EP1023994B1 - Wärmeempfindliches Bildaufzeichnungsmaterial zur Herstellung von positiv arbeitenden Flachdruckformen - Google Patents

Wärmeempfindliches Bildaufzeichnungsmaterial zur Herstellung von positiv arbeitenden Flachdruckformen Download PDF

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Publication number
EP1023994B1
EP1023994B1 EP19990200288 EP99200288A EP1023994B1 EP 1023994 B1 EP1023994 B1 EP 1023994B1 EP 19990200288 EP19990200288 EP 19990200288 EP 99200288 A EP99200288 A EP 99200288A EP 1023994 B1 EP1023994 B1 EP 1023994B1
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EP
European Patent Office
Prior art keywords
layer
imaging element
printing plate
heat mode
making
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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EP19990200288
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English (en)
French (fr)
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EP1023994A1 (de
Inventor
Eric Verschueren
Joan Vermeersch
Marc Van Damme
Guido Hauquier
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Agfa Gevaert NV
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Agfa Gevaert NV
Agfa Gevaert AG
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Publication date
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Priority to EP19990200288 priority Critical patent/EP1023994B1/de
Priority to DE1999616773 priority patent/DE69916773T2/de
Priority to US09/476,089 priority patent/US6472119B1/en
Priority to JP2000010808A priority patent/JP2000221668A/ja
Publication of EP1023994A1 publication Critical patent/EP1023994A1/de
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Publication of EP1023994B1 publication Critical patent/EP1023994B1/de
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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
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/36—Thermography ; 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
    • 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
    • B41C2210/04—Negative working, i.e. the non-exposed (non-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 comprising an IR sensitive top layer.
  • the invention is related to a heat mode imaging element for preparing a lithographic printing plate with a higher resistance of the upper layer to mechanical damage.
  • 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- 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.
  • EP-A- 97 203 129.8 and EP-A- 97 203 132.2 disclose a heat mode imaging element consisting of a lithographic base with a hydrophilic surface and a top layer which top layer is sensitive to IR-radiation, comprises a polymer, soluble in an aqueous alkaline solution and is unpenetrable for an alkaline developer containing SiO 2 as silicates
  • Said last three heat-mode imaging element have the disadvantage that the upper layer is very sensitive to damages. Especially critical are these printing plates to surface damage when a mechanical load is applied whereby at the same time a vacuum is applied. These conditions occur when the plates are transported f.i. with suction cups. Because when the vacuum is applied, there is only a small contact surface, there originares a strong mechanical load per unit of surface. Covering the upper layer with a protective layer results in a lower resolution and in a lower development lattitude, due to a smaller difference in the rate of penetration of the developing liquid between exposed and non-exposed areas. A solution for said problem 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 IR-sensitive and unpenetrable for or insoluble in an alkaline developer wherein said first layer and said top layer may be one and the same layer; characterized in that said imaging layers have a glass transition temperature of at least 57°C.
  • the top layer is also called the second layer.
  • the glass transition temperature (Tg) of the imaging layers is at least 57 °C, preferably at least 59 °C.
  • the glass transition temperature of the imaging layers can be guided by the drying parameters of the surface layer, in particular the drying temperature.
  • the first layer and the top layer are different.
  • a heat mode imaging element for making lithographic printing plates 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 sensitive to IR-radiation and which is unpenetrable or insoluble for an alkaline developer.
  • the top layer in accordance with the present invention comprises an IR-dye or pigment and preferably 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 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.
  • 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. 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.
  • 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 0.005 to 10 g/m 2 , more preferably from 0.01 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 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 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 polymers, 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 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 for all embodiments.
  • 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 for all embodiments.
  • 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, acrylate acid, methacrylate acid, hydroxyethyl acrylate, hydroxyethyl methacrylate or maleic anhydride/vinylmethylether copolymers.
  • the hydrophilicity of the (co)polymer or (co)polymer mixture used is preferably the same as or higher than the hydrophilicity of polyvinyl acetate hydrolyzed to at least an extent of 60 percent by weight, preferably 80 percent by weight.
  • the amount of crosslinking agent, in particular of tetraalkyl orthosilicate, is preferably at least 0.2 parts by weight per part by weight of hydrophilic binder, more preferably between 0.5 and 5 parts by weight, most preferably between 1.0 parts by weight and 3 parts by weight.
  • a cross-linked hydrophilic layer in a lithographic base used in accordance with the present embodiment preferably also contains substances that increase the mechanical strength and the porosity of the layer.
  • colloidal silica may be used.
  • the colloidal silica employed may be in the form of any commercially available water-dispersion of colloidal silica for example having an average particle size up to 40 nm, e.g. 20 nm.
  • inert particles of larger size than the colloidal silica may be added e.g. silica prepared according to Stöber as described in J. Colloid and Interface Sci., Vol.
  • alumina particles or particles having an average diameter of at least 100 nm which are particles of titanium dioxide or other heavy metal oxides.
  • the thickness of a cross-linked hydrophilic layer in a lithographic base in accordance with this embodiment may vary in the range of 0.2 to 25 ⁇ m and is preferably 1 to 10 ⁇ m.
  • plastic film e.g. substrated polyethylene terephthalate film, substrated polyethylene naphthalate film, cellulose acetate film, polystyrene film, polycarbonate film etc.
  • the plastic film support may be opaque or transparent.
  • 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.
  • a heat mode imaging element for making lithographic printing plates having on a lithographic base with a hydrophilic surface a top layer which top layer is sensitive to IR-radiation comprises a polymer, soluble in an aqueous alkaline solution and is unpenetrable or insoluble for an alkaline developer.
  • the IR-sensitive layer in accordance with the present invention comprises an IR-dye or pigment and a polymer, soluble in an aqueous alkaline solution.
  • a mixture of IR-dyes or pigments may be used, but it is preferred to use only one IR-dye or pigment. Suitable IR-dyes and pigments are those mentioned above in the first embodiment of the present invention.
  • the IR-dyes are present preferably in an amount between 1 and 60 parts, more preferably between 3 and 50 parts by weight of the total amount of said IR-sensitive top layer.
  • the alkali soluble polymers used in this layer are preferably hydrophobic and ink accepting polymers as used in conventional positive or negative working PS-plates e.g. carboxy substituted polymers etc. More preferably is a phenolic resin such as a hydroxystyrene units containing polymer or a novolac polymer. Most preferred is a novolac polymer. 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 polymer used in connection with the present invention is further characterised by insolubility in water and at least partial solubility/swellability in an alkaline solution and/or at least partial solubility in water when combined with a cosolvent.
  • this IR-sensitive layer is preferably a visible light- and UV-light desensitised layer. Still further said layer is preferably thermally hardenable.
  • This preferably visible light- and UV-light 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 IR-sensitive layer preferably also includes a low molecular acid, more preferably a carboxylic acid, still more preferably a benzoic acid, most preferably 3,4,5-trimethoxybenzoic acid or a benzophenone, more preferably trihydroxybenzofenone.
  • a low molecular acid more preferably a carboxylic acid, still more preferably a benzoic acid, most preferably 3,4,5-trimethoxybenzoic acid or a benzophenone, more preferably trihydroxybenzofenone.
  • the ratio between the total amount of low molecular acid or benzofenone and polymer in the IR-sensitive layer preferably ranges from 2:98 to 40:60, more preferably from 5:95 to 30:70.
  • the total amount of said IR-sensitive layer preferably ranges from 0.1 to 10 g/m 2 , more preferably from 0.3 to 2 g/m 2 .
  • a difference in the capacity of being penetrated and/or solubilised by the alkaline developer is generated upon image-wise exposure for an alkaline developer according to the invention.
  • the heat-mode imaging element is image-wise exposed and developed.
  • 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 as 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
  • 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(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 sur
  • 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 mm.
  • 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 above described lithographic base was first coated a layer from a 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 (sold by Clariant, Germany) and 12% of 3,4,5-trimethoxybenzoic acid and was dried at 120 °C for 40sec..
  • the IR-sensitive layer Upon this layer was coated with a wet coating thickness of 20 ⁇ m, the IR-sensitive layer from a 0.272% wt solution in methylethylketone/methoxypropanol 50/50 ratio. This layer was dried at a temperature of at least 100°C for at least 42 seconds.
  • the resulting IR-sensitive layer contained 35 mg/m 2 of IR-absorber I, 12.5 mg/m 2 of FLEXO-BLAU 630 TM, 2.0 mg/m 2 of TEGO WET 265 TM and 5.0 mg/m 2 of TEGO GLIDE 410 TM (both siloxanes surfactants from Goldschmitt, Germany).
  • FLEXO-BLAU 630 is commercially available by BASF, Ludwigshafen, Germany.
  • Example Tg 1 50 °C 2 54 °C 3 56 °C 4 58 °C 5 65 °C Determination of suction cup sensitivity: In an experimental apparatus, build with original suction cups from a laser imager, following test was carried out. To 12 suction cups a vacuum of 85 kPA was applied. After 30 seconds, the vacuum of 3 suction cups was released. After 60 seconds, again the vacuum of 3 further suction cups was released.
  • the element After exposure of the imaging element, the element was developed in an aqueous alkaline developing solution. These developing was carried out in a Technigraph NPX-32 processor at a speed of 1 m/min at 25°C, filled with Ozasol EP26A (Ozasol EP262A is commercially available from Agfa) and with water in the rinsing section and Ozasol RC795 gum in the gumming section.
  • Example Etching defects 1 severe 2 slight 3 very slight 4 no 5 no

Claims (9)

  1. Ein wärmeempfindliches Bilderzeugungselement zur Herstellung einer lithografischen Druckplatte, das auf einem lithografischen Träger mit einer hydrophilen Oberfläche eine erste, ein in einer wässrig-alkalischen Lösung lösliches Polymer enthaltende Schicht und auf derselben Seite des lithografischen Trägers wie die erste Schicht eine IR-empfindliche Deckschicht enthält, die undurchdringbar und unlöslich für einen alkalischen Entwickler ist, wobei die erste Schicht und die Deckschicht ein und dieselbe Schicht sein können und die erste Schicht und die Deckschicht die Bilderzeugungsschichten sind, dadurch gekennzeichnet, dass die Bilderzeugungsschichten einen Einfrierpunkt von zumindest 57°C aufweisen.
  2. Wärmeempfindliches Bilderzeugungselement zur Herstellung einer lithografischen Druckplatte nach Anspruch 1, dadurch gekennzeichnet, dass die Bilderzeugungsschichten einen Einfrierpunkt von zumindest 59°C aufweisen.
  3. Wärmeempfindliches Bilderzeugungselement zur Herstellung einer lithografischen Druckplatte nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das in einer wässrig-alkalischen Lösung lösliche Polymer wärmehärtbar ist.
  4. Wärmeempfindliches Bilderzeugungselement zur Herstellung einer lithografischen Druckplatte nach Anspruch 3, dadurch gekennzeichnet, dass das Polymer ein Polymer aus der Gruppe bestehend aus Novolak, Polyhydroxystyrol und einem carboxylsubstituierten Polymer ist.
  5. Wärmeempfindliches Bilderzeugungselement zur Herstellung einer lithografischen Druckplatte nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die das Polymer enthaltende Schicht eine löslich machende Verbindung für das Polymer enthält.
  6. Wärmeempfindliches Bilderzeugungselement zur Herstellung einer lithografischen Druckplatte nach Anspruch 5, dadurch gekennzeichnet, dass die löslich machende Verbindung eine Verbindung aus der Gruppe bestehend aus niedermolekularen Säuren und Benzophenonen ist.
  7. Wärmeempfindliches Bilderzeugungselement zur Herstellung einer lithografischen Druckplatte nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die lithografische Unterlage mit einer hydrophilen Oberfläche ein elektrochemisch gekörntes und eloxiertes Aluminiumsubstrat ist.
  8. Wärmeempfindliches Bilderzeugungselement zur Herstellung einer lithografischen Druckplatte nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die lithografische Unterlage mit einer hydrophilen Oberfläche ein biegsamer, ein gehärtetes hydrophiles Bindemittel enthaltender Träger ist.
  9. Wärmeempfindliches Bilderzeugungselement zur Herstellung einer lithografischen Druckplatte nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass das Bilderzeugungselement einen Infrarotlicht absorbierenden Farbstoff oder ein Infrarotlicht absorbierendes Pigment enthält.
EP19990200288 1999-01-26 1999-01-26 Wärmeempfindliches Bildaufzeichnungsmaterial zur Herstellung von positiv arbeitenden Flachdruckformen Expired - Lifetime EP1023994B1 (de)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP19990200288 EP1023994B1 (de) 1999-01-26 1999-01-26 Wärmeempfindliches Bildaufzeichnungsmaterial zur Herstellung von positiv arbeitenden Flachdruckformen
DE1999616773 DE69916773T2 (de) 1999-01-26 1999-01-26 Wärmeempfindliches Bildaufzeichnungsmaterial zur Herstellung von positiv arbeitenden Flachdruckformen
US09/476,089 US6472119B1 (en) 1999-01-26 2000-01-03 Heat mode sensitive imaging element for making positive working printing plates
JP2000010808A JP2000221668A (ja) 1999-01-26 2000-01-19 ポジティブ作用性印刷版の作製のためのヒ―トモ―ド感受性画像形成要素

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EP19990200288 EP1023994B1 (de) 1999-01-26 1999-01-26 Wärmeempfindliches Bildaufzeichnungsmaterial zur Herstellung von positiv arbeitenden Flachdruckformen

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ITVA20020029A1 (it) 2002-03-22 2003-09-22 Lamberti Spa Composizioni per lastre litografiche positive termiche
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DE69916773D1 (de) 2004-06-03
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JP2000221668A (ja) 2000-08-11

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