. polystyrene, polyvinyl chloride, polymethyl methacrylate, polyvinylidene chloride, polyacrylonitrile, polyvinyl carbazole etc. or copolymers and/or mixtures thereof. Most preferably used is polymethyl methacrylate.
  • The weight average molecular weight of the polymers may range from 5,000 to 1,000,000g/mol.
  • The hydrophobic particles may have a particle size from 0.01µm to 50µm, more preferably between 0.05µm and 10µm and most preferably between 0.05µm and 0.5µm.
  • The polymer particles are present as a dispersion in the aqueous coating liquid of the image forming layer and may be prepared by the methods disclosed in US-P-3.476.937. Another method especially suitable for preparing an aqueous dispersion of the thermoplastic polymer particles comprises:
    • dissolving the hydrophobic thermoplastic polymer in an organic water immiscible solvent,
    • dispersing the thus obtained solution in water or in an aqueous medium and
    • removing the organic solvent by evaporation.
  • The amount of hydrophobic thermoplastic polymer particles contained in the image forming layer is preferably above 35% by weight and more preferably above 50% by weight and most preferably above 65% by weight.
  • Suitable compounds capable of converting light into heat are preferably infrared absorbing components although the wavelength of absorption is not of particular importance as long as the absorption of the compound used is in the wavelength range of the light source used for image-wise exposure. Particularly useful compounds are for example dyes and in particular infrared dyes, carbon black, 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. It is also possible to use conductive polymer dispersion such as polypyrrole or polyaniline-based conductive polymer dispersions. The lithographic performance and in particular the print endurance obtained depends on the heat-sensitivity of the imaging element. In this respect it has been found that carbon black yields very good and favorable results.
  • A light to heat converting compound in connection with the present invention is most preferably added to the image forming layer but at least part of the light to heat converting compound may also be comprised in a neighbouring layer. Such layer can be for example the cross-linked hydrophilic layer of a lithographic base according to the second embodiment of lithographic bases explained above.
  • Suitable heat-activatable cross-linking agents for use in the image forming layer in connection with the present invention are used in a ratio between 1:100 to 200:1 by weight versus the hydrophilic binder, more preferably in a ratio between 1:50 to 50:1, most preferably in a ratio betxeen 1:10 to 10:1.
  • Suitable heat-activatable cross-linking agents for use in the image forming layer in connection with the present invention are preferably compounds that have two or more groups that can react with the hydrophilic binder, e.g. with one of the reactive groups listed above. A cross-linking agent in connection with the present invention may be a low molecular weight compound or may be an oligomer or polymer. Examples of suitable cross-linking agents for use in an image forming layer in accordance with the present invention are e.g. aldehydes such as formaldehyde, hexamethoxymethyl melamine, amine-formaldehyde resins such as e.g. melamine-formaldehyde resin or guanamine-formaldehyde resin, dimethylolurea-formaldehyde resins, phenol-formaldehyde resins, compounds having two or more expoxy groups e.g. a polymer having epoxy groups etc...
  • It is preferred in connection with the present invention to further add a catalyst to an image forming layer in connection with the present invention. Such catalyst will speed-up the cross-linking reaction and accordingly total plate making time can be reduced while maintaining a high level of cross-linking needed to obtain a high printing endurance. Particularly suitable catalysts for use in this context are acid catalysts. It may furthermore be advantageous to use a precursor of a catalyst so as to improve the selectivity of the process and to obtain the best lithographic performance. Such a precursor will convert to the actual catalyst upon heating i.e. the catalyst will be formed at least partially during the image-wise exposure.
  • Suitable precursors of a catalyst are for example precursors that release an acid upon heating. Particular examples of suitable acid releasing catalyst precursors are sulfonium compounds, in particular benzylsulfonium compounds, as disclosed in e.g. EP 612065, EP 615233, and US 5.326.677, inorganic nitrates such as e.g. Mg(NO3)2.6H2O or organic nitrates such as guanidinium nitrate, ammonium nitrate, pyridinium nitrate etc... as disclosed in EP 462763, WO 81/1755, US 4.370.401, compounds that release a sulfonic acid such as 3-sulfolenes, e.g. 2,5-dihydrothio-thiophene-1,1-dioxides as disclosed in US 5.312.721, thermolytic compounds disclosed in GB 1.204.495, co-cristalin adducts of an amine and an volatile organic acid as disclosed in US 3.669.747, aralkylcyanoforms as disclosed in US 3.166.583, thermo-acids disclosed in EP 159725 and DE 3515176, squaric acid generating compounds as disclosed in US 5.278.031, acid generating compounds disclosed in US 5.225.314 and US 5.227.277 and RD 11511 of November 1973.
  • In accordance with the method of the present invention for making a lithographic printing plate an imaging element in accordance with the present invention is image-wise exposed to light and subsequently developed preferably by rinsing it with plain water. The obtained imaged imaging element is then preferably overall heated to obtain the highest printing endurance.
  • During image-wise exposure, the compound capable of converting light into heat, absorbs the light used for image-exposure and converts this in heat so as to generate an image-wise pattern of heat in the image-forming layer. As a consequence of this heat, the hydrophobic thermoplastic polymer particles coagulate and render the image forming layer insoluble for plain water or an aqueous liquid while the non-exposed parts remain soluble in plain water or an aqueous liquid.
  • Subsequent to development, the imaged imaging element is preferably overall heated which will cause substantial cross-linking of the image-forming layer and accordingly will improve the wear resistance of the printing areas during printing. Nevertheless, even without the additional overall heating, a printing endurance can be obtained that is suitable for a number of print jobs.
  • It is particularly advantageous in connection with the present invention to apply a gum before subjecting the imaged imaging element to the overall heat treatment. This will secure the hydrophilic properties at the non-printing areas in particular when an anodised aluminium is used as a lithographic base. Suitable gums for this purpose are well-known and commercially available e.g. Polychrome PC965™ (Polychrome).
  • Image-wise exposure in connection with the present invention is preferably an image-wise scanning exposure involving the use of a laser or L.E.D.. It is highly preferred in connection with the present invention to use a laser emitting in the infrared (IR) and/or near-infrared, i.e. emitting in the wavelength range 700-1500nm. Particularly preferred for use in connection with the present invention are laser diodes emitting in the near-infrared.
  • A preferred imaging apparatus suitable for image-wise scanning exposure in accordance with the present invention preferably includes a laser output that can be provided directly to the imaging elements surface via lenses or other beam-guiding components, or transmitted to the surface of a blank imaging element from a remotely sited laser using a fiber-optic cable. A controller and associated positioning hardware maintains the beam output at a precise orientation with respect to the imaging elements surface, scans the output over the surface, and activates the laser at positions adjacent selected points or areas of the imaging element. The controller responds to incoming image signals corresponding to the original document and/or picture being copied onto the imaging element to produce a precise negative or positive image of that original. The image signals are stored as a bitmap data file on a computer. Such files may be generated by a raster image processor (RIP) or other suitable means. For example, a RIP can accept Input data in page-description language, which defines all of the features required to be transferred onto the imaging element, or as a combination of page-description language and one or more image data files. The bitmaps are constructed to define the hue of the color as well as screen frequencies and angles in case of amplitude modulation screening. However, the present invention is particularly suitable for use in combination with frequency modulation screening as disclosed in e.g. EP-A 571010, EP-A 620677 and EP-A 620674.
  • The imaging apparatus can be configured as a flatbed recorder or as a drum recorder, with the imaging element mounted to the interior or exterior cylindrical surface of the drum. In a preferred drum configuration, the requisite relative motion between the laser beam and the imaging element is achieved by rotating the drum(and the imaging element mounted thereon) about its axis and moving the beam parallel to the rotation axis, thereby scanning the imaging element circumferentially so the image "grows" in the axial direction. Alternatively, the beam can move parallel to the drum axis and, after each pass across the imaging element, increment angularly so that the image on the imaging element "grows" circumferentially. In both cases, after a complete scan by the beam and development, an image corresponding to the original will have been applied to the surface of the imaging element. In the flatbed configuration, the beam is drawn across either axis of the imaging element, and is indexed along the other axis after each pass. Of course, the requisite relative motion between the beam and the imaging element may be produced by movement of the imaging element rather than (or in addition to) movement of the beam.
  • Regardless of the manner in which the beam is scanned, it is generally preferable (for reasons of speed) to employ a plurality of lasers and guide their outputs to a single writing array. The writing array is then indexed, after completion of each pass across or along the imaging element, a distance determined by the number of beams emanating from the array, and by the desired resolution (i.e. the number of image points per unit length.
  • The present invention will now be illustrated by way of the following examples, without however the intention to limit the invention thereto. All parts are by weight unless otherwise specified.
  • EXAMPLE 1 Preparation of a lithographic base
  • A 0.2mm thick aluminium foil was degreased by immersing the foil in an aqueous solution containing 5g/l of sodium hydroxide at 50°C and rinsed with demineralised water. The foil was then electrochemically grained using an alternating current in an aqueous solution containing 4g/l of hydrochloric acid, 4 g/l of hydroboric acid and 0.5g/l of aluminium ions at a temperature of 35°C and a current density of 1200 A/m2 to form a surface topography with an average center-line roughness Ra of 0.5µm.
  • After rinsing with demineralised water the aluminium foil was then etched with an aqueous solution containing 300g/l of sulfuric acid ate 60°C for 180 seconds and rinsed with demineralised 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 at temperature of 45°c, a voltage of about 10V and a current density of 150 A/m2 for about 300 seconds to form an anodic oxidation film of 3g/m2 Al2O3, then washed with demineralised water, post treated with a solution containing 20 g/l of sodium bicarbonated at 40°C for 30s, subsequently rinsed with demineralised water of 20°C during 120s and dried.
  • The obtained lithographic base was submersed in an aqueous solution containing 5% by weight of citric at 50°C for 60s, rinsed with demineralised water and dried at 40°C.
  • Preparation of the imaging element (material)
  • An imaging element according to the invention was produced by preparing the following coating composition and coating it to the above described lithographic base in an amount of 30g/m2 (wet coating amount) and drying it at 35°C.
  • Preparation of a coating composition.
  • To 10.8g of a 20% dispersion of polymethylmethacrylate (particle diameter 90nm) stabilised with Hostapal™ B (1% vs. polymer) in deionised water was subsequently added, while stirring, 4.5g of a 15% dispersion of carbon black in water, 59.79g of water and 25g of a 2% solution of a 98% hydrolysed polyvinylacetate having a weight average molecular weight of 200000g/mol in water and 2.5g of a 1% solution of hexamethoxymethylamine in water.
  • Preparation of a printing plate and printing copies therewith
  • The obtained imaging element was subjected to an image-wise scanning exposure using an infrared laser diode emitting at 830 nm. The scanspeed was 1 m/s, spot size 10 µm and 120 mW power on the plate surface. The imaging element was subsequent developed in a Polychrome PC28E™ processor filled with water in the developing section and a gum (Polychrome PC965™) in the gumming section.
  • The obtained printing plate was then mounted on a Heidelberg GTO46 offset press equipped with K + E 125 ink and as dampening liquid Rotamatic. 15000 clear copies were obtained with no ink-acceptance in the non-image areas. Even after printing 15000 copies, no damage to the image areas could be seen.
  • EXAMPLE 2 (comparison)
  • Printing plates were prepared as described in example 1 but with the modification that hexamethoxymethylmelamine (cross-linker) was not used in the coating composition. Printing was carried out as in example 1 and only 6000 copies could be printed due to damage to the image areas.

Claims (14)

  1. An imaging element comprising (i) on a hydrophilic surface of a lithographic base an image forming layer comprising hydrophobic thermoplastic polymer particles dispersed in a hydrophilic binder and (ii) a compound capable of converting light to heat, said compound being comprised in said image forming layer or a layer adjacent thereto, characterised in that said image forming layer further comprises a cross-linking agent capable of cross-linking said hydrophilic binder upon heating in a ratio between 1 :100 and 200:1 by weight versus the hydrophilic binder.
  2. An imaging element according to claim 1 wherein said compound capable of converting light to heat is selected from the group consisting of an infrared absorbing dye, carbon black, a metal boride, a metal carbide, a metal nitride, a metal carbonitride and a conductive polymer particle.
  3. An imaging element according to claim 1 wherein said lithographic base is an anodised aluminium or comprises a flexible support having thereon a cross-linked hydrophilic layer.
  4. An imaging element according to any of the above claims wherein said thermoplastic polymer particles have a coagulation temperature of above 50°C.
  5. An imaging element according to any of the above claims wherein said hydrophilic binder in said image forming layer is selected from the group consisting of a polyvinylalcohol, a poly(meth)acrylic acid, a poly(meth)acrylamide, a polyhydroxyethyl(meth)acrylate, a polyvinylmethylether, a polysacharide.
  6. An imaging element according to any of the above claims wherein said hydrophobic thermoplastic polymer particles are selected from the group consisting of polystyrene, polyvinyl chloride, polymethyl methacrylate, polyvinylidene chloride, polyacrylonitrile, polyvinyl carbazole etc. or copolymers and/or mixtures thereof.
  7. An imaging element according to claim 1 wherein said hydrophilic binder comprises reactive groups and said cross-linking agent is capable of reacting with said reactive groups under the influence of heat.
  8. An imaging element according to claim 7 wherein said reactive group is selected from the group consisting of a hydroxy, an amine and a carboxyl group.
  9. An imaging element according to any of the above claims wherein said image forming layer further comprises a catalyst capable of catalysing said cross-linking or a precursor of said catalyst that can be converted to a catalyst upon heating.
  10. A method for making a lithographic printing plate comprising the steps of:
    (1) image-wise exposing an imaging element as defined in any of the above claims to light;
    (2) developing a thus obtained image-wise exposed imaging element with plain water or an aqueous liquid;
  11. A method according to claim 10 wherein said image-wise exposure is a scanning exposure.
  12. A method according to claim 11 wherein said scanning exposure is carried out by means of a laser or a plurality of lasers.
  13. A method according to any of claims 10 to 12 wherein said image-wise exposed imaging element is overall heated subsequent to development.
  14. A method according to claim 13 wherein said imaged imaging element is treated with a gum before overall heating.
EP19960202950 1995-11-09 1996-10-22 Heat sensitive imaging element and method for making a printing plate therewith Expired - Lifetime EP0773112B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP19960202950 EP0773112B1 (en) 1995-11-09 1996-10-22 Heat sensitive imaging element and method for making a printing plate therewith

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP95203046 1995-11-09
EP95203046 1995-11-09
EP19960202950 EP0773112B1 (en) 1995-11-09 1996-10-22 Heat sensitive imaging element and method for making a printing plate therewith

Publications (2)

Publication Number Publication Date
EP0773112A1 true EP0773112A1 (en) 1997-05-14
EP0773112B1 EP0773112B1 (en) 2001-05-30

Family

ID=26139777

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19960202950 Expired - Lifetime EP0773112B1 (en) 1995-11-09 1996-10-22 Heat sensitive imaging element and method for making a printing plate therewith

Country Status (1)

Country Link
EP (1) EP0773112B1 (en)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998021038A1 (en) * 1996-11-12 1998-05-22 Kodak Polychrome Graphics Radiation-sensitive compositions and printing plates
EP0900653A1 (en) * 1997-09-08 1999-03-10 Agfa-Gevaert AG Positive working IR sensitive mixture, thermal imageable recording material and method of producing lithographic printing plate for offset printing using said composition
EP0925916A1 (en) * 1997-12-09 1999-06-30 Agfa-Gevaert N.V. A heat sensitive non-ablatable wasteless imaging element for providing a lithographic printing plate with a difference in dye density between the image and non image areas
EP0982124A2 (en) * 1998-08-24 2000-03-01 BASF Drucksysteme GmbH Material for recording by engraving using coherent electromagnetic radiation, and printing plate prepared therewith
EP1025990A1 (en) * 1999-02-01 2000-08-09 Agfa-Gevaert N.V. Heat sensitive material , process for making lithographic printing plates and method of printing using this material
US6124425A (en) * 1999-03-18 2000-09-26 American Dye Source, Inc. Thermally reactive near infrared absorption polymer coatings, method of preparing and methods of use
US6165685A (en) * 1997-09-08 2000-12-26 Agfa-Gevaert N.V. Thermally recordable material insensitive to white light
EP1132200A2 (en) * 2000-01-14 2001-09-12 Fuji Photo Film Co., Ltd. Lithographic printing plate precursor
US6300032B1 (en) 1999-02-01 2001-10-09 Agfa-Gevaert Heat-sensitive material with improved sensitivity
EP1243413A1 (en) * 2001-03-20 2002-09-25 Agfa-Gevaert Method of making a negative-working heat-sensitive lithographic printing plate precursor
EP1243410A1 (en) * 2001-03-20 2002-09-25 Agfa-Gevaert Method of making a heat-sensitive lithographic printing plate precursor
US6551757B1 (en) 2001-05-24 2003-04-22 Eastman Kodak Company Negative-working thermal imaging member and methods of imaging and printing
EP1356926A1 (en) 2002-04-26 2003-10-29 Agfa-Gevaert Negative-working thermal lithographic printing plate precursor comprising a smooth aluminum support.
US6641976B2 (en) 2001-03-20 2003-11-04 Agfa-Gevaert Method of making a negative-working heat-sensitive lithographic printing plate precursor
EP1584470A2 (en) * 2002-03-06 2005-10-12 Agfa-Gevaert Method of developing a heat-sensitive lithographic printing plate precursor with a gum solution
EP2065211A1 (en) 2007-11-30 2009-06-03 Agfa Graphics N.V. A method for treating a lithographic printing plate
EP2098376A1 (en) 2008-03-04 2009-09-09 Agfa Graphics N.V. A method for making a lithographic printing plate support
EP2106924A1 (en) 2008-03-31 2009-10-07 Agfa Graphics N.V. A method for treating a lithographic printing plate
US8419923B2 (en) 2006-08-03 2013-04-16 Agfa Graphics Nv Lithographic printing plate support
EP3032334A1 (en) 2014-12-08 2016-06-15 Agfa Graphics Nv A system for reducing ablation debris
WO2017157575A1 (en) 2016-03-16 2017-09-21 Agfa Graphics Nv Method and apparatus for processing a lithographic printing plate
EP3637188A1 (en) 2018-10-08 2020-04-15 Agfa Nv An effervescent developer precursor for processing a lithographic printing plate precursor

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6790590B2 (en) 2003-01-27 2004-09-14 Kodak Polychrome Graphics, Llp Infrared absorbing compounds and their use in imageable elements
US6939663B2 (en) 2003-07-08 2005-09-06 Kodak Polychrome Graphics Llc Sulfated phenolic resins and printing plate precursors comprising sulfated phenolic resins

Citations (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3166583A (en) 1962-05-01 1965-01-19 Du Pont Aralkylcy anoforms
FR1561957A (en) 1966-10-24 1969-04-04
US3476937A (en) 1963-12-05 1969-11-04 Agfa Gevaert Nv Thermographic recording method employing a recording material comprising a uniform layer of discrete hydrophobic thermoplastic polymer particles
GB1204495A (en) 1967-01-03 1970-09-09 Agfa Gevaert Nv Light sensitive compounds, and compositions and recording materials containing them
US3580719A (en) 1969-08-04 1971-05-25 Agfa Gevaert Nv Thermographic recording process
US3669747A (en) 1970-07-10 1972-06-13 Minnesota Mining & Mfg Heat-sensitive copy-sheet
GB1419512A (en) 1972-01-07 1975-12-31 Kodak Ltd Presensitised lithographic material
US3971660A (en) 1974-04-04 1976-07-27 Eastman Kodak Company Lithographic printing plate comprising hydrophilic layer of polyvinylacetate crosslinked with tetraethylorthosilicate
FR2300354A1 (en) 1975-02-04 1976-09-03 Kodak Pathe Presensitised lithographic printing plates - with layer of photosensitive P-aminobenzene diazonium salt with long chain alkyl or alkoxy gp. on the amino atom
WO1981001755A1 (en) 1979-12-07 1981-06-25 Minnesota Mining & Mfg Light sensitive,thermally developable imaging system
US4284705A (en) 1977-08-09 1981-08-18 Eastman Kodak Company Photosensitive diazo salt compositions and lithographic plate comprising same
JPS57102394A (en) * 1980-12-17 1982-06-25 Konishiroku Photo Ind Co Ltd Heat sensitive recording material
US4370401A (en) 1979-12-07 1983-01-25 Minnesota Mining And Manufacturing Company Light sensitive, thermally developable imaging system
DE3515176A1 (en) 1984-04-27 1985-10-31 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa WARM-DEVELOPABLE LIGHT-SENSITIVE MATERIAL
EP0462763A1 (en) 1990-06-18 1991-12-27 Minnesota Mining And Manufacturing Company Thermally developable light-sensitive layers containing photobleachable sensitizers
EP0514145A1 (en) 1991-05-14 1992-11-19 Du Pont (UK) Limited Thermographic material
EP0514490A1 (en) 1990-02-07 1992-11-25 Univ Texas Allelic association of the human dopamine (d 2?) receptor gene in compulsive disorders such as alcoholism.
US5225314A (en) 1991-04-17 1993-07-06 Polaroid Corporation Imaging process, and imaging medium for use therein
US5227277A (en) 1991-04-17 1993-07-13 Polaroid Corporation Imaging process, and imaging medium for use therein
EP0571010A1 (en) 1992-05-22 1993-11-24 Agfa-Gevaert N.V. An improved frequency modulation halftoning method
US5278031A (en) 1992-10-23 1994-01-11 Polaroid Corporation Process for thermochemical generation of squaric acid and for thermal imaging, and imaging medium for use therein
US5312721A (en) 1991-12-24 1994-05-17 E. I. Du Pont De Nemours And Company Bleachable antihalation system
EP0599510A2 (en) * 1992-11-18 1994-06-01 Du Pont (UK) Limited Improvements in or relating to the formation of images
EP0601240A1 (en) 1992-12-11 1994-06-15 Agfa-Gevaert N.V. Water developable diazo based lithographic printing plate
US5326677A (en) 1993-02-19 1994-07-05 Eastman Kodak Company Optical retrieval apparatus using a tellurium (IV) leuco dye
EP0612065A1 (en) 1993-02-19 1994-08-24 Eastman Kodak Company Recordable optical element having a leuco dye
EP0615233A1 (en) 1993-02-19 1994-09-14 Eastman Kodak Company Recordable optical element having a leuco dye
EP0619524A1 (en) 1993-04-05 1994-10-12 Agfa-Gevaert N.V. A lithographic base and a method for making a lithographic printing plate therewith
EP0619525A1 (en) 1993-04-05 1994-10-12 Agfa-Gevaert N.V. A lithographic base and a method for making a lithographic printing plate therewith
EP0620502A1 (en) 1993-04-05 1994-10-19 Agfa-Gevaert N.V. A lithographic base and a method for making a lithographic printing plate therewith
EP0620677A1 (en) 1993-04-16 1994-10-19 Agfa-Gevaert N.V. Frequency modulation halftone screen and method for making same
EP0620674A1 (en) 1993-04-16 1994-10-19 Agfa-Gevaert N.V. Method for making a lithographic printing plate

Patent Citations (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3166583A (en) 1962-05-01 1965-01-19 Du Pont Aralkylcy anoforms
US3476937A (en) 1963-12-05 1969-11-04 Agfa Gevaert Nv Thermographic recording method employing a recording material comprising a uniform layer of discrete hydrophobic thermoplastic polymer particles
FR1561957A (en) 1966-10-24 1969-04-04
GB1204495A (en) 1967-01-03 1970-09-09 Agfa Gevaert Nv Light sensitive compounds, and compositions and recording materials containing them
US3580719A (en) 1969-08-04 1971-05-25 Agfa Gevaert Nv Thermographic recording process
US3669747A (en) 1970-07-10 1972-06-13 Minnesota Mining & Mfg Heat-sensitive copy-sheet
GB1419512A (en) 1972-01-07 1975-12-31 Kodak Ltd Presensitised lithographic material
US3971660A (en) 1974-04-04 1976-07-27 Eastman Kodak Company Lithographic printing plate comprising hydrophilic layer of polyvinylacetate crosslinked with tetraethylorthosilicate
FR2300354A1 (en) 1975-02-04 1976-09-03 Kodak Pathe Presensitised lithographic printing plates - with layer of photosensitive P-aminobenzene diazonium salt with long chain alkyl or alkoxy gp. on the amino atom
US4284705A (en) 1977-08-09 1981-08-18 Eastman Kodak Company Photosensitive diazo salt compositions and lithographic plate comprising same
WO1981001755A1 (en) 1979-12-07 1981-06-25 Minnesota Mining & Mfg Light sensitive,thermally developable imaging system
US4370401A (en) 1979-12-07 1983-01-25 Minnesota Mining And Manufacturing Company Light sensitive, thermally developable imaging system
JPS57102394A (en) * 1980-12-17 1982-06-25 Konishiroku Photo Ind Co Ltd Heat sensitive recording material
DE3515176A1 (en) 1984-04-27 1985-10-31 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa WARM-DEVELOPABLE LIGHT-SENSITIVE MATERIAL
EP0514490A1 (en) 1990-02-07 1992-11-25 Univ Texas Allelic association of the human dopamine (d 2?) receptor gene in compulsive disorders such as alcoholism.
EP0462763A1 (en) 1990-06-18 1991-12-27 Minnesota Mining And Manufacturing Company Thermally developable light-sensitive layers containing photobleachable sensitizers
US5225314A (en) 1991-04-17 1993-07-06 Polaroid Corporation Imaging process, and imaging medium for use therein
US5227277A (en) 1991-04-17 1993-07-13 Polaroid Corporation Imaging process, and imaging medium for use therein
EP0514145A1 (en) 1991-05-14 1992-11-19 Du Pont (UK) Limited Thermographic material
US5312721A (en) 1991-12-24 1994-05-17 E. I. Du Pont De Nemours And Company Bleachable antihalation system
EP0571010A1 (en) 1992-05-22 1993-11-24 Agfa-Gevaert N.V. An improved frequency modulation halftoning method
US5278031A (en) 1992-10-23 1994-01-11 Polaroid Corporation Process for thermochemical generation of squaric acid and for thermal imaging, and imaging medium for use therein
EP0599510A2 (en) * 1992-11-18 1994-06-01 Du Pont (UK) Limited Improvements in or relating to the formation of images
EP0601240A1 (en) 1992-12-11 1994-06-15 Agfa-Gevaert N.V. Water developable diazo based lithographic printing plate
US5326677A (en) 1993-02-19 1994-07-05 Eastman Kodak Company Optical retrieval apparatus using a tellurium (IV) leuco dye
EP0612065A1 (en) 1993-02-19 1994-08-24 Eastman Kodak Company Recordable optical element having a leuco dye
EP0615233A1 (en) 1993-02-19 1994-09-14 Eastman Kodak Company Recordable optical element having a leuco dye
EP0619524A1 (en) 1993-04-05 1994-10-12 Agfa-Gevaert N.V. A lithographic base and a method for making a lithographic printing plate therewith
EP0619525A1 (en) 1993-04-05 1994-10-12 Agfa-Gevaert N.V. A lithographic base and a method for making a lithographic printing plate therewith
EP0620502A1 (en) 1993-04-05 1994-10-19 Agfa-Gevaert N.V. A lithographic base and a method for making a lithographic printing plate therewith
EP0620677A1 (en) 1993-04-16 1994-10-19 Agfa-Gevaert N.V. Frequency modulation halftone screen and method for making same
EP0620674A1 (en) 1993-04-16 1994-10-19 Agfa-Gevaert N.V. Method for making a lithographic printing plate

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
J. VERMEERSCH: "A lithographic Printing plate", RESEARCH DISCLOSURE, no. 33303, HAVANT GB, XP000028114 *
PATENT ABSTRACTS OF JAPAN vol. 006, no. 196 (M - 161) 5 October 1982 (1982-10-05) *

Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5919601A (en) * 1996-11-12 1999-07-06 Kodak Polychrome Graphics, Llc Radiation-sensitive compositions and printing plates
WO1998021038A1 (en) * 1996-11-12 1998-05-22 Kodak Polychrome Graphics Radiation-sensitive compositions and printing plates
EP0900653A1 (en) * 1997-09-08 1999-03-10 Agfa-Gevaert AG Positive working IR sensitive mixture, thermal imageable recording material and method of producing lithographic printing plate for offset printing using said composition
US6165685A (en) * 1997-09-08 2000-12-26 Agfa-Gevaert N.V. Thermally recordable material insensitive to white light
EP0925916A1 (en) * 1997-12-09 1999-06-30 Agfa-Gevaert N.V. A heat sensitive non-ablatable wasteless imaging element for providing a lithographic printing plate with a difference in dye density between the image and non image areas
EP0982124A3 (en) * 1998-08-24 2001-09-26 BASF Drucksysteme GmbH Material for recording by engraving using coherent electromagnetic radiation, and printing plate prepared therewith
EP0982124A2 (en) * 1998-08-24 2000-03-01 BASF Drucksysteme GmbH Material for recording by engraving using coherent electromagnetic radiation, and printing plate prepared therewith
EP1025990A1 (en) * 1999-02-01 2000-08-09 Agfa-Gevaert N.V. Heat sensitive material , process for making lithographic printing plates and method of printing using this material
US6300032B1 (en) 1999-02-01 2001-10-09 Agfa-Gevaert Heat-sensitive material with improved sensitivity
US6124425A (en) * 1999-03-18 2000-09-26 American Dye Source, Inc. Thermally reactive near infrared absorption polymer coatings, method of preparing and methods of use
US6177182B1 (en) 1999-03-18 2001-01-23 American Dye Source, Inc. Thermally reactive near infrared absorption polymer coatings, method of preparing and methods of use
EP1132200A2 (en) * 2000-01-14 2001-09-12 Fuji Photo Film Co., Ltd. Lithographic printing plate precursor
US6740464B2 (en) 2000-01-14 2004-05-25 Fuji Photo Film Co., Ltd. Lithographic printing plate precursor
EP1132200A3 (en) * 2000-01-14 2003-12-17 Fuji Photo Film Co., Ltd. Lithographic printing plate precursor
US6641976B2 (en) 2001-03-20 2003-11-04 Agfa-Gevaert Method of making a negative-working heat-sensitive lithographic printing plate precursor
EP1243410A1 (en) * 2001-03-20 2002-09-25 Agfa-Gevaert Method of making a heat-sensitive lithographic printing plate precursor
EP1243413A1 (en) * 2001-03-20 2002-09-25 Agfa-Gevaert Method of making a negative-working heat-sensitive lithographic printing plate precursor
US6551757B1 (en) 2001-05-24 2003-04-22 Eastman Kodak Company Negative-working thermal imaging member and methods of imaging and printing
EP1584470A2 (en) * 2002-03-06 2005-10-12 Agfa-Gevaert Method of developing a heat-sensitive lithographic printing plate precursor with a gum solution
EP1584470A3 (en) * 2002-03-06 2005-10-19 Agfa-Gevaert Method of developing a heat-sensitive lithographic printing plate precursor with a gum solution
EP1356926A1 (en) 2002-04-26 2003-10-29 Agfa-Gevaert Negative-working thermal lithographic printing plate precursor comprising a smooth aluminum support.
US8419923B2 (en) 2006-08-03 2013-04-16 Agfa Graphics Nv Lithographic printing plate support
EP2065211A1 (en) 2007-11-30 2009-06-03 Agfa Graphics N.V. A method for treating a lithographic printing plate
EP2098376A1 (en) 2008-03-04 2009-09-09 Agfa Graphics N.V. A method for making a lithographic printing plate support
EP2106924A1 (en) 2008-03-31 2009-10-07 Agfa Graphics N.V. A method for treating a lithographic printing plate
EP3032334A1 (en) 2014-12-08 2016-06-15 Agfa Graphics Nv A system for reducing ablation debris
WO2017157575A1 (en) 2016-03-16 2017-09-21 Agfa Graphics Nv Method and apparatus for processing a lithographic printing plate
WO2017157571A1 (en) 2016-03-16 2017-09-21 Agfa Graphics Nv Method and apparatus for processing a lithographic printing plate
WO2017157576A1 (en) 2016-03-16 2017-09-21 Agfa Graphics Nv Method for processing a lithographic printing plate
WO2017157572A1 (en) 2016-03-16 2017-09-21 Agfa Graphics Nv Apparatus for processing a lithographic printing plate and corresponding method
WO2017157578A1 (en) 2016-03-16 2017-09-21 Agfa Graphics Nv Method for processing a lithographic printing plate
WO2017157579A1 (en) 2016-03-16 2017-09-21 Agfa Graphics Nv Method for processing a lithographic printing plate
EP3637188A1 (en) 2018-10-08 2020-04-15 Agfa Nv An effervescent developer precursor for processing a lithographic printing plate precursor
WO2020074258A1 (en) 2018-10-08 2020-04-16 Agfa Nv An effervescent developer precursor for processing a lithographic printing plate precursor

Also Published As

Publication number Publication date
EP0773112B1 (en) 2001-05-30

Similar Documents

Publication Publication Date Title
EP0773112B1 (en) Heat sensitive imaging element and method for making a printing plate therewith
JP2894550B2 (en) Thermosensitive imaging elements and methods of making printing plates therewith
JP2894549B2 (en) Thermosensitive imaging element and method of making a printing plate therewith
EP0770494B1 (en) A method for making a lithographic printing plate involving on press development
US5948591A (en) Heat sensitive imaging element and a method for producing lithographic plates therewith
US6022667A (en) Heat sensitive imaging element and a method for producing lithographic plates therewith
EP0849091B1 (en) Heat-sensitive imaging element for making lithographic printing plates comprising polymer particles with a specific particle size
EP0931647A1 (en) A heat sensitive element and a method for producing lithographic plates therewith
EP0839647B2 (en) Method for making a lithographic printing plate with improved ink-uptake
US6391516B1 (en) Heat sensitive imaging element and method for making a printing plate therewith
EP0881096B1 (en) A heat sensitive imaging element and a method for producing lithographic plates therewith
US6106996A (en) Heat sensitive imaging element and a method for producing lithographic plates therewith
US6197478B1 (en) Method for making a driographic printing plate involving the use of a heat-sensitive imaging element
EP0773113B1 (en) Heat sensitive imaging element and method for making a printing plate therewith
US5981144A (en) Heat sensitive imaging element and a method for producing lithographic plates therewith
US6605407B2 (en) Thermally convertible lithographic printing precursor
EP0800928B1 (en) A heat sensitive imaging element and a method for producing lithographic plates therewith
US6427595B1 (en) Heat-sensitive imaging element for making lithographic printing plates comprising polymer particles with a specific particle size
US6589710B2 (en) Method for obtaining a lithographic printing surface
US6071369A (en) Method for making an lithographic printing plate with improved ink-uptake
EP0881094B1 (en) A heat sensitive imaging element and a method for producing lithographic plates therewith
JPH11240270A (en) Heat-sensitive, non-ablatable wasteless imaging element for providing lithographic printing plate having difference in coloring matter density between image and non-image regions
EP0881095B1 (en) A heat sensitive imaging element and a method for producing lithographic plates therewith
US20020155374A1 (en) Thermally convertible lithographic printing precursor comprising an organic base
US20030017410A1 (en) Thermally convertible lithographic printing precursor comprising an organic acid

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

17P Request for examination filed

Effective date: 19971114

17Q First examination report despatched

Effective date: 19980915

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

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

REF Corresponds to:

Ref document number: 69613078

Country of ref document: DE

Date of ref document: 20010705

ET Fr: translation filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: AGFA-GEVAERT

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
REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 20

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

Ref country code: GB

Payment date: 20150804

Year of fee payment: 20

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

Ref country code: FR

Payment date: 20150810

Year of fee payment: 20

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

Ref country code: DE

Payment date: 20150810

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69613078

Country of ref document: DE

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20161021

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 EXPIRATION OF PROTECTION

Effective date: 20161021