EP2197678B1 - Lithographiedruckplattenvorläufer - Google Patents

Lithographiedruckplattenvorläufer Download PDF

Info

Publication number
EP2197678B1
EP2197678B1 EP08832772.1A EP08832772A EP2197678B1 EP 2197678 B1 EP2197678 B1 EP 2197678B1 EP 08832772 A EP08832772 A EP 08832772A EP 2197678 B1 EP2197678 B1 EP 2197678B1
Authority
EP
European Patent Office
Prior art keywords
group
printing plate
coating
plate precursor
precursor according
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.)
Not-in-force
Application number
EP08832772.1A
Other languages
English (en)
French (fr)
Other versions
EP2197678A1 (de
Inventor
Hubertus Van Aert
Augustin Meisters
Stefaan Lingier
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 NV
Original Assignee
Agfa Graphics NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agfa Graphics NV filed Critical Agfa Graphics NV
Priority to EP08832772.1A priority Critical patent/EP2197678B1/de
Publication of EP2197678A1 publication Critical patent/EP2197678A1/de
Application granted granted Critical
Publication of EP2197678B1 publication Critical patent/EP2197678B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/02—Cover layers; Protective layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/04—Intermediate layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/14—Location, type or constituents of the non-imaging layers in lithographic printing formes characterised by macromolecular organic compounds, e.g. binder, adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/02—Positive working, i.e. the exposed (imaged) areas are removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/06—Developable by an alkaline solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/22—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
    • 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 lithographic printing plate precursor.
  • Lithographic printing presses use a so-called printing master such as a printing plate which is mounted on a cylinder of the printing press.
  • the master carries a lithographic image on its surface and a print is obtained by applying ink to said image and then transferring the ink from the master onto a receiver material, which is typically paper.
  • ink as well as an aqueous fountain solution (also called dampening liquid) are supplied to the lithographic image which consists of oleophilic (or hydrophobic, i.e. ink-accepting, water-repelling) areas as well as hydrophilic (or oleophobic, i.e. water-accepting, ink-repelling) areas.
  • driographic printing the lithographic image consists of ink-accepting and ink-abhesive (ink-repelling) areas and during driographic printing, only ink is supplied to the master.
  • Printing masters are generally obtained by the image-wise exposure and processing of an imaging material called plate precursor.
  • plate precursor an imaging material
  • heat-sensitive printing plate precursors have become very popular in the late 1990s.
  • thermal materials offer the advantage of daylight stability and are especially used in the so-called computer-to-plate method wherein the plate precursor is directly exposed, i.e. without the use of a film mask.
  • the material is exposed to heat or to infrared light and the generated heat triggers a (physico-) chemical process, such as ablation, polymerization, insolubilization by cross linking of a polymer, heat-induced solubilization or particle coagulation of a thermoplastic polymer latex.
  • a chemical process such as ablation, polymerization, insolubilization by cross linking of a polymer, heat-induced solubilization or particle coagulation of a thermoplastic polymer latex.
  • the most popular thermal plates form an image by a heat-induced solubility difference in an alkaline developer between exposed and non-exposed areas of the coating.
  • the coating typically comprises an oleophilic binder, e.g. a phenolic resin, of which the rate of dissolution in the developer is either reduced (negative working) or increased (positive working) by the image-wise exposure.
  • the solubility differential leads to the removal of the non-image (non-printing) areas of the coating, thereby revealing the hydrophilic support, while the image (printing) areas of the coating remain on the support.
  • Typical examples of such plates are described in e.g.
  • Negative working plate precursors which do not require a pre-heat step may contain an image-recording layer that works by heat-induced particle coalescence of a thermoplastic polymer particle (latex), as described in e.g. EP-As 770 494 , 770 495 , 770 496 and 770 497 .
  • EP-As 770 494 , 770 495 , 770 496 and 770 497 disclose a method for making a lithographic printing plate comprising the steps of (1) image-wise exposing an imaging element comprising hydrophobic thermoplastic polymer particles dispersed in a hydrophilic binder and a compound capable of converting light into heat, (2) and developing the image-wise exposed element by applying fountain and/or ink.
  • Some of these thermal processes enable plate making without wet processing and are for example based on ablation of one or more layers of the coating. At the exposed areas the surface of an underlying layer is revealed which has a different affinity towards ink or fountain than the surface of the unexposed coating.
  • thermal processes which enable platemaking without wet processing are for example processes based on a heat-induced hydrophilic/oleophilic conversion of one or more layers of the coating so that at exposed areas a different affinity towards ink or fountain is created than at the surface of the unexposed coating.
  • JP 2006/330670 discloses a printing plate precursor containing a coating including a spreading agent comprising a fluoroalkyl group.
  • Printing plate precursors are susceptible to damage caused by mechanical forces applied to the surface of the coating during transport, mechanical handling and/or manual handling. After coating and drying, the thermal printing plate precursors are cut, stacked and packed in boxes by means of specified packaging equipment. During transport of the packed printing plate precursors, the plates can move relatively to each other. The degree of this slipperiness can be determined by the static coefficient of friction as measured between two stacked precursors: a low static coefficient of friction between the surface of a printing plate precursor and the interleaf sheet on top of it, or between the surface of a printing plate precursor and the aluminum back side of the plate on top of it in case no interleaf sheets are used, results in slippery plates.
  • Slippery plates do not only cause unsafe situations during transport, but also lead to damage on the surface of the plate precursor, such as for example formation of the well-known "scuff marks". Scuff marks are unacceptable from an aesthetic point of view but moreover, these areas of the coating often do not sufficiently take up ink during printing and result in a poor, sometimes unacceptable, printing quality.
  • Printing plate precursors characterized by a surface having a high static coefficient of friction on the other hand will be much less slippery, but in general, the preparation - i.e. coatability - of such printing plate precursors is difficult under industrial coating- and drying conditions. As a result, a precursor with an uneven and non-uniform surface - also referred to in the art as a surface with bad coating cosmetics - is obtained. Thus, under industrial coating- and drying conditions it is very difficult to obtain a printing plate precursor with a surface characterized by excellent coating cosmetics and at the same time a high static coefficient of friction.
  • a heat-sensitive positive-working lithographic printing plate precursor which comprises on a support having a hydrophilic surface or which is provided with a hydrophilic layer, a heat- and/or light sensitive coating comprising a surfactant, characterized in that said surfactant comprises a polyether block including a pendant fluoroalkylgroup and a urethane linking group.
  • the surfactants used in the present invention in contrast to surfactants of the prior art, not only provide a good coatability to the coating - i.e. good coating cosmetics or a coating with an even and smooth surface - but at the same time provide a coating with a sufficiently high coefficient of friction.
  • the lithographic printing plate precursor of the present invention comprises a heat and/or light sensitive coating on a support.
  • the imaging mechanism of such printing plate precursors can be triggered by direct exposure to heat, e.g. by means of a thermal head, or by the light absorption of one or more compounds in the coating that are capable of converting light, more preferably infrared light, into heat.
  • the coating comprises a surfactant which comprises a polyether block including a pendant fluoroalkyl group and a urethane linking group.
  • the fluoroalkyl group may be straight or branched and includes a -(CF 2 )- and/or a -(CHF)- unit. The number of such units may be 1, i.e. -(CF 3 ), -(CHF 2 ) or -(CH 2 F); or more than 1, preferably less than 20; more preferably less than 15 and most preferably between 2 and 10.
  • the polyether block includes a pendant alkoxyfluoroalkyl group.
  • the alkoxyfluoroalkyl group includes a -[(CR a R b ) g -O-(CR c R d ) h -fluoroalkyl] -unit wherein R a , R b , R c and R d independently represent hydrogen, an alkyl or a fluoroalkyl group and g and h independently represent an integer ⁇ 0.
  • the urethane linking group present in the surfactant may be linked to the polyether block including a pendant fluoroalkyl group and/or alkoxyfluoroalkyl group; or may be linked to another polymeric block such as a polyether, polyester, polyurethane or polyvinyl alcohol block optionally present in the surfactant.
  • the surfactant used in the present invention preferably comprises the structural unit represented by the following formula (I): wherein a and b independently represent an integer ⁇ 0; c represents an integer ranging between 1 and 40, preferably an integer ranging between 2 and 20; Y 1 represents a fluoroalkyl group or an alkoxyfluoroalkyl group; Y 2 represents hydrogen; an optionally substituted alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl or pentyl group, a fluoroalkyl group or an alkoxyfluoroalkyl group; R 1 to R 4 independently represent hydrogen, fluoride, an optionally substituted alkyl group such as for example a methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl or pentyl group; a fluoroalkyl group or an optionally substituted aryl group.
  • the optional substituents on the alkyl or aryl group may be a halogen such as F, Cl, Br or I; an alkyl group or a fluoroalkyl group.
  • the fluoroalkyl group and the alkoxyfluoroalkyl group are defined above.
  • the surfactant comprises the structural unit represented by the formula (I) wherein:
  • the surfactant includes a polyether block including a pendant alkoxyfluoroalkyl group and a urethane linking group represented by the formula (II): wherein d and e represent an integer ⁇ 0; X represents a fluoroalkyl group; Y 3 represents hydrogen or an optionally substituted alkyl group such as a methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl or pentyl group; and f represents an integer ranging between 1 and 40, preferably an integer ranging between 2 and 20.
  • the optional substituents on the alkyl group may be a halogen such as F, Cl, Br or I; an alkyl group or a fluoroalkyl group.
  • the surfactant used in the present invention may further comprise one or more polyether blocks as represented by formula (III): wherein R 5 represents hydrogen; an optionally substituted alkyl or cycloalkyl group such as methyl, ethyl, propyl, isopropyl, cyclopentyl; an optionally substituted aryl, aralkyl or heteroalkyl group; and k represents an integer ranging between 1 and 40, preferably an integer ranging between 2 and 20.
  • the optional substituents on the alkyl or aryl group may be a halogen such as F, Cl, Br or I; an alkyl group or a fluoroalkyl group.
  • the structural units represented by the formula's (I) and/or (II) may be linked together and/or they may be linked, optionally via a linking group, to a polyether block represented by formula (III), a polyester, polyurethane or polyvinyl alcohol block forming diblock copolymers.
  • a polyether block represented by formula (III) a polyester, polyurethane or polyvinyl alcohol block forming diblock copolymers.
  • diblock copolymers By further linking diblock copolymers, multiblock copolymers may be formed.
  • Such diblock copolymers may for example be prepared by reacting a mono-hydroxyterminated polyether comprising a pendant fluoroalkyl or alkoxyfluoroalkyl group with one, two or more isocyanate functional groups of a mono-, di or multi-isocyanate compound, optionally followed by a reaction of the remaining isocyanate functional group(s) with a polyether optionally comprising a pendant fluoroalkyl or alkoxyfluoroalkyl group, a polyester, polyurethane or polyvinyl alcohol.
  • triblock or multiblock copolymers are obtained by reaction with mono-, di- and/or multi-isocyanate compounds.
  • These tri- or multiblock copolymers may comprise for example the following structural units: wherein independently in each of the structures above m, n, o, p and w independely represent an integer ranging between 1 and 40, preferably an integer ranging between 2 and 20.
  • Hydroxyterminated polyethers comprising a pendant fluoroalkyl or alkoxyfluoroalkyl group can be obtained by for example cationic ringopening polymerisation of a fluoroalkyl or an alkoxyfluoroalkyl substituted oxethane with an alcohol as initiator.
  • the alcohol initiator may be a monofunctional alcohol or a multifunctional alcohol such as a diol, a triol or a tetra-alcohol. They may have a low molecular weight (i.e. non polymeric) or may be polymeric alcohols such as condensation polymers e.g. mono- or dihydroxy terminated polyurethanes, polyesters or polyethers or addition polymers e.g. polyvinyl alcohol.
  • alohols are mono-functional, mono-hydroxyterminated fluoroalkyl and/or alkoxyfluoroalkyl polyethers are obtained; when the alohols are multifunctional, multi-hydroxyterminated fluoroalkyl and/or alkoxyfluoroalkyl polyethers are obtained such as for example bis-, tris- or tetra-hydroxyterminated (star branched) fluoroalkyl and/or alkoxyfluoroalkyl polyethers.
  • Suitable fluoroalkyl and alkoxyfluoroalkyl substituted oxethanes for the preparation of the surfactants include:
  • Suitable isocyanates for the preparation of the surfactants include monofunctional isocyanates such as phenyl isocyanate, stearyl isocyanate, 2-(methacryloxy)ethyl isocyanate, methyl isocyanate, isocyanatocyclohexane, ethyl isocyanate, 1-(isocyanatomethyl)benzene, 4-methoxyphenyl isocyanate, isopropyl isocyanate, m-anisyl isocyanate and 2-tolyl isocyanate; diisocyanates such as 1,6-hexylene diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, tolylene diisocyanate, 4,4'-diisocyanato-dicyclohexylmethane, 1,4-phenylene diisocyanate, tetramethylene isocyanate, dodecamethylene diisocyanate,
  • a specific di-isocyanate of interest is the following isophorone di-isocyanate:
  • the linking group which may link the structural units represented by the formula's (I), (II) and/or (III) and/or other polymeric blocks such as for example polyester, polyurethane or polyvinyl alcohol blocks, may have up to 20 carbon atoms and may contain at least one atom selected from C, H, N, O and S.
  • Preferred linking groups are a linear alkylene group having 1 to 18 carbon atoms, a linear, branched, or cyclic group having 3 to 18 carbon atoms, an alkynylene group having 2 to 18 carbon atoms and an arylene group having 6 to 20 atoms, -O-, -S-, -CO-, -CO-O-, -O-CO-, - CS-, -NR n R o -, -CO-NR n -, -NR n -CO-, -NR n -CO-O-, -O-CO-NR n -, - NR n -CO-NR o -, -NR n -CS-NR o -, a phenylene group, a naphtalene group, an anthracene group, a heterocyclic group, or combinations thereof, wherein R n and R o each independently represent hydrogen or an optionally substituted alkyl, alken
  • Suitable examples of diblock and multiblock surfactants include the following surfactants: wherein independently in each of the structures above m, n, o, p, r, s, t, x, y, u, q and v independely represent an integer ranging between 1 and 40, preferably an integer ranging between 2 and 20.
  • the amount of surfactant in the coating is preferably ranging between 0.05 %wt and 5 %wt, more preferably between 0.1 %wt and 3 %wt and most preferably between 0.15 %wt and 1.5 %wt.
  • the thermal printing plate precursor comprises a heat and/or light sensitive coating and is positive working. Its working mechanism is based on a heat-induced solubilization of an oleophilic resin.
  • the oleophilic resin is preferably a polymer that is soluble in an aqueous developer, more preferably an aqueous alkaline developing solution with a pH between 7.5 and 14.
  • Preferred polymers are phenolic resins e.g. novolac, resoles, polyvinyl phenols and carboxy substituted polymers. Typical examples of these polymers are described in DE 4007428 , DE 4027301 and DE 4445820 .
  • the amount of phenolic resin present in the coating is preferably at least 50% by weight, preferably at least 80% by weight relative to the total weight of all the components present in the coating.
  • the oleophilic resin is preferably a phenolic resin wherein the phenyl group or the hydroxy group is chemically modified with an organic substituent.
  • the phenolic resins which are chemically modified with an organic substituent may exhibit an increased chemical resistance against printing chemicals such as fountain solutions or plate treating liquids such as plate cleaners.
  • EP 934 822 examples include EP 1 072 432 ; US 5,641,608 ; EP 982 123 ; WO 99/01795 ; EP 2 102 446 , EP 2 102 444 ; EP 2 102 445 ; EP 2 102 443 ; EP 3 102 522 ; WO04/035310 ; WO04/035686 ; WO04/035645 ; WO04/035687 or EP 1 506 858 .
  • the novolac resin or resol resin may be prepared by polycondensation of at least one member selected from aromatic hydrocarbons such as phenol, o-cresol, p-cresol, m-cresol, 2,5-xylenol, 3,5-xylenol, resorcinol, pyrogallol, bisphenol, bisphenol A, trisphenol, o-ethylphenol, p-etylphenol, propylphenol, n-butylphenol, t-butylphenol, 1-naphtol and 2-naphtol, with at least one aldehyde or ketone selected from aldehydes such as formaldehyde, glyoxal, acetoaldehyde, propionaldehyde, benzaldehyde and furfural and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, in the presence of an acid catalyst.
  • the weight average molecular weight, measured by gel permeation chromatography using universal calibration and polystyrene standards, of the novolac resin is preferably from 500 to 150,000 g/mol, more preferably from 1,500 to 50,000 g/mol.
  • the poly(vinylphenol) resin may also be a polymer of one or more hydroxy-phenyl containing monomers such as hydroxystyrenes or hydroxy-phenyl (meth)acrylates.
  • hydroxystyrenes are o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2-(o-hydroxyphenyl)propylene, 2-(m-hydroxyphenyl)propylene and 2-(p-hydroxyphenyl)propylene.
  • Such a hydroxystyrene may have a substituent such as chlorine, bromine, iodine, fluorine or a C 1-4 alkyl group, on its aromatic ring.
  • An example of such hydroxy-phenyl (meth)acrylate is 2-hydroxy-phenyl methacrylate.
  • the poly(vinylphenol) resin may usually be prepared by polymerizing one or more hydroxy-phenyl containing monomer in the presence of a radical initiator or a cationic polymerization initiator.
  • the poly(vinylphenol) resin may also be prepared by copolymerizing one or more of these hydroxy-phenyl containing monomers with other monomeric compounds such as acrylate monomers, methacrylate monomers, acrylamide monomers, methacrylamide monomers, vinyl monomers, aromatic vinyl monomers or diene monomers.
  • the weight average molecular weight, measured by gel permeation chromatography using universal calibration and polystyrene standards, of the poly(vinylphenol) resin is preferably from 1,000 to 200,000 g/mol, more preferably from 1,500 to 50,000 g/mol.
  • phenolic resins examples are:
  • the coating may comprise a second layer that comprises a polymer or copolymer (i.e.(co)polymer) comprising at least one monomeric unit that comprises at least one sulfonamide group.
  • This layer is located between the layer described above comprising the oleophilic resin and the hydrophilic support.
  • a (co)polymer comprising at least one monomeric unit that comprises at least one sulfonamide group' is also referred to as "a sulphonamide (co)polymer”.
  • the sulphonamide (co)polymer is preferably alkali soluble.
  • the sulphonamide group is preferably represented by -NR-SO 2 -, -SO 2 -NR- or -SO 2 -NRR' wherein R and R' each independently represent hydrogen or an organic substituent.
  • the surfactant used in the present invention may be present in the first layer, the second layer or an optional other layer. Most preferably, the surfactant is present in the layer comprising the oleophilic resin.
  • Sulfonamide (co)polymers are preferably high molecular weight compounds prepared by homopolymerization of monomeric units containing at least one sulfonamide group or by copolymerization of such monomeric units and other polymerizable monomeric units.
  • Examples of monomeric units containing at least one sulfonamide group include monomeric units further containing at least one polymerizable unsaturated bond such as an acryloyl, allyl or vinyloxy group. Suitable examples are disclosed in U.S. 5,141,838 , EP 1 545 878 ; EP 909,657 , EP 0 894 622 and EP 1,120,246 .
  • Examples of monomeric units copolymerized with the monomeric units containing at least one sulfonamide group include monomeric units as disclosed in EP 1,262,318 , EP 1,275,498 , EP 909,657 , EP 1,120,246 , EP 0 894 622 and EP 1,400,351 .
  • EP-A 933 682 Suitable examples of sulfonamide (co)polymers and/or their method of preparation are disclosed in EP-A 933 682 , EP-A 982 123 , EP-A 1 072 432 , WO 99/63407 and EP 1,400,351 .
  • a highly preferred example of a sulfonamide (co)polymer is a homopolymer or copolymer comprising a structural unit represented by the following general formula (IV): wherein:
  • the structural unit represented by the general formula (IV) has preferably the following groups:
  • sulphonamide (co)polymers are polymers comprising N-(p-aminosulfonylphenyl) (meth)acrylamide, N-(m-aminosulfonylphenyl) (meth)acrylamide and/or N-(o-aminosulfonylphenyl) (meth)acrylamide.
  • a particularly preferred sulphonamide (co)polymer is a polymer comprising N-(p-aminosulphonylphenyl) methacrylamide wherein the sulphonamide group comprises an optionally substituted straight, branched, cyclic or heterocyclic alkyl group, an optionally substituted aryl group or an optionally substituted heteroaryl group.
  • the layer comprising the sulphonamide (co)polymer may further comprise additional hydrophobic binders such as a phenolic resin (e.g. novolac, resoles or polyvinyl phenols), a chemically modified phenolic resin or a polymer containing a carboxyl group, a nitrile group or a maleimide group.
  • additional hydrophobic binders such as a phenolic resin (e.g. novolac, resoles or polyvinyl phenols), a chemically modified phenolic resin or a polymer containing a carboxyl group, a nitrile group or a maleimide group.
  • the dissolution behavior of the coating can be fine-tuned by optional solubility regulating components. More particularly, development accelerators and development inhibitors can be used. In the embodiment where the coating comprises more than one layer, these ingredients can be added to the first layer, to the second layer and/or to an optional other layer of the coating.
  • Development accelerators are compounds which act as dissolution promoters because they are capable of increasing the dissolution rate of the coating.
  • cyclic acid anhydrides, phenols or organic acids can be used in order to improve the aqueous developability.
  • the cyclic acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endoxy-4-tetrahydro-phthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, alpha -phenylmaleic anhydride, succinic anhydride, and pyromellitic anhydride, as described in U.S. Patent No.
  • Examples of the phenols include bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxy-benzophenone, 4-hydroxybenzophenone, 4,4',4"-trihydroxy-triphenylmethane, and 4,4',3",4"-tetrahydroxy-3,5,3',5'-tetramethyltriphenyl-methane, and the like.
  • Examples of the organic acids include sulphonic acids, sulfinic acids, alkylsulfuric acids, phosphonic acids, phosphates, and carboxylic acids, as described in, for example, JP-A Nos. 60-88,942 and 2-96,755 .
  • organic acids include p-toluenesulphonic acid, dodecylbenzenesulphonic acid, p-toluenesulfinic acid, ethylsulfuric acid, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, 3,4,5-trimethoxybenzoic acid, 3,4,5-trimethoxycinnamic acid, phthalic acid, terephthalic acid, 4-cyclohexene-1,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, and ascorbic acid.
  • the amount of the cyclic acid anhydride, phenol, or organic acid contained in the coating is preferably in the range of 0.05 to 20% by weight, relative to the coating as a whole.
  • Polymeric development accelerators such as phenolic-formaldehyde resins comprising at least 70 mol% meta-cresol as recurring monomeric units are also suitable development accelerators.
  • the coating also contains developer resistance means, also called development inhibitors, i.e. one or more ingredients which are capable of delaying the dissolution of the unexposed areas during processing.
  • developer resistance means also called development inhibitors
  • the dissolution inhibiting effect is preferably reversed by heating, so that the dissolution of the exposed areas is not substantially delayed and a large dissolution differential between exposed and unexposed areas can thereby be obtained.
  • the compounds described in e.g. EP-A 823 327 and WO97/3989 are believed to act as dissolution inhibitors due to interaction, e.g. by hydrogen bridge formation, with the alkali-soluble resin(s) in the coating.
  • Inhibitors of this type typically comprise at least one hydrogen bridge forming group such as nitrogen atoms, onium groups, carbonyl (-CO-), sulfinyl (-SO-) or sulfonyl (-SO 2 -) groups and a large hydrophobic moiety such as one or more aromatic rings.
  • hydrogen bridge forming group such as nitrogen atoms, onium groups, carbonyl (-CO-), sulfinyl (-SO-) or sulfonyl (-SO 2 -) groups and a large hydrophobic moiety such as one or more aromatic rings.
  • Suitable inhibitors improve the developer resistance because they delay the penetration of the aqueous alkaline developer into the coating.
  • Such compounds can be present in the first layer and/or, if present, in the second layer as described in e.g. EP-A 950 518 , and/or in a development barrier layer on top of said layer, as described in e.g. EP-A 864 420 , EP-A 950 517 , WO 99/21725 and WO 01/45958 .
  • the solubility of the barrier layer in the developer or the penetrability of the barrier layer by the developer can be increased by exposure to heat or infrared light.
  • inhibitors which delay the penetration of the aqueous alkaline developer into the coating include the following:
  • the above mentioned inhibitor of type (b) and (c) tends to position itself, due to its bifunctional structure, at the interface between the coating and air and thereby forms a separate top layer even when applied as an ingredient of the coating solution of the first and/or of the optional second layer.
  • the surfactants also act as a spreading agent which improves the coating quality.
  • the separate top layer thus formed seems to be capable of acting as the above mentioned barrier layer which delays the penetration of the developer into the coating.
  • the inhibitor of type (a) to (c) can be applied in a separate solution, coated on top of the first, optional second and/or other layers of the coating.
  • a solvent in the separate solution that is not capable of dissolving the ingredients present in the other layers so that a highly concentrated water-repellent or hydrophobic phase is obtained at the top of the coating which is capable of acting as the above mentioned development barrier layer.
  • first or optional second layer and/or other layer may comprise polymers that further improve the run length and/or the chemical resistance of the plate.
  • examples thereof are polymers comprising imido (-CO-NR-CO-) pendant groups, wherein R is hydrogen, optionally substituted alkyl or optionally substituted aryl, such as the polymers described in EP-A 894 622 , EP-A 901 902 , EP-A 933 682 and WO 99/63407 .
  • the coating of the heat-sensitive printing plate precursor preferably also contains an infrared light absorbing dye or pigment which, in the embodiment where the coating comprises more than one layer, may be present in the first layer, and/or in the second layer, and/or in an optional other layer.
  • Preferred IR absorbing dyes are cyanine dyes, merocyanine dyes, indoaniline dyes, oxonol dyes, pyrilium dyes and squarilium dyes. Examples of suitable IR dyes are described in e.g. EP-As 823327 , 978376 , 1029667 , 1053868 , 1093934 ; WO 97/39894 and 00/29214 .
  • a preferred compound is the following cyanine dye:
  • the concentration of the IR-dye in the coating is preferably between 0.25 and 15.0 %wt, more preferably between 0.5 and 10.0 %wt, most preferably between 1.0 and 7.5 %wt relative to the coating as a whole.
  • the coating may further comprise one or more colorant(s) such as dyes or pigments which provide a visible color to the coating and which remain in the coating at the image areas which are not removed during the processing step. Thereby a visible image is formed and examination of the lithographic image on the developed printing plate becomes feasible.
  • dyes are often called contrast dyes or indicator dyes.
  • the dye has a blue color and an absorption maximum in the wavelength range between 600 nm and 750 nm.
  • Typical examples of such contrast dyes are the amino-substituted tri- or diarylmethane dyes, e.g. crystal violet, methyl violet, victoria pure blue, flexoblau 630, basonylblau 640, auramine and malachite green.
  • dyes which are discussed in depth in EP 400 706 are suitable contrast dyes. Dyes which, combined with specific additives, only slightly color the coating but which become intensively colored after exposure, as described in for example WO2006/005688 may also be used as colorants.
  • the protective layer generally comprises at least one water-soluble binder, such as polyvinyl alcohol, polyvinylpyrrolidone, partially hydrolyzed polyvinyl acetates, gelatin, carbohydrates or hydroxyethylcellulose, and can be produced in any known manner such as from an aqueous solution or dispersion which may, if required, contain small amounts - i.e. less than 5% by weight based on the total weight of the coating solvents for the protective layer - of organic solvents.
  • the thickness of the protective layer can suitably be any amount, advantageously up to 5.0 ⁇ m, preferably from 0.1 to 3.0 ⁇ m, particularly preferably from 0.15 to 1.0 ⁇ m.
  • the coating may further contain additional ingredients such as further surfactants, silicon or titanium dioxide particles or polymers particles such as matting agents and spacers.
  • any coating method can be used for applying two or more coating solutions to the hydrophilic surface of the support.
  • the multi-layer coating can be applied by coating/drying each layer consecutively or by the simultaneous coating of several coating solutions at once.
  • the volatile solvents are removed from the coating until the coating is self-supporting and dry to the touch.
  • the residual solvent content may be regarded as an additional composition variable by means of which the composition may be optimized. Drying is typically carried out by blowing hot air onto the coating, typically at a temperature of at least 70°C, suitably 80-150°C and especially 90-140°C. Also infrared lamps can be used.
  • the drying time may typically be 15-600 seconds.
  • a heat treatment and subsequent cooling may provide additional benefits, as described in WO99/21715 , EP-A 1074386 , EP-A 1074889 , WO00/29214 , and WO/04030923 , WO/04030924 , WO/04030925 .
  • the support of the lithographic printing plate precursor may be a sheet-like material such as a plate or it may be a cylindrical element such as a sleeve which can be slid around a print cylinder of a printing press.
  • the lithographic support is a grained and anodized aluminum support.
  • the aluminum support has usually a thickness of about 0.1-0.6 mm. However, this thickness can be changed appropriately depending on the size of the printing plate used and/or the size of the plate-setters on which the printing plate precursors are exposed.
  • the aluminum is preferably grained by electrochemical graining, and anodized by means of anodizing techniques employing phosphoric acid or a sulphuric acid/phosphoric acid mixture. Methods of both graining and anodization of aluminum are very well known in the art.
  • the surface roughness is often expressed as arithmetical mean center-line roughness Ra (ISO 4287/1 or DIN 4762) and may vary between 0.05 and 1.5 ⁇ m.
  • the aluminum substrate of the current invention has preferably an Ra value below 0.45 ⁇ m, more preferably below 0.40 ⁇ m and most preferably below 0.30 ⁇ m.
  • the lower limit of the Ra value is preferably about 0.1 ⁇ m. More details concerning the preferred Ra values of the surface of the grained and anodized aluminum support are described in EP 1 356 926.
  • the anodic weight (g/m 2 Al 2 O 3 formed on the aluminum surface) varies between 1 and 4 g/m 2 , preferably between 1 and 3,5 g/m 2 .
  • the anodic weight is preferably ⁇ 3 g/m 2 , more preferably ⁇ 3.5 g/m 2 .
  • the grained and anodized aluminum support may be subject to a so-called post-anodic treatment to improve the hydrophilic properties of its surface.
  • the aluminum support may be silicated by treating its surface with a 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.
  • Another useful post-anodic treatment may be carried out with a solution of polyacrylic acid or a polymer comprising at least 30 mol% of acrylic acid monomeric units, e.g. GLASCOL E15, a polyacrylic acid, commercially available from Ciba Speciality Chemicals.
  • the support can also be a flexible support, which may be provided with a hydrophilic layer, hereinafter called 'base layer'.
  • the flexible support is e.g. paper, plastic film or aluminum.
  • Preferred examples of plastic film are polyethylene terephthalate film, polyethylene naphthalate film, cellulose acetate film, polystyrene film, polycarbonate film, etc.
  • the plastic film support may be opaque or transparent.
  • the base layer is preferably a cross-linked hydrophilic layer obtained from a hydrophilic binder cross-linked with a hardening agent such as formaldehyde, glyoxal, polyisocyanate or a hydrolyzed tetra-alkylorthosilicate.
  • a hardening agent such as formaldehyde, glyoxal, polyisocyanate or a hydrolyzed tetra-alkylorthosilicate.
  • the thickness of the hydrophilic base layer may vary in the range of 0.2 to 25 ⁇ m and is preferably 1 to 10 ⁇ m. More details of preferred embodiments of the base layer can be found in e.g. EP-A 1 025 992 .
  • the heat-sensitive plate precursor can be image-wise exposed directly with heat, e.g. by means of a thermal head, or indirectly by infrared light, preferably near infrared light.
  • the infrared light is preferably converted into heat by an IR light absorbing compound as discussed above.
  • the heat-sensitive lithographic printing plate precursor is preferably not sensitive to visible light, i.e. no substantial effect on the dissolution rate of the coating in the developer is induced by exposure to visible light. Most preferably, the coating is not sensitive to ambient daylight.
  • the printing plate precursor can be exposed to infrared light by means of e.g. LEDs or a laser.
  • the light used for the exposure is a laser emitting near infrared light having a wavelength in the range from about 750 to about 1500 nm, more preferably 750 to 1100 nm, such as a semiconductor laser diode, a Nd:YAG or a Nd:YLF laser.
  • the required laser power depends on the sensitivity of the plate precursor, the pixel dwell time of the laser beam, which is determined by the spot diameter (typical value of modern plate-setters at 1/e 2 of maximum intensity: 5-25 ⁇ m), the scan speed and the resolution of the exposure apparatus (i.e. the number of addressable pixels per unit of linear distance, often expressed in dots per inch or dpi; typical value: 1000-4000 dpi).
  • ITD plate-setters for thermal plates are typically characterized by a very high scan speed up to 500 m/sec and may require a laser power of several Watts.
  • An XTD platesetter equipped with one or more laserdiodes emitting in the wavelength range between 750 and 850 nm is an especially preferred embodiment for the method of the present invention.
  • the known plate-setters can be used as an off-press exposure apparatus, which offers the benefit of reduced press down-time.
  • XTD plate-setter configurations can also be used for on-press exposure, offering the benefit of immediate registration in a multi-color press. More technical details of on-press exposure apparatuses are described in e.g. US 5,174,205 and US 5,163,368 .
  • the precursor is preferably developed by means of immersing the precursor in a developing solution; this may be combined with mechanical rubbing, e.g. by using a rotating brush.
  • a developing solution e.g. a developer solution
  • the developer solution preferably has a pH above 10, more preferably above 12.
  • any water-soluble layer present is preferably also removed.
  • the development step is preferably carried out at temperatures ranging between 20 and 40°C in automated processing units as customary in the art.
  • EP 1614538 More details concerning the development step can be found in for example EP 1614538 , EP 1614539 , EP 1614540 and WO/2004071767 .
  • the developing solution preferably contains a buffer such as for example a silicate-based buffer or a phosphate buffer.
  • concentration of the buffer in the developer preferably ranges bewteen 3 to 14%wt.
  • Silicate-based developers which have a ratio of silicon dioxide to alkali metal oxide of at least 1 are advantageous because they ensure that the alumina layer (if present) of the substrate is not damaged.
  • Preferred alkali metal oxides include Na 2 O and K 2 O, and mixtures thereof.
  • a particularly preferred silicate-based developer solution is a developer solution comprising sodium or potassium metasilicate, i.e. a silicate where the ratio of silicon dioxide to alkali metal oxide is 1.
  • the developing solution may optionally contain further components as known in the art: other buffer substances, chelating agents, surfactants, complexes, inorganic salts, inorganic alkaline agents, organic alkaline agents, antifoaming agents, organic solvents in small amounts i.e. preferably less than 10%wt and more preferably less than 5%wt, nonreducing sugars, glycosides, dyes and/or hydrotropic agents. These components may be used alone or in combination.
  • replenishing solution hereinafter also referred to as replenisher
  • More than one replenishing solution containing different ingredients and/or different amounts of the ingredients may be added to the developing solution.
  • Alkali metal silicate solutions having alkali metal contents of from 0.6 to 2.0 mol/l can suitably be used. These solutions may have the same silica/alkali metal oxide ratio as the developer (generally, however, it is lower) and likewise optionally contain further additives.
  • the (co)polymer of the present invention is present in the replenisher(s); preferably at a concentration of at least 0.5 g/l, more preferably in a concentration ranging between 1 and 50 g/l most preferably between 2 and 30 g/l.
  • the replenishing solution has preferably a pH value of at least 10, more preferably of at least 11, most preferably of at least 12.
  • the development step may be followed by a rinsing step, a gumming step, a drying step and/or a post-baking step.
  • the heat-sensitive printing plates can be used for conventional, so-called wet offset printing, in which ink and an aqueous dampening liquid are supplied to the plate.
  • Another suitable printing method uses so-called single-fluid ink without a dampening liquid.
  • Suitable single-fluid inks have been described in US 4,045,232 ; US 4,981,517 and US 6,140,392 .
  • the single-fluid ink comprises an ink phase, also called the hydrophobic or oleophilic phase, and a polyol phase as described in WO 00/32705 .
  • the printing plate precursor of the present invention can also be used for treating thermo-resists, for example on a PCB (printed circuit board) application as described in US 2003/0003406 A1 .
  • a 0.30 mm thick aluminum foil was degreased by immersing the foil in an aqueous solution containing 34 g/l of sodium hydroxide at 70°C for 6 seconds and rinsed with demineralized water for 3.6 seconds.
  • the foil was then electrochemically grained during 8 seconds using an alternating current in an aqueous solution containing 15 g/l HCl, 15 g/l SO 4 2- ions and 5 g/l Al 3+ at a temperature of 37°C and a current density of 100 A/dm 2 .
  • the aluminum foil was then desmutted by etching with an aqueous solution containing 145 g/l of sulfuric acid at 80°C for 5 seconds and rinsed with demineralized water for 4 seconds.
  • the foil was subsequently subjected to anodic oxidation during 10 seconds in an aqueous solution containing 145 g/l of sulfuric acid at a temperature of 57°C and a current density of 25 A/dm 2 , then washed with demineralized water for 7 seconds and post-treated for 4 seconds with a solution containing 2.2 g/l of polyvinylphosphonic acid at 70°C, rinsed with demineralized water for 3.5 seconds and dried at 120°C for 7 seconds.
  • the support thus obtained was characterized by a surface roughness Ra of 0.35-0.40 ⁇ m (measured with interferometer NT1100) and an anodic weight of 3.0 g/m 2 .
  • a first layer was coated on an aluminum substrate (described above) with the first coating solution with the composition as defined in Table 1 at a wet coating thickness of 20 ⁇ m.
  • Table 1 composition of the first coating solution.
  • Composition first coating solution g Dowanol PM (1) 270.98 THF (2) 576.55 Binder-01(25 wt%) (3) 53.75 Crystal Violet (1 wt%) (4) 58.24 Tegoglide 410 (1 wt%) (5) 5.82 (1) Propyleneglycol-monomethylether (1-methoxy-2-propanol) commercially available from Dow Chemical Company; (2) THF is tetrahydrofuran; (3) Binder-01: preparation see 2.2; (4) 1 wt% solution of Crystal Violet in Dowanol PM, Crystal Violet is commercially available from Ciba-Geigy GmbH; (5) 1 wt% solution of Tegoglide 410 in Dowanol PM; Tegoglide 410 is a copolymer of polysiloxane and poly(
  • the total dry coating weight amounts to 0.671 g/m 2 .
  • the dry weight of the ingredients in the first coating is shown in Table 2.
  • Table 2 Dry coating weight of first coating. Dry Weight first Coating* mg/m 2 Binder-01 660 Crystal Violet 10 Tegoglide 410 1 * ingredients as defined in Table 1.
  • a second coating solution with the composition as defined in Table 3 (coating solutions 1 to 16) was coated at a wet coating thickness of 16 ⁇ m resulting in the printing plate precursors PPP-01 to PPP-16.
  • the total dry coating weight of the second coatings and their respective ingredients are given in Table 4.
  • Table 4 dry coating weight of the second coating. Dry Weight second Coating * mg/m 2 Alnovol SPN402 653.0 TMCA 56.0 Adagio 25.0 Crystal Violet 10.0 Perfluoro surfactant 5.0 or 10.0 Total: 749 or 754 *:the dry coating weight of the second coating of PPP-01 amounted to only 744 mg/m 2 ; the ingredients of the coating are defined in Table 3.
  • the printing plate precursors PPP-01 to PPP-16 were imaged on a Creo TrendSetter with a 40 W imaging head (commercially available from Kodak) at 140 rpm and 2400 dpi and then developed in an Agfa Autolith TP105 processor (commercially available form Agfa Graphics NV) with Agfa Energy Elite developer (commercially available from Agfa Graphics NV) in the developer section (temperature 23°C, dwell time 25 sec.) and tap water (room temperature) in the finisher section.
  • an Agfa Autolith TP105 processor commercially available form Agfa Graphics NV
  • Agfa Energy Elite developer commercially available from Agfa Graphics NV
  • the static coefficient of friction of the surface of the precursors was measured. A value of at least 0.45 is required in order to prevent the occurrence of plates shifting over each other during transport, giving rise to "scuff mark" defects.
  • the static coefficient of friction was measured in line with standard ASTM D 1894.
  • the following experimental set-up was used: wherein a: gauge which measures the frictional force between d and g; b: pulley; c: nylon thread; d: part of a typical interleaf paper (Pleiderer Pergo-Tec 37 g/m 2 ); e: stainless steel block; f: support; g: the printing plate precursor with the photosensitive layer facing upwards.
  • the static coefficient of friction is defined as the maximum power (N) in order to move the stainless steel block e, divided by the weight of the stainless steel block.
  • step 1 Drying conditions used in step 1: wherein a is a hair dryer (WIGO Taifun 110ch, power 1000W, commercially available from WIGO) used at the maximum available air blowing capacity setting 2.
  • b is the printing plate precursor.
  • a value of at least 4 of the cosmetics or coatability of the surface is required in order to be able to coat the layer with sufficient latitude under industrial conditions.
  • the right exposure (RE) sensitivity is the energy density value (in mJ/cm 2 ) where the 1x1 checkerboard pattern on the plate after processing reads 52% (Gretag-MacBeth D19C densitometer, automatic colour filter setting).
  • inventive printing plate precursors comprising the surfactants PolyFox PF-652 and PolyFox PF-651, PPP-13 to PPP-16, allow for a good coatability - i.e. a coating cosmetics level of at least 4 - AND at the same time a sufficiently high static coefficient of friction - i.e. a static coefficient of friction of at least 0.45.
  • PolyFox PF-652 has the additional feature that it shows a very consistent behaviour over the concentration range used.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Photolithography (AREA)

Claims (13)

  1. Wärmeempfindliche positivarbeitende lithografische Druckplattenvorstufe, die auf einem aufgerauten und anodisierten Aluminiumträger mit einer hydrophilen Oberfläche oder einem mit einer hydrophilen Schicht versehenen aufgerauten und anodisierten Aluminiumträger mit einem Gewicht der Aluminiumoxidschicht zwischen 1 und 4 g/m2 eine wärmeempfindliche und/oder lichtempfindliche, ein Tensid enthaltende Beschichtung umfasst, dadurch gekennzeichnet, dass das Tensid einen Polyetherblock mit einer Fluoralkylseitengruppe und einer Urethanverbindungsgruppe umfasst.
  2. Druckplattenvorstufe nach Anspruch 1, dadurch gekennzeichnet, dass das Gewicht der Aluminiumoxidschicht zwischen 1 und 3,5 g/m2 liegt.
  3. Druckplattenvorstufe nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Fluoralkylgruppe eine Alkoxyfluoralkylgruppe ist.
  4. Druckplattenvorstufe nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das Tensid folgende Struktureinheit enthält :
    Figure imgb0073
     in der :
    a und b unabhängig voneinander eine ganze Zahl ≥ 0 bedeuten, c eine ganze Zahl zwischen 1 und 40 bedeutet,
    Y1 eine Fluoralkylgruppe oder eine Alkoxyfluoralkylgruppe bedeutet,
    Y2 ein Wasserstoffatom, eine gegebenenfalls substituierte Alkylgruppe, eine Fluoralkylgruppe oder eine Alkoxyfluoralkylgruppe bedeutet, und
    R1 bis R4 unabhängig voneinander ein Wasserstoffatom, Fluorid, eine Fluoralkylgruppe, eine gegebenenfalls substituierte Alkylgruppe oder eine gegebenenfalls substituierte Arylgruppe bedeuten.
  5. Druckplattenvorstufe nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das Tensid folgende Struktureinheit enthält :
    Figure imgb0074
     in der :
    d und e eine ganze Zahl ≥ 0 bedeuten,
    X eine Fluoralkylgruppe bedeutet,
    Y3 ein Wasserstoffatom oder eine gegebenenfalls substituierte Alkylgruppe bedeutet, und
    f eine ganze Zahl zwischen 1 und 40 bedeutet.
  6. Druckplattenvorstufe nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das Tensid folgende Struktureinheit enthält :
    Figure imgb0075
     in der :
    R5 ein Wasserstoffatom, eine gegebenenfalls substituierte Alkylgruppe oder eine gegebenenfalls substituierte Arylgruppe,
    Aralkylgruppe oder Heteroalkylgruppe bedeutet,
    und k eine ganze Zahl zwischen 1 und 40 bedeutet.
  7. Druckplattenvorstufe nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das Tensid folgende Struktureinheit enthält :
    Figure imgb0076
     und/oder
    Figure imgb0077
     in denen m, n, o und p in jeder der Verbindungen unabhängig voneinander eine ganze Zahl zwischen 1 und 40 bedeuten.
  8. Druckplattenvorstufe nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das Tensid eine der folgenden Verbindungen ist :
    Figure imgb0078
    Figure imgb0079
    Figure imgb0080
    Figure imgb0081
    Figure imgb0082
    Figure imgb0083
     in denen m, n, o, p, x, y, q und v in jeder der Verbindungen unabhängig voneinander eine ganze Zahl zwischen 1 und 40 bedeuten.
  9. Druckplattenvorstufe nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das Tensid in einer Menge zwischen 0,1 Gew.-% und 3 Gew.-% in der Plattenbeschichtung enthalten ist.
  10. Druckplattenvorstufe nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die Plattenbeschichtung aus mindestens zwei Schichten aufgebaut ist :
    - einer ersten Schicht, die ein oleophiles Harz enthält, und
    - einer zweiten Schicht, die ein Sulfonamidbindemittel enthält und zwischen dem Träger und der das oleophile Harz enthaltenden Schicht eingebettet wird,
    und dadurch gekennzeichnet, dass das Tensid in der das oleophile Harz enthaltenden Schicht enthalten ist.
  11. Druckplattenvorstufe nach Anspruch 10, dadurch gekennzeichnet, dass das Sulfonamidbindemittel folgender Formel entspricht :
    Figure imgb0084
     in der :
    R9 ein Wasserstoffatom oder eine Kohlenwasserstoffgruppe mit bis 12 Kohlenstoffatomen bedeutet,
    X1 eine Einfachbindung oder eine divalente Verbindungsgruppe bedeutet,
    Y4 eine bivalente Sulfonamidgruppe bedeutet und
    Z1 eine Endgruppe bedeutet.
  12. Verfahren zur Herstellung einer lithografischen Druckplattenvorstufe nach einem der vorstehenden Ansprüche, wobei das Verfahren folgende Schritte umfasst :
    - Auftrag einer wie in einem der vorstehenden Ansprüche definierten Beschichtung und
    - Trocknung der Vorstufe.
  13. Verfahren zur Herstellung einer lithografischen Druckplatte, wobei das Verfahren folgende Schritte umfasst :
    - Bereitstellen einer Druckplattenvorstufe nach einem der vorstehenden Ansprüche,
    - Erwärmen und/oder Infrarotbestrahlung der Vorstufe und
    - Entwicklung der erwärmten und/oder bestrahlten Vorstufe mit einer wässrig-alkalischen Lösung.
EP08832772.1A 2007-10-09 2008-09-23 Lithographiedruckplattenvorläufer Not-in-force EP2197678B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08832772.1A EP2197678B1 (de) 2007-10-09 2008-09-23 Lithographiedruckplattenvorläufer

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US97849307P 2007-10-09 2007-10-09
EP20070118085 EP2047988B1 (de) 2007-10-09 2007-10-09 Lithographiedruckplattenvorläufer
PCT/EP2008/062663 WO2009047112A1 (en) 2007-10-09 2008-09-23 A lithographic printing plate precursor
EP08832772.1A EP2197678B1 (de) 2007-10-09 2008-09-23 Lithographiedruckplattenvorläufer

Publications (2)

Publication Number Publication Date
EP2197678A1 EP2197678A1 (de) 2010-06-23
EP2197678B1 true EP2197678B1 (de) 2013-11-06

Family

ID=39146935

Family Applications (2)

Application Number Title Priority Date Filing Date
EP20070118085 Not-in-force EP2047988B1 (de) 2007-10-09 2007-10-09 Lithographiedruckplattenvorläufer
EP08832772.1A Not-in-force EP2197678B1 (de) 2007-10-09 2008-09-23 Lithographiedruckplattenvorläufer

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP20070118085 Not-in-force EP2047988B1 (de) 2007-10-09 2007-10-09 Lithographiedruckplattenvorläufer

Country Status (4)

Country Link
EP (2) EP2047988B1 (de)
CN (1) CN101821097B (de)
ES (1) ES2436000T3 (de)
WO (1) WO2009047112A1 (de)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2941349B1 (de) 2013-01-01 2017-07-19 AGFA Graphics NV (ethylen-,vinylacetal-)copolymere und ihre verwendung in lithographiedruckplattenvorläufern
EP2933278B1 (de) 2014-04-17 2018-08-22 Agfa Nv (Ethylen-,Vinylacetal-)Copolymere und ihre Verwendung in Lithographiedruckplattenvorläufern
ES2617557T3 (es) 2014-05-15 2017-06-19 Agfa Graphics Nv Copolímeros (de etileno, vinilacetal) y su uso en precursores de plancha de impresión litográfica
EP2955198B8 (de) 2014-06-13 2018-01-03 Agfa Nv Ethylenvinylacetal-Copolymere und deren Verwendung in lithographischen Druckplattenvorläufer
EP2963496B1 (de) 2014-06-30 2017-04-05 Agfa Graphics NV Lithografiedruckplattenvorläufer mit (Ethylen-, Vinylacetal-) Copolymeren
EP3032334B1 (de) 2014-12-08 2017-10-18 Agfa Graphics Nv System zur Reduzierung von Ablationsrückständen
EP3130465B1 (de) 2015-08-12 2020-05-13 Agfa Nv Wärmeempfindlicher lithografiedruckplattenvorläufer
EP3170662B1 (de) 2015-11-20 2019-08-14 Agfa Nv Flachdruckplattenvorläufer
CN108778744A (zh) 2016-03-16 2018-11-09 爱克发有限公司 加工平版印刷版的方法和设备
EP3637188A1 (de) 2018-10-08 2020-04-15 Agfa Nv Sprudelnder entwicklervorläufer zur verarbeitung eines lithografischen druckplattenvorläufers
CN113632003B (zh) * 2019-03-28 2024-06-11 东洋纺Mc株式会社 柔版印刷版用显影液组合物、显影液及印刷原版的制造方法
EP3778253A1 (de) 2019-08-13 2021-02-17 Agfa Nv Verfahren zur verarbeitung einer lithografiedruckplatte
EP4382306A1 (de) 2022-12-08 2024-06-12 Eco3 Bv Make-ready-verfahren für eine lithographische druckmaschine

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4678551A (en) * 1984-10-11 1987-07-07 Fuji Photo Film Co., Ltd. Process for producing an aluminum support for a lithographic printing plate
WO2008106010A1 (en) * 2007-02-28 2008-09-04 Eastman Kodak Company Positive-working radiation-sensitive compositions and elements

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5163368B1 (en) 1988-08-19 1999-08-24 Presstek Inc Printing apparatus with image error correction and ink regulation control
US5174205B1 (en) 1991-01-09 1999-10-05 Presstek Inc Controller for spark discharge imaging
DE69517815T2 (de) * 1995-12-14 2001-02-01 Agfa-Gevaert N.V., Mortsel Wärmeempfindliches Aufzeichnungselement und Verfahren zur Herstellung von Flachdruckformen damit
JP3779444B2 (ja) 1997-07-28 2006-05-31 富士写真フイルム株式会社 赤外線レーザ用ポジ型感光性組成物
EP0901902A3 (de) 1997-09-12 1999-03-24 Fuji Photo Film Co., Ltd. Positiv arbeitende lichtempfindliche Zusammensetzung für Infrarot Bebilderung
DE19803564A1 (de) 1998-01-30 1999-08-05 Agfa Gevaert Ag Polymere mit Einheiten aus N-substituiertem Maleimid und deren Verwendung in strahlungsempfindlichen Gemischen
GB9811813D0 (en) 1998-06-03 1998-07-29 Horsell Graphic Ind Ltd Polymeric compounds
US6613494B2 (en) 2001-03-13 2003-09-02 Kodak Polychrome Graphics Llc Imageable element having a protective overlayer
DE602004008224T2 (de) * 2003-02-11 2008-05-15 Agfa Graphics N.V. Wärmeempfindlicher lithographischer druckplattenvorläufer
EP1614538B1 (de) 2004-07-08 2009-03-04 Agfa Graphics N.V. Verfahren zur Herstellung einer negativarbeitenden, wärmeempfindlichen, lithographischen Druckplattenvorstufe
EP1614540B1 (de) 2004-07-08 2008-09-17 Agfa Graphics N.V. Verfahren zur Herstellung einer lithographischen Druckplatte
EP1614539B1 (de) 2004-07-08 2008-09-17 Agfa Graphics N.V. Verfahren zur Herstellung einer lithographischen Druckplatte
JP2006330670A (ja) 2005-04-28 2006-12-07 Konica Minolta Medical & Graphic Inc 感光性平版印刷版及びその画像形成方法
DE602005005657T2 (de) 2005-06-30 2009-04-16 Agfa Graphics N.V. Wärmeempfindlicher lithographischer Druckplattenvorläufer

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4678551A (en) * 1984-10-11 1987-07-07 Fuji Photo Film Co., Ltd. Process for producing an aluminum support for a lithographic printing plate
WO2008106010A1 (en) * 2007-02-28 2008-09-04 Eastman Kodak Company Positive-working radiation-sensitive compositions and elements

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KOZO HOSHINO ET AL: "Developments and Future Trends in Aluminum Products with Improved Surface Functions", KOBELCO TECHNOLOGY REVIEW, 26 January 2006 (2006-01-26), pages 63 - 69, XP055008628, Retrieved from the Internet <URL:http://www.kobelco.co.jp/english/ktr/pdf/ktr_26/063-069.pdf> [retrieved on 20111004] *

Also Published As

Publication number Publication date
EP2047988B1 (de) 2014-03-12
CN101821097A (zh) 2010-09-01
EP2047988A1 (de) 2009-04-15
ES2436000T3 (es) 2013-12-26
CN101821097B (zh) 2012-04-18
WO2009047112A1 (en) 2009-04-16
EP2197678A1 (de) 2010-06-23

Similar Documents

Publication Publication Date Title
EP2197678B1 (de) Lithographiedruckplattenvorläufer
EP1826021B1 (de) Positiv arbeitende Lithografiedruckformen
EP2941349B1 (de) (ethylen-,vinylacetal-)copolymere und ihre verwendung in lithographiedruckplattenvorläufern
EP2263874B1 (de) Lithographiedruckplattenvorläufer
EP2955198B1 (de) Ethylenvinylacetal-Copolymere und deren Verwendung in lithographischen Druckplattenvorläufer
EP1554346B1 (de) Polymer für wärmeempfindliche lithographische druckplattenvorläufer
EP2933278B1 (de) (Ethylen-,Vinylacetal-)Copolymere und ihre Verwendung in Lithographiedruckplattenvorläufern
EP1738901B1 (de) Wärmeempfindlicher lithographischer Druckplattenvorläufer
US10221269B2 (en) (Ethylene, vinyl acetal) copolymers and their use in lithographic printing plate precursors
WO2004035310A1 (en) Heat-sensitive lithographic printing plate precursor
US7425402B2 (en) Heat-sensitive lithographic printing plate precursor
EP1554324A1 (de) Polymer für wärmeempfindlichen vorläufer einer lithographischen druckplatte
US7678533B2 (en) Heat-sensitive lithographic printing plate precursor
US8455177B2 (en) Method for making a lithographic printing plate
EP1738900A1 (de) Wärmeempfindlicher Flachdruckplattenvorläufer
US7458320B2 (en) Polymer for heat-sensitive lithographic printing plate precursor
US20070003869A1 (en) Heat-sensitive lithographic printing plate-precursor

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

17P Request for examination filed

Effective date: 20090327

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA MK RS

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

DAX Request for extension of the european patent (deleted)
GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

GRAL Information related to payment of fee for publishing/printing deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR3

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20130513

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 639161

Country of ref document: AT

Kind code of ref document: T

Effective date: 20131215

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2436000

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20131226

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602008028640

Country of ref document: DE

Effective date: 20140109

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 639161

Country of ref document: AT

Kind code of ref document: T

Effective date: 20131106

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

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

Ref country code: HR

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: 20131106

Ref country code: IS

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: 20140306

Ref country code: SE

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: 20131106

Ref country code: NO

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: 20140206

Ref country code: FI

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: 20131106

Ref country code: LT

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: 20131106

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

Ref country code: AT

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: 20131106

Ref country code: LV

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: 20131106

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: 20131106

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

Ref country code: PT

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: 20140306

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

Ref country code: EE

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: 20131106

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602008028640

Country of ref document: DE

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

Ref country code: PL

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: 20131106

Ref country code: SK

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: 20131106

Ref country code: CZ

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: 20131106

Ref country code: RO

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: 20131106

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

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

Ref country code: DK

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: 20131106

26N No opposition filed

Effective date: 20140807

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602008028640

Country of ref document: DE

Effective date: 20140807

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

Ref country code: SI

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: 20131106

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

Ref country code: MC

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: 20131106

Ref country code: LU

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: 20140923

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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

Ref country code: CH

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

Effective date: 20140930

Ref country code: LI

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

Effective date: 20140930

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

Ref country code: IE

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

Effective date: 20140923

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

Ref country code: BG

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: 20131106

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

Ref country code: MT

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: 20131106

Ref country code: CY

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: 20131106

Ref country code: GR

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: 20140207

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

Ref country code: TR

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: 20131106

Ref country code: HU

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

Effective date: 20080923

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 9

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 10

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602008028640

Country of ref document: DE

Owner name: AGFA NV, BE

Free format text: FORMER OWNER: AGFA GRAPHICS NV, 2640 MORTSEL, BE

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

Owner name: AGFA NV

Effective date: 20180308

REG Reference to a national code

Ref country code: NL

Ref legal event code: HC

Owner name: AGFA NV; BE

Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), CHANGE OF OWNER(S) NAME; FORMER OWNER NAME: AGFA GRAPHICS NV

Effective date: 20180126

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

REG Reference to a national code

Ref country code: FR

Ref legal event code: CD

Owner name: AGFA NV, BE

Effective date: 20180628

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

Ref country code: NL

Payment date: 20190730

Year of fee payment: 12

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

Ref country code: IT

Payment date: 20190920

Year of fee payment: 12

Ref country code: FR

Payment date: 20190731

Year of fee payment: 12

Ref country code: DE

Payment date: 20190731

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: 20190731

Year of fee payment: 12

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

Ref country code: ES

Payment date: 20191023

Year of fee payment: 12

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602008028640

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20201001

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

Effective date: 20200923

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

Ref country code: NL

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

Effective date: 20201001

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: 20210401

Ref country code: FR

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

Effective date: 20200930

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: 20200923

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

Ref country code: IT

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

Effective date: 20200923

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20220118

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

Ref country code: ES

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

Effective date: 20200924