EP0960728B1 - Wärmeempfindliches Aufzeichnungsmaterial für die Herstellung von positiv arbeitenden Druckformen - Google Patents

Wärmeempfindliches Aufzeichnungsmaterial für die Herstellung von positiv arbeitenden Druckformen Download PDF

Info

Publication number
EP0960728B1
EP0960728B1 EP19980201800 EP98201800A EP0960728B1 EP 0960728 B1 EP0960728 B1 EP 0960728B1 EP 19980201800 EP19980201800 EP 19980201800 EP 98201800 A EP98201800 A EP 98201800A EP 0960728 B1 EP0960728 B1 EP 0960728B1
Authority
EP
European Patent Office
Prior art keywords
layer
imaging element
mode imaging
top layer
heat mode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP19980201800
Other languages
English (en)
French (fr)
Other versions
EP0960728A1 (de
Inventor
Eric C/O Agfa-Gevaert N.V. Verschueren
Huub c/o Agfa-Gevaert N.V. Van Aert
Joan C/O Agfa-Gevaert N.V. Vermeersch
Marc C/O Agfa-Gevaert N.V. Van Damme
Guido C/O Agfa-Gevaert N.V. Hauquier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert NV
Original Assignee
Agfa Gevaert NV
Agfa Gevaert AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert NV, Agfa Gevaert AG filed Critical Agfa Gevaert NV
Priority to DE1998614820 priority Critical patent/DE69814820T2/de
Priority to EP19980201800 priority patent/EP0960728B1/de
Priority to US09/280,659 priority patent/US6152036A/en
Priority to JP14658899A priority patent/JP2000056462A/ja
Publication of EP0960728A1 publication Critical patent/EP0960728A1/de
Application granted granted Critical
Publication of EP0960728B1 publication Critical patent/EP0960728B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • B41C2210/04—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
    • B41C2210/24—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

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 better physical properties.
  • 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 their physical and chemical resistance is low.
  • Heat mode imaging elements with the convenient processing of said last three heat-mode imaging element but with an improved physical and chemical resistance would be appreciated.
  • the top layer is also called the second layer.
  • the top layer of a heat mode imaging element according to the invention comprises at least one compound containing epoxy units
  • epoxy resins As compounds with epoxy units there can be used the technically most important class of epoxy resins. These polymers are produced by the condensation of epichlorohydrin and Bisphenol A or F.
  • thermoplast or thermoset modified polymers comprising epoxy-units.
  • Commercially available products are polymers such as epoxy novolac resins, rubber modified epoxy resins, butadiene-acrylonitrile polymer modified epoxy resins, Bisphenol A based polyester resins, epoxidised o-cresylic novolacs, urethane modified epoxy resins, phosphate modified Bisphenol A epoxy resins.
  • These polymers can have various molecular weights so that they can be liquid, semi-solid or solid products. Also these products can be used as dispersions in a liquid such as water or another solvent.
  • the functionality is a very important parameter in view of the crosslinking behavior. This is expressed as the epoxide equivalent weight (the weight of epoxy functions per molecular weight). This is a measure of the potentional crosslink density of the polymer. This epoxide equivalent weight lies preferably between 0.03 and 0.8, more preferably between 0.05 and 0.6.
  • the above mentioned epoxy resins can be hardened with a variety of compounds.
  • the most preferred compounds are those belonging to class of the amines, preferably low viscous amines. These can be monomolecular amines, or can also be polymeric products containing amino groups.
  • amines such as ethylenediamine, diethylenetetramine, dipropylene triamine, monomethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, 2-(2-aminoethoxy)ethanol, morpholine, N-methylmorpholine, N-ethylmorpholine.
  • propylamines such as dimethylaminopropylamine, aminopropylmorpholine, methoxypropylamine can be used.
  • piperazines like N-aminoethylpiperazine are effective hardening agents.
  • Other suitable amines are cycloaliphatic polyamines such as isophorone diamine, aromatic polyamines or araliphatic polyamines.
  • Suitable amines are polymeric amines.
  • a very preferred class of epoxy-hardeners are polyoxyalkyleneamines. These are commercially available as monoamines, diamines and triamines in a great range of molecular weight.
  • the polyether backbone can be based on propylene oxide, ethylene oxide or mixed propylene oxide/ethylene oxide.
  • hardeners are modified products of basic amines such as polyaminoamides, Mannich bases, polyether modified amines preferably polyether diamines, urethaneamines, polyether urethaneamines, polyamides, dimerized fatty acid-polyamine reaction products.
  • 2-Methylimidazole is also preferred as a hardener for compounds with an epoxy function. This results predominantly in the homopolymerization of the epoxy functions.
  • Imidazoles can be used as such or in combination with another amine or hardener. It is preferably used in an amount between 1 to 10 % by mole of the epoxy units
  • a trimethylsilane modified polyethyleneimine is also a preferred hardener. Preferably it is used in an amount of 2 to 90 weight percent versus the epoxy content.
  • the top layer also contains coupling agents.
  • coupling agents are considered as molecules comprising at least two groups with different affinities for the different compounds in the top layer.
  • Typical products are these with an amine or derivative functionality on one side of the molecule and on the other side of the molecule a group capable of absorbing on the carbon black in case of IR-sensibilisation with carbon black.
  • Typical products are trialkylsilanes, aminoalkylsilanes, aminoalkyl-alkoxysilanes such as 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane and 3- (2-aminoethylamino)-propyl-trimethoxysilane, alkoxysilanes, glycidyl ether alkoxysilanes, alkoxysilane modified polyethyleneamines, modified alkoxysilanes containing mercapto groups and isocyanatoalkyl trialkoxysilanes.
  • These coupling agents are preferably used in an amount of 5 to 30 mole percent versus the epoxy content.
  • 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 for an alkaline developer.
  • 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.
  • 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 0.05 to 10 g/m 2 , more preferably from 0.1 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 first layer and/or the top (also called the second) layer preferably comprises a surfactant.
  • Said surfactant can be a cationic, an anionic or an amphoteric surfactant, but is more preferably a non-ionic surfactant.
  • the surfactant is most preferably selected from the group consisting of perfluoroalkyl surfactants, alkylphenyl surfactants and particularly preferably polyether-modified polysiloxane surfactants.
  • 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 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 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 or pigments 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 benzofenone, 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 benzofenone, 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 .
  • the top layer preferably comprises a surfactant.
  • Said surfactant can be a cationic, an anionic or an amphoteric surfactant, but is more preferably a non-ionic surfactant.
  • the surfactant is most preferably selected from the group consisting of perfluoroalkyl surfactants, alkylphenyl surfactants and particularly preferably polysiloxane surfactants such as polysiloxane polyethers, polysiloxane copolymers, alkyl-aryl modified methyl-polysiloxanes and acylated polysiloxanes.
  • 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 .
  • 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 (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 alky
  • 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 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.
  • Upon this layer was coated with a wet coating thickness of 20 ⁇ m, the IR-sensitive layer from a 0.735% wt solution in methylethylketone/methoxypropanol 50/50 ratio. This layer was dried on a temperature of at least 120°C for at least 40 seconds.
  • 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, 11.3 mg/m 2 of SOLSPERSE 28000 TM (both dispersing agents of Zeneca specialities, G.B.), 2.0 mg/m 2 of TEGO WET 265 TM and 5.0 mg/m 2 of TEGO GLIDE 410 TM (both polysiloxane surfactants of Tego, Germany).
  • lithographic base described in example 1 On the lithographic base described in 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 coated with a wet coating thickness of 20 ⁇ m, the IR-sensitive layer from a 0.2720% wt solution in methylethylketone/methoxypropanol 50/50 ratio. This layer was dried on a temperature of at least 120°C for at least 40 seconds.
  • the resulting IR-sensitive layer contained 35 mg/m 2 of IR-absorber ST798 TM: 2-(2-(2-Chloro-3-(2-dihydro-1,1,3-trimethyl-2H-benzo(e)indole-2-ylidene)-ethylidene)-1-cyclohexen-1-yl)-ethenyl)-1,1,3-trimethyl-1H-benzo(e)indolium 4-methylbenzenesulfonate, 12.4 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.
  • ST798 is commercially available by Synthon Wolfen Germany
  • FLEXO-BLAU 630 is commercially available by BASF, Ludwigshafen, Germany.
  • lithographic base described in example 1 On the lithographic base described in 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 coated with a wet coating thickness of 20 ⁇ m, the IR-sensitive layer from a 1.0095% wt solution in methylethylketone/methoxypropanol 50/50 ratio. This layer was dried on a temperature of at least 120°C for at least 40 seconds.
  • the resulting IR-sensitive layer contained 115 mg/m 2 of carbon black, 25.2 mg/m 2 of EPI-REZ 3510 W-60 TM, 29.8 mg/m 2 of TB 3354H TM, 11.5 mg/m 2 of nitrocellulose, 2.1 mg/m 2 of SOLSPERSE 5000 TM, 11.3 mg/m 2 of SOLSPERSE 28000 TM, 2.0 mg/m 2 of TEGO WET 265 TM and 5.0 mg/m 2 of TEGO GLIDE 410 TM.
  • EPI-REZ 3510 W-60 is a waterborne dispersion of a liquid Bisphenol A epoxy resin, commercially available at Shell Chemicals.
  • TB 3354H is an aminehardener for water soluble epoxies, commercially available at Witco GmbH.
  • lithographic base described in example 1 On the lithographic base described in 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 coated with a wet coating thickness of 20 ⁇ m, the IR-sensitive layer from a 1.0095% wt solution in methylethylketone/methoxypropanol 50/50 ratio. This layer was dried on a temperature of at least 120°C for at least 40 seconds.
  • the resulting IR-sensitive layer contained 115 mg/m 2 of carbon black, 25.0 mg/m 2 of EPI-REZ 3510 W-60 TM, 30.0 mg/m 2 of EUREDUR 115 TM, 11.5 mg/m 2 of nitrocellulose, 2.1 mg/m 2 of SOLSPERSE 5000 TM, 11.3 mg/m 2 of SOLSPERSE 28000 TM, 2.0 mg/m 2 of TEGO WET 265 TM and 5.0 mg/m 2 of TEGO GLIDE 410 TM.
  • EPI-REZ 3510 W-60 is a waterborne dispersion of a liquid Bisphenol A epoxy resin, commercially available at Shell Chemicals.
  • EUREDUR 115 is a polyamidoamino, commercially available at Witco GmbH.
  • lithographic base described in example 1 On the lithographic base described in 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 coated with a wet coating thickness of 20 ⁇ m, the IR-sensitive layer from a 1.0095% wt solution in methylethylketone/methoxypropanol 50/50 ratio. This layer was dried on a temperature of at least 120°C for at least 40 seconds.
  • the resulting IR-sensitive layer contained 115 mg/m 2 of carbon black, 25.8 mg/m 2 of EPI-REZ 3510 W-60 TM, 29.2 mg/m 2 of JEFFAMINE ED900 TM, 11.5 mg/m 2 of nitrocellulose, 2.1 mg/m 2 of SOLSPERSE 5000 TM, 11.3 mg/m 2 of SOLSPERSE 28000 TM, 2.0 mg/m 2 of TEGO WET 265 TM and 5.0 mg/m 2 of TEGO GLIDE 410 TM.
  • EPI-REZ 3510 W-60 is a waterborne dispersion of a liquid Bisphenol A epoxy resin, commercially available at Shell Chemicals.
  • JEFFAMINE ED900 is a polyetherdiamine which is based on a predominately polyethyleneoxide backbone, commercially available at Huntsman Corporation, Houston.
  • lithographic base described in example 1 On the lithographic base described in 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 coated with a wet coating thickness of 20 ⁇ m, the IR-sensitive layer from a 1.0095% wt solution in methylethylketone/methoxypropanol 50/50 ratio. This layer was dried on a temperature of at least 120°C for at least 40 seconds.
  • the resulting IR-sensitive layer contained 115 mg/m 2 of carbon black, 22.7 mg/m 2 of EPI-REZ 6006 W-70 TM, 32.3 mg/m 2 of TB 3354H TM, 11.5 mg/m 2 of nitrocellulose, 2.1 mg/m 2 of SOLSPERSE 5000 TM, 11.3 mg/m 2 of SOLSPERSE 28000 TM, 2.0 mg/m 2 of TEGO WET 265 TM and 5.0 mg/m 2 of TEGO GLIDE 410 TM.
  • EPI-REZ 6006 W-70 is an epoxidised o-cresolnovolac resin, commercially available at Shell Chemicals.
  • TB 3354H is an aminehardener for water soluble epoxies, commercially available at Witco GmbH.
  • lithographic base described in example 1 On the lithographic base described in 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 coated with a wet coating thickness of 20 ⁇ m, the IR-sensitive layer from a 1.0095% wt solution in methylethylketone/methoxypropanol 50/50 ratio. This layer was dried on a temperature of at least 120°C for at least 40 seconds.
  • the resulting IR-sensitive layer contained 115 mg/m 2 of carbon black, 32.2 mg/m 2 of EPI-REZ 5520 W-60 TM, 22.8 mg/m 2 of TB 3354H TM, 11.5 mg/m 2 of nitrocellulose, 2.1 mg/m 2 of SOLSPERSE 5000 TM, 11.3 mg/m 2 of SOLSPERSE 28000 TM, 2.0 mg/m 2 of TEGO WET 265 TM and 5.0 mg/m 2 of TEGO GLIDE 410 TM.
  • EPI-REZ 5520 W-60 is an urethane modified epoxy resin, commercially available at Shell Chemicals.
  • TB 3354H is an aminehardener for water soluble epoxies, commercially available at Witco GmbH.
  • lithographic base described in example 1 On the lithographic base described in 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 coated with a wet coating thickness of 20 ⁇ m, the IR-sensitive layer from a 1.0095% wt solution in methylethylketone/methoxypropanol 50/50 ratio. This layer was dried on a temperature of at least 120°C for at least 40 seconds.
  • the resulting IR-sensitive layer contained 115 mg/m 2 of carbon black, 6.5 mg/m 2 of EPI-REZ 3510 W-60 TM, 48.5 mg/m 2 of JEFFAMINE M3003 TM , 11.5 mg/m 2 of nitrocellulose, 2.1 mg/m 2 of SOLSPERSE 5000 TM, 11.3 mg/m 2 of SOLSPERSE 28000 TM, 2.0 mg/m 2 of TEGO WET 265 TM and 5.0 mg/m 2 of TEGO GLIDE 410 TM.
  • EPI-REZ 3510 W-60 is a waterborne dispersion of a liquid Bisphenol A epoxy resin, commercially available at Shell Chemicals.
  • JEFFAMINE M3003 is a monoamine with a propyleneoxide/ethyleneoxide ratio of 8/49 and molecular weight about 3000, commercially available at Huntsman Corporation, Houston.
  • lithographic base described in example 1 On the lithographic base described in 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 coated with a wet coating thickness of 20 ⁇ m, the IR-sensitive layer from a 1.0095% wt solution in methylethylketone/methoxypropanol 50/50 ratio. This layer was dried on a temperature of at least 120°C for at least 40 seconds.
  • the resulting IR-sensitive layer contained 115 mg/m 2 of carbon black, 37.2 mg/m 2 of EPI-REZ 3510 W-60 TM, 17.8 mg/m 2 of EPI-CURE 3140 TM, 11.5 mg/m 2 of nitrocellulose, 2.1 mg/m 2 of SOLSPERSE 5000 TM, 11.3 mg/m 2 of SOLSPERSE 28000 TM, 2.0 mg/m 2 of TEGO WET 265 TM and 5.0 mg/m 2 of TEGO GLIDE 410 TM.
  • EPI-REZ 3510 W-60 is a waterborne dispersion of a liquid Bisphenol A epoxy resin, commercially available at Shell Chemicals.
  • EPI-CURE 3140 is a low viscosity polyamide, also commercially available at Shell Chemicals.
  • lithographic base described in example 1 On the lithographic base described in 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 coated with a wet coating thickness of 20 ⁇ m, the IR-sensitive layer from a 1.0095% wt solution in methylethylketone/methoxypropanol 50/50 ratio. This layer was dried on a temperature of at least 120°C for at least 40 seconds.
  • the resulting IR-sensitive layer contained 115 mg/m 2 of carbon black, 52.4 mg/m 2 of EPI-REZ 3510 W-60 TM, 2.6 mg/m 2 of poly(ethyleneimine) substituted trimethoxysilyl propyl, 11.5 mg/m 2 of nitrocellulose, 2.1 mg/m 2 of SOLSPERSE 5000 TM , 11.3 mg/m 2 of SOLSPERSE 28000 TM, 2.0 mg/m 2 of TEGO WET 265 TM and 5.0 mg/m 2 of TEGO GLIDE 410 TM.
  • EPI-REZ 3510 W-60 is a waterborne dispersion of a liquid Bisphenol A epoxy resin, commercially available at Shell Chemicals. Poly(ethyleneimine) substituted trimethoxysilyl propyl is commercially available at ABCR.
  • lithographic base described in example 1 On the lithographic base described in 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 coated with a wet coating thickness of 20 ⁇ m, the IR-sensitive layer from a 1.0095% wt solution in methylethylketone/methoxypropanol 50/50 ratio. This layer was dried on a temperature of at least 120°C for at least 40 seconds.
  • the resulting IR-sensitive layer contained 115 mg/m 2 of carbon black, 31.4 mg/m 2 of EPI-REZ 3510 W-60 TM, 23.6 mg/m 2 of JEFFAMINE T403 TM, 11.5 mg/m 2 of nitrocellulose, 2.1 mg/m 2 of SOLSPERSE 5000 TM, 11.3 mg/m 2 of SOLSPERSE 28000TM, 2.0 mg/m 2 of TEGO WST 265 TM and 5.0 mg/m 2 of TEGO GLIDE 410 TM.
  • EPI-REZ 3510 W-60 is a waterborne dispersion of a liquid Bisphenol A epoxy resin, commercially available at Shell Chemicals.
  • JEFFAMINE T403 is a trifunctional propyleneoxide amine, commercially available at Witco GmbH.
  • lithographic base described in example 1 On the lithographic base described in 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 coated with a wet coating thickness of 20 ⁇ m, the IR-sensitive layer from a 1.2345% wt solution in methylethylketone/methoxypropanol 50/50 ratio. This layer was dried on a temperature of at least 120°C for at least 40 seconds.
  • the resulting IR-sensitive layer contained 115 mg/m 2 of carbon black, 95.2 mg/m 2 of EPI-REZ 3510 W-60 TM, 4.8 mg/m 2 of 2-methylimidazole, 11.5 mg/m 2 of nitrocellulose, 2.1 mg/m 2 of SOLSPERSE 5000 TM, 11.3 mg/m 2 of SOLSPERSE 28000 TM, 2.0 mg/m 2 of Tego Wet 265 TM and 5.0 mg/m 2 of TEGO GLIDE 410 TM.
  • EPI-REZ 3510 W-60 is a waterborne dispersion of a liquid Bisphenol A epoxy resin, commercially available at Shell Chemicals. For 2-methylimidazole, a 99% grade was used, commercially available at Aldrich Chemie.
  • lithographic base described in example 1 On the lithographic base described in 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 coated with a wet coating thickness of 20 ⁇ m, the IR-sensitive layer from a 1.0095% wt solution in methylethylketone/methoxypropanol 50/50 ratio. This layer was dried on a temperature of at least 120°C for at least 40 seconds.
  • the resulting IR-sensitive layer contained 115 mg/m 2 of carbon black, 22.9 mg/m 2 of EPI-REZ 3510 W-60 TM, 27.5 mg/m 2 of EUREDUR 115 TM, 4.6 mg/m 2 of 3-aminopropyltriethoxysilane, 11.5 mg/m 2 of nitrocellulose, 2.1 mg/m 2 of SOLSPERSE 5000 TM, 11.3 mg/m 2 of SOLSPERSE 28000 TM, 2.0 mg/m 2 of TEGO WET 265 TM and 5.0 mg/m 2 of TEGO GLIDE 410 TM.
  • EPI-REZ 3510 W-60 is a waterborne dispersion of a liquid Bisphenol A epoxy resin, commercially available at Shell Chemicals.
  • EUREDUR 115 is a polyamidoamino, commercially available at Witco GmbH.
  • lithographic base described in example 1 On the lithographic base described in 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 coated with a wet coating thickness of 20 ⁇ m, the IR-sensitive layer from a 1.0095% wt solution in methylethylketone/methoxypropanol 50/50 ratio. This layer was dried on a temperature of at least 120°C for at least 40 seconds.
  • the resulting IR-sensitive layer contained 115 mg/m 2 of carbon black, 36.2 mg/m 2 of EUREPOX 7001/75W TM, 9.4 mg/m 2 of EUREDUR 115 TM, 9.4 mg/m 2 of 3-(2-aminoethyl amino)-propyl-trimethoxysilane, 11.5 mg/m 2 of nitrocellulose, 2.1 mg/m 2 of SOLSPERSE 5000 TM, 11.3 mg/m 2 of SOLSPERSE 28000 TM, 2.0 mg/m 2 of TEGO WET 265 TM and 5.0 mg/m 2 of TEGO GLIDE 410 TM.
  • EUREPOX 7001/75W is a Bisphenol A - epoxy resin, commercially available by Witco GmbH.
  • EUREDUR 115 is a polyamidoamino, commercially available at Witco GmbH.
  • KBM-603 from Shin Etsu Chemicals Co, Ltd was used.
  • lithographic base described in example 1 On the lithographic base described in 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 coated with a wet coating thickness of 20 ⁇ m, the IR-sensitive layer from a 1.0095% wt solution in methylethylketone/methoxypropanol 50/50 ratio. This layer was dried on a temperature of at least 120°C for at least 40 seconds.
  • the resulting IR-sensitive layer contained 115 mg/m 2 of carbon black, 36.2 mg/m 2 of EUREPOX 7001/75W TM, 9.4 mg/m 2 of EUREDUR 115 TM, 9.4 mg/m 2 of DYNASILAN AMMO TM, 11.5 mg/m 2 of nitrocellulose, 2.1 mg/m 2 of SOLSPERSE 5000 TM, 11.3 mg/m 2 of SOLSPERSE 28000 TM, 2.0 mg/m 2 of Tego Wet 265 TM and 5.0 mg/m 2 of TEGO GLIDE 410 TM.
  • DYNASILAN AMMO 3-aminopropyl trimethoxyysilane to the dispersion before adding the epoxy resin or hardener.
  • EUREPOX 7001/75W is a Bisphenol A - epoxy resin, commercially available by Witco GmbH.
  • EUREDUR 115 is a polyamidoamino, commercially available at Witco GmbH.
  • DYNASILAN AMMO is a commercial product of Hills AG.
  • lithographic base described in example 1 On the lithographic base described in 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 coated with a wet coating thickness of 20 ⁇ m, the IR-sensitive layer from a 0.4220% wt solution in methylethylketone/methoxypropanol 50/50 ratio. This layer was dried on a temperature of at least 120°C for at least 40 seconds.
  • the resulting IR-sensitive layer contained 35 mg/m 2 of IR-absorber ST798 TM: 2-(2-(2-Chloro-3-(2-dihydro-1,1,3-trimethyl-2H-benzo(e)indole-2-ylidene)-ethylidene)-1-cyclohexen-1-yl)-ethenyl)-1,1,3-trimethyl-1H-benzo(e)indolium 4-methylbenzenesulfonate, 12.4 mg/m 2 of FLEXO-BLAU 630 TM, 13.8 mg/m 2 of EPI-REZ 3510 W-60 TM, 16.2 mg/m 2 of TB 3354H TM, 2.0 mg/m 2 of TEGO WET 265TM and 5.0 mg/m 2 of TEGO GLIDE 410 TM.
  • EPI-REZ 3510 W-60 is a waterborne dispersion of a liquid Bisphenol A epoxy resin, commercially available at Shell Chemicals.
  • TB 3354H is an aminehardener for water soluble epoxies, commercially available at Witco GmbH.
  • lithographic base described in example 1 On the lithographic base described in 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 coated with a wet coating thickness of 20 ⁇ m, the IR-sensitive layer from a 0.4220% wt solution in methylethylketone/methoxypropanol 50/50 ratio. This layer was dried on a temperature of at least 120°C for at least 40 seconds.
  • the resulting IR-sensitive layer contained 35 mg/m 2 of IR-absorber ST798 TM: 2-(2-(2-Chloro-3-(2-dihydro-1,1,3-trimethyl-2H-benzo(e)indole-2-ylidene)-ethylidene)-1-cyclohexen-1-yl)-ethenyl)-1,1,3-trimethyl-1H-benzo(e)indolium 4-methylbenzenesulfonate, 12.4 mg/m 2 of FLEXO-BLAU 630 TM, 22.7 mg/m 2 of EUREPOX 7001/75W TM, 3.6 mg/m 2 of EUREDUR 115 TM, 3.6 mg/m 2 of 3-aminopropyltriethoxysilane, 2.0 mg/m 2 of TEGO WET 265 TM and 5.0 mg/m 2 of TEGO GLIDE 410 TM.
  • EUREPOX 7001/75W is a Bisphenol A - epoxy resin, commercially available by Witco GmbH.
  • EUREDUR 115 is a polyamidoamino, commercially available at Witco GmbH. For the 3-aminopropyltriethoxysilane a 98% purity grade from Aldrich Chemie Steinheim was used.
  • the element After exposure of prepared 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 EP262A TM (OZASOL EP262A is commercially available from Agfa) and with water in the rinsing section and OZASOL RC795 TM gum in the gumming section.
  • OZASOL EP262A is commercially available from Agfa
  • the plates are printed on a Heidelberg GTO46 printing machine with a conventional ink (K+E) and fountain solution (Rotamatic).
  • K+E conventional ink
  • Rotamatic fountain solution
  • the 15 scratches are controlled on width of damage and given a corresponding quotation as indicated in table 1.
  • Quotation Width of scratch 0 no scratch visible 1 scratch smaller than 50 ⁇ m 2 width between 50 and 100 ⁇ m 3 width between 100 and 150 ⁇ m 4 width between 150 and 200 ⁇ m 5 width greater than 200 ⁇ m
  • a summation of all given quotations results in the scratch resistance of the material. The lower the value, the better the scratch resistance.
  • Print quality OK means: no visible scumming on non-image parts and good ink-uptake.

Landscapes

  • 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)
  • Printing Plates And Materials Therefor (AREA)

Claims (10)

  1. Ein wärmeempfindliches Bilderzeugungselement zur Herstellung einer lithografischen Druckplatte, wobei das Bilderzeugungselement auf einer lithografischen Unterlage mit einer hydrophilen Oberfläche eine erste Schicht mit einem in einer wäßrig-alkalischen Lösung löslichen Polymer und auf der gleichen Seite der lithografischen Unterlage wie die erste Schicht eine Deckschicht enthält, die empfindlich gegenüber Infrarotstrahlung und undurchdringbar für einen alkalischen Entwickler ist, wobei die erste Schicht und die Deckschicht ein und dieselbe Schicht sein können, dadurch gekennzeichnet, daß die Deckschicht zumindest eine Epoxideinheiten und einen Härter enthaltende Verbindung in einer Menge zwischen 20 und 500 mg/m2 enthält.
  2. Ein wärmeempfindliches Bilderzeugungselement nach Anspruch 1, dadurch gekennzeichnet, daß die Epoxideinheiten enthaltende Verbindung ein Kondensationsprodukt von Epichlorhydrin und Bisphenol A ist.
  3. Ein wärmeempfindliches Bilderzeugungselement nach Anspruch 1, dadurch gekennzeichnet, daß die Epoxideinheiten enthaltende Verbindung eine Verbindung aus der Gruppe bestehend aus epoxidierten o-Kresol-Novolak-Harzen und urethanmodifizierten Epoxyharzen ist.
  4. Ein wärmeempfindliches Bilderzeugungselement nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Deckschicht ein niederviskoses Amin als Härter enthält.
  5. Ein wärmeempfindliches Bilderzeugungselement nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Deckschicht als Härter eine Verbindung aus der Gruppe bestehend aus Polyaminoamiden und Polyamiden enthält.
  6. Ein wärmeempfindliches Bilderzeugungselement nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Deckschicht als Härter eine Verbindung aus der Gruppe bestehend aus Monoaminpolyoxyalkylenaminen, Diaminpolyoxyalkylenaminen und Triaminpolyoxyalkylenaminen enthält.
  7. Ein wärmeempfindliches Bilderzeugungselement nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Deckschicht ein mit Trimethylsilan modifiziertes Polyethylenimin als Härter enthält.
  8. Ein wärmeempfindliches Bilderzeugungselement nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Deckschicht 2-Methylimidazol als Härter enthält.
  9. Ein wärmeempfindliches Bilderzeugungselement nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß die Deckschicht ein Aminoalkyltrialkoxysilan als Kuppler enthält.
  10. Ein durch die nachstehenden Schritte gekennzeichnetes Verfahren zur Herstellung einer lithografischen Druckplatte :
    bildmäßige Belichtung mit Infrarotstrahlung eines wärmeempfindlichen Bilderzeugungselements nach einem der Ansprüche 1 bis 9 und
    Entwicklung des bildmäßig belichteten wärmeempfindlichen Bilderzeugungselements mit einem wäßrig-alkalischen Entwickler, wobei die belichteten Bereiche der ersten Schicht und der Deckschicht, die ein und dieselbe Schicht sein können, gelöst und die unbelichteten Bereiche der ersten Schicht nicht gelöst werden.
EP19980201800 1998-05-28 1998-05-28 Wärmeempfindliches Aufzeichnungsmaterial für die Herstellung von positiv arbeitenden Druckformen Expired - Lifetime EP0960728B1 (de)

Priority Applications (4)

Application Number Priority Date Filing Date Title
DE1998614820 DE69814820T2 (de) 1998-05-28 1998-05-28 Wärmeempfindliches Aufzeichnungsmaterial für die Herstellung von positiv arbeitenden Druckformen
EP19980201800 EP0960728B1 (de) 1998-05-28 1998-05-28 Wärmeempfindliches Aufzeichnungsmaterial für die Herstellung von positiv arbeitenden Druckformen
US09/280,659 US6152036A (en) 1998-05-28 1999-03-29 Heat mode sensitive imaging element for making positive working printing plates
JP14658899A JP2000056462A (ja) 1998-05-28 1999-05-26 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

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19980201800 EP0960728B1 (de) 1998-05-28 1998-05-28 Wärmeempfindliches Aufzeichnungsmaterial für die Herstellung von positiv arbeitenden Druckformen

Publications (2)

Publication Number Publication Date
EP0960728A1 EP0960728A1 (de) 1999-12-01
EP0960728B1 true EP0960728B1 (de) 2003-05-21

Family

ID=8233774

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19980201800 Expired - Lifetime EP0960728B1 (de) 1998-05-28 1998-05-28 Wärmeempfindliches Aufzeichnungsmaterial für die Herstellung von positiv arbeitenden Druckformen

Country Status (3)

Country Link
EP (1) EP0960728B1 (de)
JP (1) JP2000056462A (de)
DE (1) DE69814820T2 (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6893783B2 (en) 2003-10-08 2005-05-17 Kodak Polychrome Graphics Lld Multilayer imageable elements
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
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

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001260553A (ja) * 2000-03-21 2001-09-25 Fuji Photo Film Co Ltd 感熱性平版印刷用原板
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
US6555291B1 (en) * 2000-08-14 2003-04-29 Kodak Polychrome Graphics, Llc Thermal digital lithographic printing plate
US6846613B2 (en) * 2001-04-09 2005-01-25 Agfa-Gevaert Positive-working lithographic printing plate precursors
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
US6800426B2 (en) 2001-12-13 2004-10-05 Kodak Polychrome Graphics Llc Process for making a two layer thermal negative plate
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
US6858359B2 (en) 2002-10-04 2005-02-22 Kodak Polychrome Graphics, Llp Thermally sensitive, multilayer imageable element
US6803167B2 (en) 2002-12-04 2004-10-12 Kodak Polychrome Graphics, Llc Preparation of lithographic printing plates
US6844141B1 (en) 2003-07-23 2005-01-18 Kodak Polychrome Graphics Llc Method for developing multilayer imageable elements
US6992688B2 (en) 2004-01-28 2006-01-31 Eastman Kodak Company Method for developing multilayer imageable elements
BRPI0500293A (pt) * 2005-01-28 2006-09-12 Ibf Ind Brasileira De Filmes L chapas de impressão litográfica e processo para sua produção
US7160653B1 (en) 2005-10-25 2007-01-09 Eastman Kodak Company Multilayer imageable element containing epoxy resin
JP5068681B2 (ja) * 2008-02-27 2012-11-07 富士フイルム株式会社 平版印刷版原版

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
EP0819985B1 (de) * 1996-07-19 2002-06-05 Agfa-Gevaert Strahlungsempfindliches Bildaufzeichnungselement und Verfahren zur Herstellung von lithographischen Druckplatten mit diesem Element

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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

Also Published As

Publication number Publication date
DE69814820T2 (de) 2004-03-04
DE69814820D1 (de) 2003-06-26
EP0960728A1 (de) 1999-12-01
JP2000056462A (ja) 2000-02-25

Similar Documents

Publication Publication Date Title
EP0960728B1 (de) Wärmeempfindliches Aufzeichnungsmaterial für die Herstellung von positiv arbeitenden Druckformen
US6152036A (en) Heat mode sensitive imaging element for making positive working printing plates
EP0950517B1 (de) Wärmeempfindliches Aufzeichnungsmaterial zur Herstellung von positiv arbeitenden Druckplatten
EP0950518B1 (de) Wärmeempfindliches Aufzeichnungsmaterial zur Herstellung von positiv arbeitenden Druckplatten
EP1025992B1 (de) Verfahren zur Herstellung positiv arbeitender Druckplatten
US6083663A (en) Method for making positive working printing plates from a heat mode sensitive image element
US6153353A (en) Method for making positive working printing plates from a heat mode sensitive imaging element
EP0908307B1 (de) Verfahren zur Herstellung einer positiv arbeitenden Druckplatte aus einem Wärmeempfindlichen Bildaufzeichnungsmaterial
EP1023994B1 (de) Wärmeempfindliches Bildaufzeichnungsmaterial zur Herstellung von positiv arbeitenden Flachdruckformen
EP0908305B1 (de) Verfahren zur Herstellung einer positiv arbeitenden Druckplatte aus wärmeempflindlichem Bildaufzeichnungsmaterial
EP0908779B1 (de) Verfahren zur Herstellung positiv arbeitender Druckplatten aus einem wärmeempfindlichen Bildaufzeichnungselement
EP0943451B3 (de) Verfahren zur Herstellung einer positiv arbeitenden Druckplatte aus einem wärmeempfindlichem Bildaufzeichnungsmaterial
EP0997272B1 (de) Im Wärmeverfahren arbeitendes Aufzeichnungsmaterial zur Herstellung von positiv arbeitenden Druckplatten
US6340815B1 (en) Heat mode sensitive imaging element for making positive working printing plates
US6192799B1 (en) Heat mode sensitive imaging element for making positive working printing plates
US6472119B1 (en) Heat mode sensitive imaging element for making positive working printing plates
EP0950514B1 (de) Wärmeempfindliches Aufzeichnungsmaterial zur Herstellung von positiv arbeitenden Druckplatten
US6251563B1 (en) Method for making positive working printing plates from a heat mode sensitive image element
US6569594B2 (en) Heat mode sensitive imaging element for making positive working printing plates
US6458510B1 (en) Method for making positive working printing plates
EP0950513B1 (de) Wärmeempfindliches Aufzeichnungsmaterial zur Herstellung von positiv arbeitenden Druckplatten
US6489079B1 (en) Heat mode sensitive imaging element for making positive working printing plates
EP1025991B1 (de) Verfahren zur Herstellung positiv arbeitender Druckplatten
EP0950516B1 (de) Wärmeempfindliches Aufzeichnungsmaterial zur Herstellung von positiv arbeitenden Druckplatten
EP0914941B1 (de) Verfahren zur Herstellung einer positiv arbeitenden lithographischen Druckplatte unter Verwendung eines wärmeempfindlichen Materials

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE FR GB

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17P Request for examination filed

Effective date: 20000602

AKX Designation fees paid

Free format text: BE DE FR GB

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: AGFA-GEVAERT

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE DE FR GB

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20030521

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 69814820

Country of ref document: DE

Date of ref document: 20030626

Kind code of ref document: P

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20040224

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

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

Ref country code: FR

Payment date: 20090420

Year of fee payment: 12

Ref country code: DE

Payment date: 20090421

Year of fee payment: 12

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

Ref country code: GB

Payment date: 20090421

Year of fee payment: 12

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20100528

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20110131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20101201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100528