EP0943451B1 - Elément pour l'enregistrement de l'image thermosensible et le procédé pour la fabrication d'une plaque d'impression positive à partir de cet élément - Google Patents

Elément pour l'enregistrement de l'image thermosensible et le procédé pour la fabrication d'une plaque d'impression positive à partir de cet élément Download PDF

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Publication number
EP0943451B1
EP0943451B1 EP99200336A EP99200336A EP0943451B1 EP 0943451 B1 EP0943451 B1 EP 0943451B1 EP 99200336 A EP99200336 A EP 99200336A EP 99200336 A EP99200336 A EP 99200336A EP 0943451 B1 EP0943451 B1 EP 0943451B1
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EP
European Patent Office
Prior art keywords
layer
imaging element
mode imaging
heat mode
printing plate
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
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EP99200336A
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German (de)
English (en)
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EP0943451A1 (fr
EP0943451B3 (fr
Inventor
Marc Van Damme
Joan Vermeersch
Eric Verschueren
Jörg Dr. Jung
Helmuth Haberhauer
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Agfa Gevaert NV
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Agfa Gevaert NV
Agfa Gevaert AG
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Priority to EP99200336.8A priority Critical patent/EP0943451B3/fr
Priority to DE69901642.8T priority patent/DE69901642T3/de
Publication of EP0943451A1 publication Critical patent/EP0943451A1/fr
Publication of EP0943451B1 publication Critical patent/EP0943451B1/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
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • B41C1/1016—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials characterised by structural details, e.g. protective layers, backcoat layers or several imaging layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/02—Positive working, i.e. the exposed (imaged) areas are removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/06—Developable by an alkaline solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/14—Multiple imaging layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/20—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by inorganic additives, e.g. pigments, salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
    • B41C2210/262—Phenolic condensation polymers, e.g. novolacs, resols

Definitions

  • the present invention relates to a heat mode imaging element for preparing a lithographic printing plate comprising an IR sensitive top layer. More specifically the invention is related to a heat mode imaging element for preparing a lithographic printing plate with a higher sensitivity.
  • 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.
  • printing plates are known that include a photosensitive coating that upon image-wise exposure is rendered soluble at the exposed areas. Subsequent development then removes the exposed areas.
  • a typical example of such photosensitive coating is a quinone-diazide based coating.
  • the above described photographic materials from which the printing plates are made are camera-exposed through a photographic film that contains the image that is to be reproduced in a lithographic printing process.
  • Such method of working is cumbersome and labor intensive.
  • the printing plates thus obtained are of superior lithographic quality.
  • GB-1 492 070 discloses a method wherein a metal layer or a layer containing carbon black is provided on a photosensitive coating. This metal layer is then ablated by means of a laser so that an image mask on the photosensitive layer is obtained. The photosensitive layer is then overall exposed by UV-light through the image mask. After removal of the image mask, the photosensitive layer is developed to obtain a printing plate.
  • This method however still has the disadvantage that the image mask has to be removed prior to development of the photosensitive layer by a cumbersome processing.
  • thermoplastic polymer particles By image-wise exposure to an infrared laser, the thermoplastic polymer particles are image-wise coagulated thereby rendering the surface of the imaging element at 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.
  • US-P- 4 708 925 discloses imaging elements including a photosensitive composition comprising an alkali-soluble novolac resin and an onium-salt. This composition may optionally contain an IR-sensitizer. After image-wise exposing said imaging element to UV - visible - or IR-radiation followed by a development step with an aqueous alkali liquid there is obtained a positive or negative working printing plate. The printing results of a lithographic plate obtained by irradiating and developing said imaging element are poor.
  • EP-A- 625 728 discloses an imaging element comprising a layer which is sensitive to UV- and IR-irradiation and which may be positive or negative working. This layer comprises a resole resin, a novolac resin, a latent Bronsted acid and an IR-absorbing substance. The printing results of a lithographic plate obtained by irradiating and developing said imaging element are poor.
  • US-P- 5 340 699 is almost identical with EP-A- 625 728 but discloses the method for obtaining a negative working IR-laser recording imaging element.
  • the IR-sensitive layer comprises a resole resin, a novolac resin, a latent Bronsted acid and an IR-absorbing substance.
  • the printing results of a lithographic plate obtained by irradiating and developing said imaging element are poor.
  • EP-A- 678 380 discloses a method wherein a protective layer is provided on a grained metal support underlying a laser-ablatable surface layer. Upon image-wise exposure the surface layer is fully ablated as well as some parts of the protective layer. The printing plate is then treated with a cleaning solution to remove the residu of the protective layer and thereby exposing the hydrophilic surface layer.
  • EP-A- 573 092 discloses a method for making an image comprising the steps of:
  • EP-A- 823 327 discloses a positive photosensitive composition showing a difference in solubility in alkali developer as between an exposed portion and a non-exposed portion, which comprises as components inducing the difference in solubility ,
  • FR-A- 1 561 957 discloses a process in order of registering or reproducing information by means of electromagnetic radiation and also discloses elements sensible for heat containing substances wherein heat is produced by exposure to electromagnetic radiation.
  • US-A- 5 641 608 discloses a process for the direct production of an imaged pattern of resist on a substrate, which process utilizes thermo-resist rather than photoresist, i.e. compositions which undergo thermally-induced, rather than photo-induced, chemical transformations.
  • a film of thermo-resist composition applied to the surface substrate is scanned by a focused heat source in a predetermined pattern, without a phototool, to bring about localized thermally-induced chemical transformations of the composition which either directly produce the resist pattern or produce in the film a developable latent image of the pattern.
  • GB-A- 1 208 415 discloses a method of recording information comprising information-wise heating a recording material comprising a support bearing, with or without an inter-layer, a heat-sensitive recording layer constituted so that such information-wise heating creates a record of the information in terms of a difference in the water-permeability of different areas of the recording layer, treating the recording material with an aqueous liquid which penetrates through the water-permeable or more water permeable areas of the recrding layer and is constituted so as to effect a permanent physical and/or chemical change of at least the surface portions of the underlying support or inter-layer in the corresponding areas, and removing the whole of the recording layer to expose said information-wise changed underlying support or inter-layer.
  • US-A- 5 466 557 discloses a radiation sensitive composition especially adapted to prepare a lithographic printing plate that is sensitive to both ultraviolet and infrared radiation and capable of functioning in either a positive-working or negative-working manner, comprised of (1) a resole resin, (2) a novolac resin, (3) a latent Bronsted acid, (4) an infrared absorber, and (5) terephthalaldehyde.
  • the solubility of the composition in aqueous alkaline developing solution is both reduced in exposed areas and increased in unexposed areas by the steps of imagewise exposure to activating radiation and heating.
  • GB-A-1 245 924 discloses an information-recording method wherein a recording material is used comprising a heat-sensitive recording layer of a composition such that the solubility of any given area of the layer in a given solvent can be increased by heating that area of the layer, wherein the said layer is information-wise heated to produce a record of the information in terms of a difference in the solubilities in the said solvent of different areas of the recording layer , and wherein the whole layer is then contacted with such solvent to cause the portions of the recording layer which are soluble or most soluble in such solvent to be removed or penetrated by such solvent, the said method being characterized in that the said recording layer is wholly or mainly composed of one or more heat-sensitive polymeric compounds.
  • GB-A- 1 155 035 discloses a method of recording information, wherein a recording material is used comprising a layer of a polymeric material which when any given area of the layer is sufficiently heated undergoes in that area a modification resulting in a decrease in the solubility of that area of the layer in water or an aqueous medium, such layer also incorporating a substance or substances distributed over the whole area of the layer and being capable of being heated by exposing the layer to intense radiant energy which is absorbed by such substance or substances, and wherein the said material is exposed to intense radiant energy which is distributed over the material in a pattern determined by the information to be recorded and which is at least partly absorbed by said distributed substance or substances, so that a corresponding heat pattern is generated in the material, whereby such information is recorded in terms of a difference in the solubilities in water or an aqueous medium of different areas of said layer.
  • EP-A- 97 200 588.8 discloses a heat mode imaging element for making lithographic printing plates comprising on a lithographic base having a hydrophilic surface an intermediate layer comprising a polymer, soluble in an aqueous alkaline solution and a top layer that is sensitive to IR-radiation wherein said top layer upon exposure to IR-radiation has a decreased or increased capacity for being penetrated and/or solubilised by an aqueous alkaline solution.
  • Said last heat-mode imaging element has the disadvantage that the sensitivity is marginal.
  • An analogous material with a higher IR-sensitivity would be appreciated.
  • a heat mode imaging element for making a lithographic printing plate having on a lithographic base with a hydrophilic surface a first layer including a polymer, soluble in an aqueous alkaline solution and a top layer on the same side of the lithographic base as the first layer which top layer is unpenetrable for or insoluble in an alkaline developer containing SiO 2 in the form of silicates before imagewise IR exposure, imaged parts being capable of removal during development without solubilising and/or damaging non-imaged parts; characterized in that said first layer and said top layer comprise a compound capable of converting IR-light into heat. Also provided is a method of making alithographic printing plate according to claim 10.
  • a heat-sensitive imaging element according to the invention has a high sensitivity and yields a lithographic printing plate of high quality.
  • the first layer and the top (also called the second) layer comprise a compound capable of converting IR-light into heat.
  • Said compound capable of converting IR-light into heat is preferably an IR dye or pigment.
  • a mixture of IR-dyes or pigments may be used, but it is preferred to use only one IR-dye or pigment.
  • IR-dyes are IR-cyanines dyes.
  • Particularly useful IR-cyanine dyes are cyanines dyes with at least two acid groups, more preferably with at least two sulphonic groups . Still more preferably are cyanines dyes with two indolenine and at least two sulphonic acid groups.
  • Particularly useful IR-absorbing pigments are 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. W02.9.
  • 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.
  • the top layer in accordance with the present invention comprises a compound capable of converting IR-light into heat, preferably an IR-dye or pigment as set out above and preferably a binder resin.
  • the compound capable of converting IR-light into heat is present in said top layer preferably in an amount between 1 and 99 parts, more preferably between 50 and 95 parts by weight of the total weight of said IR-sensitive top layer.
  • the top layer may preferably comprise as binder a water insoluble polymer, more preferably an alkaline insoluble polymer such as a cellulose ester, a copolymer of vinylidene chloride and acrylonitrile, poly(meth)acrylates, polyvinyl chloride, silicone resins, etc.
  • binder is nitrocellulose resin.
  • the total amount of the top layer preferably ranges from 0.1 to 10 g/m 2 , more preferably from 0.3 to 2 g/m 2 .
  • top layer a difference in the capacity of being penetrated and/or solubilised by the aqueous alkaline solution is generated upon image-wise exposure according to the invention.
  • the said capacity is increased upon image-wise IR exposure to such degree that the imaged parts will be cleaned out during development without solubilising and/or damaging the non-imaged parts.
  • the development with the aqueous alkaline solution is preferably done within an interval of 5 to 120 seconds.
  • the present invention comprises a first layer soluble in an aqueous developing solution, more preferably an aqueous alkaline developing solution with preferentially a pH between 7.5 and 14.
  • Said layer is preferably contiguous to the top layer but other layers may be present between the top layer and the first layer.
  • Said layer comprise a compound capable of converting IR-light into heat, preferably an IR dye or pigment and an alkali soluble binder.
  • Said compound capable of converting IR-light into heat is present in said first layer in an amount of 0.1 to 30 parts, more preferably in an amount between 1 and 20 parts by weight of the total weight of said first layer.
  • Said compound capable of converting IR-light into heat preferably does not decrease the solubility of the first layer in aqueous alkaline solution.
  • the alkali soluble binders used in this layer are preferably hydrophobic binders as used in conventional positive or negative working PS-plates e.g. novolac resins, polymers containing hydroxystyrene units, carboxy substituted polymers etc. Typical examples of these polymers are descibed in DE-A- 4 007 428, DE-A- 4 027 301 and DE-A- 4 445 820 .
  • the hydrophobic binder used in connection with the present invention is further characterised by insolubility in water and in an alkaline solution and/or partial solubility in water when combined with a cosolvent.
  • this aqueous alkali soluble layer is preferably a visible light- and UV-light desensitised layer. Said layer is preferably thermally hardenable.
  • This preferably visible light- and UV-desensitised layer does not comprise photosensitive ingredients such as diazo compounds, photoacids, photoinitiators, quinone diazides, sensitisers etc. which absorb in the wavelength range of 250nm to 650nm. In this way a daylight stable printing plate may be obtained.
  • Said first layer preferably also includes a low molecular acid, preferably a carboxylic acid, still more preferably a benzoic acid, most preferably 3,4,5-trimethoxybenzoic acid or a benzophenone.
  • a low molecular acid preferably a carboxylic acid, still more preferably a benzoic acid, most preferably 3,4,5-trimethoxybenzoic acid or a benzophenone.
  • the ratio between the total amount of low molecular acid or benzophenone and polymer in the first layer preferably ranges from 2:98 to 40:60, more preferably from 5:95 to 20:80.
  • the total amount of said first layer preferably ranges from 0.1 to 10 g/m 2 , more preferably from 0.3 to 2 g/m 2 .
  • the lithographic base may be an anodised aluminum.
  • 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 having 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, 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, 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, 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 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.
  • Image-wise exposure in connection with the present invention is an image-wise scanning exposure involving the use of a laser that operates in the infrared or near-infrared, i.e. wavelength range of 700-1500 nm. Most preferred are laser diodes emitting in the near-infrared. Exposure of the imaging element may be performed with lasers with a short as well as with lasers with a long pixel dwell time. Preferred are lasers with a pixel dwell time between 0.005 ⁇ s and 20 ⁇ s.
  • the heat mode imaging element is developed by rinsing it with an aqueous alkaline solution containing SiO 2 in the form of silicates .
  • the aqueous alkaline solutions used in the present invention are those that are used for developing conventional positive working presensitised printing plates and have preferably a pH between 11.5 and 14.
  • the imaged parts of the top layer that were rendered more penetrable for the aqueous alkaline solution upon exposure are cleaned-out whereby a positive working printing plate is obtained.
  • the composition of the developer used is also very important.
  • the developers and replenishers for developer used in the invention are preferably aqueous solutions mainly composed of alkali metal silicates and alkali metal hydroxides represented by MOH or their oxyde, represented by M 2 O, wherein said developer comprises SiO 2 .of 0.5 to 1.5 and a concentration of SiO 2 of 0.5 to 5% by weight.
  • alkali metal silicates preferably used are, for instance, sodium silicate, potassium silicate, lithium silicate and sodium metasilicate.
  • alkali metal hydroxides preferred are sodium hydroxide, potassium hydroxide and lithium hydroxide.
  • the developers used in the invention may simultaneously contain other alkaline agents.
  • other alkaline agents include such inorganic alkaline agents as ammonium hydroxide, sodium tertiary phosphate, sodium secondary phosphate, potassium tertiary phosphate, potassium secondary phosphate, ammonium tertiary phosphate, ammonium secondary phosphate, sodium bicarbonate, sodium carbonate, potassium carbonate and ammonium carbonate; and such organic alkaline agents as mono-, di- or triethanolamine, mono-, di- or trimethylamine, mono-, di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine and tetramethylammonium hydroxide.
  • the concentration of SiO 2 in the developer and replenisher preferably ranges from 1 to 4 % by weight. Such limitation of the concentration of SiO 2 makes it possible to stably provide lithographic printing plates having good finishing qualities even when a large amount of plates according to the invention are processed for a long time period.
  • an aqueous solution of an alkali metal silicate having a molar ratio [SiO 2 ] / [M 2 O], which ranges from 1.0 to 1.5 and a concentration of SiO 2 of 1 to 4 % by weight is used as a developer.
  • a replenisher having alkali strength equal to or more than that of the developer is employed.
  • a molar ratio, [SiO 2 ] / [M 2 O] of the replenisher is equal to or smaller than that of the developer, or that a concentration of SiO 2 is high if the molar ratio of the developer is equal to that of the replenisher.
  • organic solvents having solubility in water at 20 °C of not more than 10 % by weight according to need.
  • organic solvents are such carboxilic acid esters as ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, ethylene glycol monobutyl acetate, butyl lactate and butyl levulinate; such ketones as ethyl butyl ketone, methyl isobutyl ketone and cyclohexanone; such alcohols as ethylene glycol monobutyl ether, ethylene glycol benzyl ether, ethylene glycol monophenyl ether, benzyl alcohol, methylphenylcarbinol, n-amyl alcohol and methylamyl alcohol; such alkyl-substituted aromatic hydrocarbons as xylene; and such halogenated hydrocarbons
  • organic solvents may be used alone or in combination. Particularly preferred is benzyl alcohol in the invention. These organic solvents are added to the developer or replenisher therefor generally in an amount of not more than 5 % by weight and preferably not more than 4 % by weight.
  • the developers and replenishers used in the present invention may simultaneously contain a surfactant for the purpose of improving developing properties thereof.
  • surfactants include salts of higher alcohol (C8 - C22) sulfuric acid esters such as sodium salt of lauryl alcohol sulfate, sodium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, Teepol B-81 (trade mark, available from Shell Chemicals Co., Ltd.) and disodium alkyl sulfates; salts of aliphatic alcohol phosphoric acid esters such as sodium salt of cetyl alcohol phosphate; alkyl aryl sulfonic acid salts such as sodium salt of dodecylbenzene sulfonate, sodium salt of isopropylnaphthalene sulfonate,sodium salt of dinaphthalene disulfonate and sodium salt of metanitrobenzene sulfonate; sulfonic acid salts of alkyl
  • Examples of such compounds are neutral salts such as NaCl, KCl and KBr as disclosed in JN-A- 58- 75 152; chelating agents such as EDTA and NTA as disclosed in JN-A- 58- 190 952 (U.S-A- 4 469 776), complexes such as [Co(NH3)6]Cl3 as disclosed in JN-A- 59- 121 336 (US-A- 4 606 995); ionizable compounds of elements of the group IIa, IIIa or IIIb of the Periodic Table such as those disclosed in JN-A- 55- 25 100; anionic or amphoteric surfactants such as sodium alkyl naphthalene sulfonate and N-tetradecyl-N,N-dihydroxythyl betaine as disclosed in JN-A- 50- 51 324; tetramethyldecyne diol as disclosed in US-A- 4 374 920; non-ionic surfactants as
  • any known means of supplementing a replenisher for developer may be employed.
  • Examples of such methods preferably used are a method for intermittently or continuously supplementing a replenisher as a function of the amount of PS plates processed and time as disclosed in JN-A- 55- 115 039 ( GB-A- 2 046 931 ) , a method comprising disposing a sensor for detecting the degree of light-sensitive layer dissolved out in the middle portion of a developing zone and supplementing the replenisher in proportion to the detected degree of the light-sensitive layer dissolved out as disclosed in JN-A- 58- 95 349 ( US-A- 4 537 496 ); a method comprising determining the impedance value of a developer and processing the detected impedance value by a computer to perform supplementation of a replenisher as disclosed in GB-A- 2 208 249.
  • the printing plate of the present invention can also be used in the printing process as a seamless sleeve printing plate.
  • the printing plate is soldered in a cylindrical form by means of a laser.
  • This cylindrical printing plate which has as diameter the diameter of the print cylinder is slided on the print cylinder instead of applying in a classical way a classically formed printing plate. More details on sleeves are given in "Grafisch Nieuws" ed. Keesing, 15, 1995, page 4 to 6.
  • the obtained plate After the development of an image-wise exposed imaging element with an aqueous alkaline solution and drying, the obtained plate can be used as a printing plate as such. However, to improve durability it is still possible to bake said plate at a temperature between 200°C and 300°C for a period of 30 seconds to 5 minutes. Also the imaging element can be subjected to an overall post-exposure to UV-radiation to harden the image in order to increase the run lenght of the printing plate.
  • Example 1 (comparative): Material with no IR-absorbing compound in the first layer
  • Example 2 Material with 2.5 % w/w carbon black as IR-absorbing compound in the first layer.
  • Example 3 Material with 5 % w/w carbon black as IR-absorbing compound in the first layer.
  • the first layer was coated on a lithographic base as described in example 1 from THF/2-methoxypropanol (in a ratio of 55/45) at a wet thickness of 14 ⁇ m resulting in a dry coating weight of 1.10 g/m 2 .
  • Example 4 Material with an increased concentration of carbon black in the top layer.
  • Examples 1,2,3 and 4 were imaged with a CREO Trendsetter 3244T (2400dpi). After imaging the materials were developed at 1 m/min at 25oC in a Technigraph NPX-32T processor using an Ozasol EP262A developer (Ozasol EP262A developer commercially available from Agfa). The IR-exposed areas dissolved very rapidly without any attack in the non IR-exposed areas, resulting in a positive working printing plate. The resulting plates were printed on a Heidelberg GTO46 printing machine with a conventional ink (K+E) and fountain solution (Rotamatic), resulting in good prints, i.e. no scumming in IR-exposed areas and good ink-uptake in the non exposed areas.
  • K+E conventional ink
  • Rotamatic fountain solution
  • the values are listed in table 1. It is clear that the IR-sensitivity is enhanced when using a IR-absorbing compound in the first layer. Increasing the carbon concentration in the top layer (with a comparable amount as used in the first layer of example 3) does not lead to an increase in IR-sensitivity, on the contrary, an IR-sensitivity decrease is observed.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Materials For Photolithography (AREA)

Claims (10)

  1. Elément de formation d'image thermosensible pour fabriquer un cliché d'impression lithographique possédant, sur une base lithographique comprenant une surface hydrophile, une première couche englobant un polymère soluble dans une solution alcaline aqueuse et une couche de protection du même côté de la base lithographique que celui où est située la première couche, ladite couche de protection étant impénétrable pour et insoluble à un révélateur alcalin contenant du SiO2 sous la forme de silicates avant l'exposition en forme d'image à un rayonnement infrarouge, les parties contenant une image pouvant être éliminées au cours du développement sans donner lieu à une solubilisation et/ou à une dégradation des parties exemptes d'image ; caractérisé en ce que ladite première couche et ladite couche de protection comprennent un composé capable de transformer de la lumière infrarouge en chaleur.
  2. Elément de formation d'image thermosensible pour fabriquer un cliché d'impression lithographique selon la revendication 1, dans lequel ledit polymère inclus dans la première couche est un polymère hydrophobe.
  3. Elément de formation d'image thermosensible pour fabriquer un cliché d'impression lithographique selon la revendication 2, dans lequel ledit polymère est une résine de novolaque ou un polymère comprenant des unités d'hydroxystyrène.
  4. Elément de formation d'image thermosensible pour fabriquer un cliché d'impression lithographique selon l'une quelconque des revendications 1 à 3, dans lequel ladite première couche comprend en outre un composé choisi parmi le groupe constitué par des acides à bas poids moléculaire et par des benzophénones.
  5. Elément de formation d'image thermosensible pour fabriquer un cliché d'impression lithographique selon l'une quelconque des revendications 1 à 4, dans lequel ledit composé capable de transformer de la lumière infrarouge en chaleur est un colorant ou un pigment infrarouge.
  6. Elément de formation d'image thermosensible pour fabriquer un cliché d'impression lithographique selon l'une quelconque des revendications 1 à 5, dans lequel ledit composé capable de transformer de la lumière infrarouge en chaleur ne diminue pas la solubilité de la première couche dans une solution alcaline aqueuse.
  7. Elément de formation d'image thermosensible pour fabriquer un cliché d'impression lithographique selon l'une quelconque des revendications 1 à 6, dans lequel ledit composé capable de transformer de la lumière infrarouge en chaleur est présent dans ladite première couche en une quantité de 0,1 à 30 parties en poids du poids total de ladite première couche.
  8. Elément de formation d'image thermosensible pour fabriquer un cliché d'impression lithographique selon l'une quelconque des revendications 1 à 7, dans lequel ladite couche de protection comprend un liant qui est insoluble dans une solution alcaline aqueuse.
  9. Elément de formation d'image thermosensible pour fabriquer un cliché d'impression lithographique selon l'une quelconque des revendications 5 à 8, dans lequel ledit colorant ou ledit liant infrarouge est présent dans ladite couche de protection en une quantité entre 1 et 99 parties en poids du poids total de ladite couche de protection.
  10. Procédé de fabrication d'un cliché d'impression lithographique, comprenant les étapes consistant à :
    a) exposer en forme d'image à un rayonnement infrarouge, un élément de formation d'image thermosensible selon l'une quelconque des revendications 1 à 9 ; et
    b) développer ledit élément de formation d'image thermosensible exposé en forme d'image avec ledit révélateur alcalin, de telle sorte que les zones exposées de la première couche et de la couche de protection sont éliminées et que les zones non exposées de la première couche subsistent.
EP99200336.8A 1998-03-14 1999-02-05 Procédé pour la fabrication d'une plaque d'impression positive à partir d'un élément pour l'enregistrement de l'image thermosensible Expired - Lifetime EP0943451B3 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP99200336.8A EP0943451B3 (fr) 1998-03-14 1999-02-05 Procédé pour la fabrication d'une plaque d'impression positive à partir d'un élément pour l'enregistrement de l'image thermosensible
DE69901642.8T DE69901642T3 (de) 1998-03-14 1999-02-05 Verfahren zur Herstellung einer positiv arbeitenden Druckplatte aus einem wärmeempfindlichem Bildaufzeichnungsmaterial

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP98200831 1998-03-14
EP98200831 1998-03-14
EP99200336.8A EP0943451B3 (fr) 1998-03-14 1999-02-05 Procédé pour la fabrication d'une plaque d'impression positive à partir d'un élément pour l'enregistrement de l'image thermosensible

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EP0943451A1 EP0943451A1 (fr) 1999-09-22
EP0943451B1 true EP0943451B1 (fr) 2002-06-05
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1258369B1 (fr) 1997-10-17 2005-03-30 Fuji Photo Film Co., Ltd. Produit formateur d'image photosensible travaillant en positif pour laser infra-rouge et composition travaillant en positif pour laser infra-rouge
US6352811B1 (en) 1998-06-23 2002-03-05 Kodak Polychrome Graphics Llc Thermal digital lithographic printing plate
EP1506857B1 (fr) * 1998-06-23 2007-04-25 Eastman Kodak Company Elément thermique travaillant en positif et formateur d'images et plaque d'impression lithographique travaillant en positif
US6534238B1 (en) 1998-06-23 2003-03-18 Kodak Polychrome Graphics, Llc Thermal digital lithographic printing plate
DE60119824T3 (de) 2000-04-07 2012-05-31 Fujifilm Corp. Wärmeempfindlicher lithographischer Druckplattevorläufer
JP2001324818A (ja) * 2000-05-15 2001-11-22 Fuji Photo Film Co Ltd 平版印刷版現像液の補充方法
JP4137345B2 (ja) 2000-06-05 2008-08-20 富士フイルム株式会社 平版印刷版原版
JP2002062663A (ja) * 2000-08-14 2002-02-28 Fuji Photo Film Co Ltd 平版印刷版の品質管理方法
US6649324B1 (en) * 2000-08-14 2003-11-18 Kodak Polychrome Graphics Llc Aqueous developer for lithographic printing plates
BR0102218B1 (pt) * 2001-05-31 2012-10-16 produto sensìvel à radiação, e processo de impressão ou revelação de imagem utilizando o referido produto.
JP2002357894A (ja) * 2001-06-01 2002-12-13 Fuji Photo Film Co Ltd 平版印刷版用原版およびその処理方法
US7341815B2 (en) 2001-06-27 2008-03-11 Fujifilm Corporation Planographic printing plate precursor
US6699636B2 (en) 2001-12-12 2004-03-02 Kodak Polychrome Graphics Llc Imaging element comprising a thermally activated crosslinking agent

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Publication number Priority date Publication date Assignee Title
GB1160221A (en) * 1965-05-17 1969-08-06 Agfa Gevaert Nv Photothermographic Materials and Processes
GB1154568A (en) * 1965-11-26 1969-06-11 Agfa Gevaert Nv Improvements relating to Thermographic Copying.
NL6608712A (fr) * 1966-06-23 1966-11-25
GB1208415A (en) * 1966-10-24 1970-10-14 Agfa Gevaert Nv Improvements relating to thermo-copying
GB1208414A (en) * 1966-10-24 1970-10-14 Agfa Gevaert Nv Improvements relating to thermo recording
GB1245924A (en) * 1967-09-27 1971-09-15 Agfa Gevaert Improvements relating to thermo-recording
EP0573092A1 (fr) * 1992-06-05 1993-12-08 Agfa-Gevaert N.V. Procédé d'obtention d'une image utilisant un matériau d'enregistrement thermosensible
US5466557A (en) * 1994-08-29 1995-11-14 Eastman Kodak Company Radiation-sensitive composition containing a resole resin, a novolac resin, a latent bronsted acid, an infrared absorber and terephthalaldehyde and use thereof in lithographic printing plates
US5641608A (en) * 1995-10-23 1997-06-24 Macdermid, Incorporated Direct imaging process for forming resist pattern on a surface and use thereof in fabricating printing plates
JP3814961B2 (ja) * 1996-08-06 2006-08-30 三菱化学株式会社 ポジ型感光性印刷版

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EP0943451A1 (fr) 1999-09-22
EP0943451B3 (fr) 2018-12-12

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