EP0950518B1 - Wärmeempfindliches Aufzeichnungsmaterial zur Herstellung von positiv arbeitenden Druckplatten - Google Patents

Wärmeempfindliches Aufzeichnungsmaterial zur Herstellung von positiv arbeitenden Druckplatten Download PDF

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Publication number
EP0950518B1
EP0950518B1 EP19990200511 EP99200511A EP0950518B1 EP 0950518 B1 EP0950518 B1 EP 0950518B1 EP 19990200511 EP19990200511 EP 19990200511 EP 99200511 A EP99200511 A EP 99200511A EP 0950518 B1 EP0950518 B1 EP 0950518B1
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EP
European Patent Office
Prior art keywords
imaging element
layer
printing plate
heat mode
making
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EP19990200511
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English (en)
French (fr)
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EP0950518A1 (de
Inventor
Marc Van Damme
Joan Vermeersch
Guido Hauquier
Eric Verschueren
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Agfa Gevaert NV
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Agfa Gevaert NV
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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
    • B41C2210/22—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. More specifically the invention is related to a heat mode imaging element for preparing a lithographic printing plate whereof the difference in the top layer of being penetrated and/or solubilised in the exposed areas and in the non-exposed areas by an aqueous developer is increased.
  • 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.
  • 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 interlayer 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 permeabilities 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 recording 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 support or interlayer.
  • JP-A-01-46739 discloses a method for preventing the line-like unequalities generated by foam by dissolving a photosensitive composition containing at least a photosensitive material, fluorine surfactant and defoaming agent into a coating solvent, then coating the solution on a base and drying the coating.
  • JP-A-02-29750 discloses a method for obtaining a photosensitive composition suitable for a positive photosensitive printing plate by using o-naphthoquinonediazide sulphonic acid, an alkali-soluble resin, and a non-ionic surfactant such as polyoxyethylene naphthol.
  • EP-A- 527.369 discloses a light sensitive recording material comprising a support and a positive working light sensitive layer with a rough surface, which comprises as light sensitive compound at least a 1,2-quinonediazide and as water insoluble and in water-alkaline solutions soluble or swellable binder a polycondensate or polymer and a filler, wherein the light-sensitive layer at a layer weight of 3g/m 2 or less (i) comprises as filler silica with a mean diameter from 3 to 5 ⁇ m and a final limit of 15 ⁇ m in an amount, which yields a slipperiness according to Beck from 20 till 100 seconds and (ii) furthermore comprises a surfactant with polysiloxane units.
  • EP-A- 823 327 discloses a positive photosensitive composition showing a difference in solubility in an alkali developer as between an exposed portion and a non-exposed portion, which comprises, as components inducing the difference in solubility, (a) a photo-thermal conversion material, and (b) a high molecular compound, of which the solubility in an alkali developer is changeable mainly by a change other than a chemical change.
  • 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 864 420 which is prior art under Art 54(3)EPC, discloses the use of Solsperse surfactants, availaible from ICI (later Zeneca, now Avecia Ltd.) in heat-mode lithographic printing plates.
  • 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 polymerthat is soluble in an aqueous alkaline solution and a top layer on the same side of the lithographic base as the first layer that is IR-sensitive and unpenetrable for an alkaline developer; characterized in that at least one of said first layer and said top layer comprises a surfactant, with the proviso that the surfactant is not Solsperse 5000 or Solsperse 28000.
  • the first layer and/or the top (also called the second) layer comprises a surfactant.
  • Said surfactant can be a cationic, an anionic or an amphoteric surfactant, but is preferably a non-ionic surfactant.
  • the surfactant is preferably selected from the group consisting of perfluoroalkyl surfactants, alkylphenyl surfactants and most preferably polysiloxane surfactants. Still more preferably a combination of at least two polysiloxane surfactants is used.
  • the surfactant is preferably present in the top layer.
  • the amount of surfactant lies preferably in the range from 0.001 to 0.3g/m 2 , more preferably in the range from 0.003 to 0.050g/m 2 .
  • the top layer in accordance with the present invention comprises an IR-dye or pigment and a binder resin.
  • a mixture of IR-dyes or pigments may be used, but it is preferred to use only one IR-dye or pigment.
  • Preferably said IR-dyes are IR-cyanines dyes.
  • Particularly useful IR-cyanine dyes are cyanines dyes with two indolenine groups. Most preferably is compound I with the structure as indicated
  • 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. WO2.9.
  • 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.
  • said top layer contains an IR-dye
  • said top layer preferably also contains a dye or a pigment that absorbs in the visible region in order to be able to visually inspect the image formed after IR-radiation and development in an aqueous alkaline developer.
  • the IR-absorbing dyes or pigments are present preferably in an amount between 1 and 99 parts, more preferably between 50 and 95 parts by weight of the total amount of said IR-sensitive top layer.
  • the top layer may preferably comprise as binder a water 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 0.010 to 5 g/m 2 more preferably from 0.020 to 1 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 for an alkaline developer 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.
  • 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.
  • hydrophobic binder used in connection with the present invention is further characterised by insolubility in water and partial solubility/swellability 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 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, 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.
  • aqueous alkaline solutions used in the present invention are those that are used for developing conventional positive working presensitised printing plates, preferably containing SiO 2 in the form of silicates and having 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 and M 2 O in a molar ratio .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 as
  • 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 (C 8 ⁇ C 22 ) 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 al
  • 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(NH 3 ) 6 ]Cl 3 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
  • 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.
  • a 0.30 mm thick aluminum foil was degreased by immersing the foil in an aqueous solution containing 5 g/l of sodium hydroxide at 50°C and rinsed with demineralized water.
  • the foil was then electrochemically grained using an alternating current in an aqueous solution containing 4 g/l of hydrochloric acid, 4 g/l of hydroboric acid and 5 g/l of aluminum ions at a temperature of 35°C and a current density of 1200 A/m 2 to form a surface topography with an average center-line roughness Ra of 0.5 ⁇ m.
  • the aluminum foil was then etched with an aqueous solution containing 300 g/l of sulfuric acid at 60°C for 180 seconds and rinsed with demineralized water at 25°C for 30 seconds.
  • the foil was subsequently subjected to anodic oxidation in an aqueous solution containing 200 g/l of sulfuric acid at a temperature of 45°C, a voltage of about 10 V and a current density of 150 A/m 2 for about 300 seconds to form an anodic oxidation film of 3.00 g/m 2 of Al 2 O 3 then washed with demineralized water, posttreated with a solution containing polyvinylphosphonic acid and subsequently with a solution containing aluminum trichloride, rinsed with demineralized water at 20°C during 120 seconds and dried.
  • lithographic base On the lithographic base was first coated a layer from an 8.6% wt solution in tetrahydrofuran/methoxypropanol 55/45 ratio, with a wet coating thickness of 14 ⁇ m.
  • the resulting layer contained 88% of ALNOVOL SPN452 TM and 12% of 3,4,5-trimethoxybenzoic acid.
  • Upon this layer was then coated with a wet coating thickness of 20 ⁇ m, the IR-sensitive layer from a 0.885% wt solution in methylethylketone/methoxypropanol 50/50 ratio. This layer was dried on a temperature of 120°C.
  • the resulting IR-sensitive layer contained 115 mg/m 2 of carbon black, 11.5 mg/m 2 of nitrocellulose, 2.1 mg/m 2 of SOLSPERSE 5000 TM, ( available from Zeneca Specialities, GB) 11.3 mg/m 2 of SOLSPERSE 28000 TM and 14 mg/m 2 of FLUORAD FC 431 TM.
  • FLUORAD FC 431 TM is a non-ionic perfluoroaliphatic polymeric ester, available from 3M,USA.
  • lithographic base of example 1 On the lithographic base of example 1 was first coated a layer from an 8.6% wt solution in tetrahydrofuran/methoxypropanol 55/45 ratio, with a wet coating thickness of 14 ⁇ m. The resulting layer contained 88% of ALNOVOL SPN452 TM and 12% of 3,4,5-trimethoxybenzoic acid. Upon this layer was then coated with a wet coating thickness of 20 ⁇ m, the IR-sensitive layer from a 0.3% wt solution in methylethylketone/methoxypropanol 50/50 ratio. This layer was dried on a temperature of 120°C. .
  • the resulting IR-sensitive layer contained 35 mg/m 2 IR-dye compound 1, 10 mg/m 2 dye BASONYL-BLAU 636 TM (a triarylmethane dye commercially available from BASF), 2 mg/m 2 TEGOGLIDE 265 TM (polyether siloxane copolymer) and 5 mg/m 2 TEGOGLIDE 410 TM (polyether modified polysiloxane) (both silicon surfactants commercially available from Tego Chemie Service GmbH).
  • BASONYL-BLAU 636 TM a triarylmethane dye commercially available from BASF
  • 2 mg/m 2 TEGOGLIDE 265 TM polyether siloxane copolymer
  • 5 mg/m 2 TEGOGLIDE 410 TM polyether modified polysiloxane
  • This material was imaged with a CREO TRENDSETTER 3244-T TM external drum platesetter (available from Creo)at 2400 dpi with an energy-density of 186 mJ/cm 2 at 150 rpm.
  • the IR-exposed areas dissolved very rapidly without any attack in the non IR-exposed areas, resulting in a positive working printing plate.
  • the plate was printed on a Heidelberg GTO46 printing machine with a conventional ink (K+E800) and fountain solution (Rotamatic), resulting in good prints, i.e. no scumming in IR-exposed areas and good ink-uptake in the non imaged areas.
  • K+E800 conventional ink
  • Rotamatic fountain solution
  • the surfactants TEGO GLIDE 265 TM and TEGO GLIDE 410 TM were left out of the IR-sensitive top layer of the heat-mode imaging element 2.
  • This material was imaged with a CREO TRENDSETTER 3244-T TM external drum platesetter at 2400 dpi with an energy-density of 186 mJ/cm 2 at 150 rpm.
  • the material was developer at 1 m/min at 25°C in a TECHNIGRAPH NPX-32T TM processor using OZASOL EP26 TM developer (commercially available from Agfa).

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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. Ein wärmeempfindliches Bilderzeugungselement zur Herstellung einer lithografischen Druckplatte, das aus einem lithografischen Träger mit einer hydrophilen Oberfläche eine erste Schicht mit einem in einer wäßrig-alkalischen Lösung löslichen Polymer und auf der gleichen Seite des lithografischen Trägers wie die erste Schicht eine Deckschicht enthält, die gegenüber IR-Strahlung empfindlich ist und nicht durch einen alkalischen Entwickler durchdringbar ist, dadurch gekennzeichnet, daß die erste Schicht und/oder die Deckschicht ein Tensid enthält (enthalten), mit der Voraussetzung, daß als Tensid nicht Solsperse 5000 oder Solsperse 28000 benutzt wird.
  2. Ein wärmeempfindliches Bilderzeugungselement zur Herstellung einer lithografischen Druckplatte nach Anspruch 1, dadurch gekennzeichnet, daß das Tensid aus der Gruppe bestehend aus Perfluoralkyltensiden und Alkylphenyltensiden gewählt wird.
  3. Ein wärmeempfindliches Bilderzeugungselement zur Herstellung einer lithografischen Druckplatte nach Anspruch 1, dadurch gekennzeichnet, daß das Tensid ein Polysiloxantensid ist.
  4. Ein wärmeempfindliches Bilderzeugungselement zur Herstellung einer lithografischen Druckplatte nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das Tensid in einer Menge zwischen 0,003 und 0,050 g/m2 enthalten ist.
  5. Ein wärmeempfindliches Bilderzeugungselement zur Herstellung einer lithografischen Druckplatte nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das Polymer in der ersten Schicht ein hydrophobes Polymer ist.
  6. Ein wärmeempfindliches Bilderzeugungselement zur Herstellung einer lithografischen Druckplatte nach Anspruch 5, dadurch gekennzeichnet, daß das hydrophobe Polymer ein Novolakharz oder ein Hydroxystyroleinheiten enthaltendes Polymer ist.
  7. Ein wärmeempfindliches Bilderzeugungselement zur Herstellung einer lithografischen Druckplatte nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die erste Schicht eine Verbindung aus der Gruppe bestehend aus niedermolekularen Säuren und Benzophenonen enthält.
  8. Ein wärmeempfindliches Bilderzeugungselement zur Herstellung einer lithografischen Druckplatte nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß der lithografische Träger ein elektrochemisch gekörnter und eloxierter Aluminiumträger ist.
  9. Ein wärmeempfindliches Bilderzeugungselement zur Herstellung einer lithografischen Druckplatte nach Anspruch 8, dadurch gekennzeichnet, daß der elektrochemisch gekörnte und eloxierte Aluminiumträger mit Polyvinylphosphonsäure, Polyvinylmethylphosphonsäure, Phosphorsäureestern von Polyvinylalkohol, Polyvinylsulfonsäure, Polyvinylbenzolsulfonsäure, Schwefelsäureestern von Polyvinylalkohol und Acetalen von Polyvinylalkoholen, die durch Reaktion mit einem sulfonierten alifatischen Aldehyd gebildet sind, verarbeitet ist. 10.Ein durch die nachstehenden Schritte gekennzeichnetes Verfahren zur Herstellung einer lithografischen Druckplatte :
    a) bildmäßige Belichtung eines nach einem der Ansprüche 1 bis 9 definierten wärmeempfindlichen Bilderzeugungselements mit IR-Strahlung,
    b) Entwicklung des bildmäßig belichteten wärmeempfindlichen Bilderzeugungselements mit einem wäßrig-alkalischen Entwickler, wodurch die belichteten Bereiche der Deckschicht und die unterliegenden Bereiche der ersten Schicht gelöst werden und die unbelichteten Bereiche der ersten Schicht ungelöst zurückbleiben.
EP19990200511 1998-04-15 1999-02-23 Wärmeempfindliches Aufzeichnungsmaterial zur Herstellung von positiv arbeitenden Druckplatten Expired - Lifetime EP0950518B1 (de)

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US7049045B2 (en) 2003-08-14 2006-05-23 Kodak Polychrome Graphics Llc Multilayer imageable elements
US7163777B2 (en) 2001-09-07 2007-01-16 Eastman Kodak Company Thermally sensitive imageable element
US7229744B2 (en) 2003-03-21 2007-06-12 Eastman Kodak Company Method for preparing lithographic printing plates
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US6593055B2 (en) 2001-09-05 2003-07-15 Kodak Polychrome Graphics Llc Multi-layer thermally imageable element
US6723490B2 (en) 2001-11-15 2004-04-20 Kodak Polychrome Graphics Llc Minimization of ablation in thermally imageable elements
US6699636B2 (en) 2001-12-12 2004-03-02 Kodak Polychrome Graphics Llc Imaging element comprising a thermally activated crosslinking agent
US6852464B2 (en) 2002-01-10 2005-02-08 Kodak Polychrome Graphics, Llc Method of manufacturing a thermally imageable element
US6830862B2 (en) 2002-02-28 2004-12-14 Kodak Polychrome Graphics, Llc Multi-layer imageable element with a crosslinked top layer
US6887642B2 (en) 2002-04-05 2005-05-03 Kodak Polychrome Graphies Llc Multi-layer negative working imageable element
US6849372B2 (en) 2002-07-30 2005-02-01 Kodak Polychrome Graphics Method of manufacturing imaging compositions
JP2004126050A (ja) 2002-09-30 2004-04-22 Fuji Photo Film Co Ltd 平版印刷版原版
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US6858359B2 (en) 2002-10-04 2005-02-22 Kodak Polychrome Graphics, Llp Thermally sensitive, multilayer imageable element
US20060234161A1 (en) 2002-10-04 2006-10-19 Eric Verschueren Method of making a lithographic printing plate precursor
US6803167B2 (en) 2002-12-04 2004-10-12 Kodak Polychrome Graphics, Llc Preparation of lithographic printing plates
US8110337B2 (en) 2002-12-18 2012-02-07 Fujifilm Corporation Polymerizable composition and lithographic printing plate precursor
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US6992688B2 (en) 2004-01-28 2006-01-31 Eastman Kodak Company Method for developing multilayer imageable elements
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ES2344668T3 (es) 2007-11-30 2010-09-02 Agfa Graphics N.V. Metodo para tratar una plancha de impresion litografica.
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US7229744B2 (en) 2003-03-21 2007-06-12 Eastman Kodak Company Method for preparing lithographic printing plates
US6942957B2 (en) 2003-07-17 2005-09-13 Kodak Polychrome Graphics Llc Ionic liquids as developability enhancing agents in multilayer imageable elements
US7049045B2 (en) 2003-08-14 2006-05-23 Kodak Polychrome Graphics Llc Multilayer imageable elements
US6893783B2 (en) 2003-10-08 2005-05-17 Kodak Polychrome Graphics Lld Multilayer imageable elements
US7060415B2 (en) 2003-10-08 2006-06-13 Kodak Polychrome Graphics Llc Printing plate precursor comprising solvent-resistant copolymer
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