US20220066318A1 - Lithographic printing plate precursor - Google Patents

Lithographic printing plate precursor Download PDF

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Publication number
US20220066318A1
US20220066318A1 US17/312,517 US201917312517A US2022066318A1 US 20220066318 A1 US20220066318 A1 US 20220066318A1 US 201917312517 A US201917312517 A US 201917312517A US 2022066318 A1 US2022066318 A1 US 2022066318A1
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Prior art keywords
printing plate
image
plate precursor
ppp
coating
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US17/312,517
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English (en)
Inventor
Peter Hendrikx
Thomas BILLIET
Johan Loccufier
Katleen HIMSCHOOT
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Eco3 BV
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Agfa NV
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Publication of US20220066318A1 publication Critical patent/US20220066318A1/en
Assigned to AGFA OFFSET BV reassignment AGFA OFFSET BV ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AGFA NV
Assigned to ECO3 BV reassignment ECO3 BV CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: AGFA OFFSET BV
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • B41C1/1033—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 by laser or spark ablation
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/016—Diazonium salts or compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/016—Diazonium salts or compounds
    • G03F7/0166—Diazonium salts or compounds characterised by the non-macromolecular additives
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/3035—Imagewise removal using liquid means from printing plates fixed on a cylinder or on a curved surface; from printing cylinders
    • 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

Definitions

  • Lithographic printing typically involves the use of a so-called printing master such as a printing plate which is mounted on a cylinder of a rotary 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
  • 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-adhesive (ink-repelling) areas and during driographic printing, only ink is supplied to the master.
  • Lithographic printing masters are generally obtained by the image-wise exposure and processing of a radiation sensitive layer on a lithographic support. Imaging and processing renders the so-called lithographic printing plate precursor into a printing plate or master.
  • Image-wise exposure of the radiation sensitive coating to heat or light typically by means of a digitally modulated exposure device such as a laser, triggers a (physico-)chemical process, such as ablation, polymerization, insolubilization by cross-linking of a polymer or by particle coagulation of a thermoplastic polymer latex, solubilization by the destruction of intermolecular interactions or by increasing the penetrability of a development barrier layer.
  • the most popular lithographic plate precursors require wet processing since the exposure produces a difference in solubility or difference in rate of dissolution in a developer between the exposed and the non-exposed areas of the coating.
  • positive working lithographic plate precursors the exposed areas of the coating dissolve in the developer while the non-exposed areas remain resistant to the developer.
  • negative working lithographic plate precursors the non-exposed areas of the coating dissolve in the developer while the exposed areas remain resistant to the developer.
  • lithographic plate precursors contain a hydrophobic coating on a hydrophilic support, so that the areas which remain resistant to the developer define the ink-accepting, hence printing areas of the plate while the hydrophilic support is revealed by the dissolution of the coating in the developer at the non-printing areas.
  • Photopolymer printing plates rely on a working-mechanism whereby the coating—which typically includes free radically polymerisable compounds—hardens upon exposure. “Hardens” means that the coating becomes insoluble or non-dispersible in the developing solution and may be achieved through polymerization and/or crosslinking of the photosensitive coating upon exposure to light.
  • Photopolymer plate precursors can be sensitized to blue, green or red light i.e. wavelengths ranging between 450 and 750 nm, to violet light i.e. wavelengths ranging between 350 and 450 nm or to infrared light i.e. wavelengths ranging between 750 and 1500 nm.
  • the exposure step is followed by a heating step to enhance or to speed-up the polymerization and/or crosslinking reaction.
  • a toplayer or protective overcoat layer over the imageable layer is required to act as an oxygen barrier to provide the desired sensitivity to the plate.
  • a toplayer typically includes water-soluble or water-swellable polymers such as for example polyvinylalcohol. Besides acting as barrier for oxygen, the toplayer should best be easily removable during processing and be sufficiently transparent for actinic radiation, e.g. from 300 to 450 nm or from 450 to 750 nm or from 750 to 1500 nm.
  • the lithographic printing plate precursors often contain a colorant such as a dye or a pigment in the coating.
  • colorants provide, after processing, a contrast between the image areas containing the colorant and the hydrophilic support where the coating has been removed which enables the end-user to evaluate the image quality and/or to establish whether or not the precursor has been exposed to light.
  • the leuco dye technology involves a switch between two chemical forms whereby one is colourless. If the colour switch is caused by for example pH or temperature, the transformation is reversible. Irreversible switches are based on redox reactions.
  • the printing plate precursor defined in claim 1 with preferred embodiments defined in the dependent claims.
  • the invention has the specific feature that the printing plate material includes a coating comprising an onium compound having an anion as counter ion and at least one sensitizer which are capable of forming a printout image upon UV exposure.
  • the CIE 1976 colour distance ⁇ E measured before development and after exposure with UV light having an energy density between 10 and 150 mJ/cm 2 , more preferably between 15 and 120 mJ/cm 2 , most preferably of maximum between 20 and 100 mJ/cm 2 , between the exposed and non-exposed areas preferably has a value of at least 5.
  • the development is preferably carried out by treating the precursor with a gum solution, however more preferably by mounting the precursor on a plate cylinder of a lithographic printing press and rotating the plate cylinder while feeding dampening liquid and/or ink to the precursor.
  • the lithographic printing plate precursor of the current invention comprises a coating including at least one sensitizer.
  • Preferred sensitizers are blue, light absorbing sensitizers having an absorption spectrum between 320 nm and 500 nm.
  • the sensitizer has a structure according to the following Formula's I or II:
  • R 1′ to R 5′ and R 1 ′′ to R 5 ′′ independently represent hydrogen, an alkyl group, an alkoxy group, a cyano group or a halogen;
  • R 1 to R 14 independently represent hydrogen, an alkyl group, an alkoxy group, a cyano group or a halogen.
  • R 1′ to R 5′ or R 1 ′′ to R 5 ′′ in Formula I preferably represents an alkoxy group having more than 1 carbon atom.
  • R 1′ , R 5′ , R 1 ′′, R 5 ′′ in Formula I independently represent hydrogen, fluorine, chlorine, R 2′ to R 4′ and R 2 ′′ to R 4 ′′ in Formula I independently represent an alkoxy group; and at least two of the alkoxy groups are branched and have from 3 to 15 carbon atoms
  • R 1′ , R 5′ , R 1 ′′, R 5 in Formula I represent hydrogen and R 2′ to R 4′ and R 2 ′′ to R 4 ′′ in Formula I independently represent an alkoxy group; and at least two of the alkoxy groups are branched and have from 3 to 15 carbon atoms.
  • R 2′ , R 4′ , R 2 ′′, R 4 ′′ in Formula I represent a methoxy group and R 3′ and R 3 ′′ in Formula I independently represent branched alkoxy groups having 3 to 15 carbon atoms.
  • R 1 to R 10 in Formula II preferably represents an alkoxy group having more than 1 carbon atom.
  • R 1 , R 5 , R 6 , R 10 , R 11 , R 12 , R 13 and R 14 in Formula II independently represent hydrogen, fluorine, chlorine, R 2 to R 4 and R 7 to R 9 in Formula II independently represent an alkoxy group; and at least two of the alkoxy groups are branched and have from 3 to 15 carbon atoms
  • R 1 , R 5 , R 6 , and R 10 in Formula II represent hydrogen and R 2 to R 4 , and R 7 to R 9 in Formula II independently represent an alkoxy group; and at least two of the alkoxy groups are branched and have from 3 to 15 carbon atoms.
  • R 2 , R 4 , R 7 and R 9 in Formula II represent a methoxy group and R 3 and R 8 in Formula II independently represent branched alkoxy groups having 3 to 15 carbon atoms.
  • the sensitizers can be used as single compound or as mixture of several compounds.
  • the overall amount of these compounds is preferably comprised between 0.1 to 25% by weight, more preferably between 0.5 to 20% by weight by weight and most preferably between 1.0 to 15% by weight with respect to the total weight of the non-volatile compounds in the composition.
  • the print-out image is already obtained at a low concentration of sensitizer; for example at an amount of 0.1% wt to 6% wt.
  • the coating of the printing plate precursor of the present invention most preferably contains at least one of the following compounds:
  • the three sensitizers according to Formulae III to V may be used in the coating as a mixture.
  • the mixture preferably contains between 30 and 45% by weight of Formula (III); between 35 and 55% by weight of Formula (IV) and between 5 and 25% by weight of Formula (V).
  • the coating of the printing plate precursor includes at least one onium salt including an anion as counter ion.
  • Preferred onium salts include iodonium salts and sulfonium salts.
  • One or a mixture of two or more onium salts may be present in the coating.
  • iodonium salts without being limited thereto include optionally substituted diaryl iodonium salts or diheteroaryl iodonium salts.
  • Diaryl iodonium salts or diheteroaryl iodonium salts substituted with Specific examples of the diaryliodonium salts include diphenyliodonium, 4-methoxyphenyl-4-(2-methylpropyl) phenyliodonium, 4-chlorophenyl-4-phenyliodonium, 4-(2-methylpropyl) phenyl-tolyl iodonium, 4-hexyloxyphenyl-2,4,6-trimethoxyphenyliodonium, 4-hexyloxyphenyl-2,4-diethoxyphenyliodonium, 4-octyloxyphenyl-6-trimethoxyphenyliodonium, bis (4-tert-butylphenyl) iodonium and bis (4-iso
  • triarylsulfonium salts without being limited thereto include triphenylsulfonium, dialkylphenacylsulfonium, dialkyl-4-hydroxyphenylsulfonium, bis (4-chlorophenyl) phenylsulfonium, triphenylsulfonium benzoyl formate, bis (4-chlorophenyl) phenylsulfonium benzoyl formate, bis (4-chlorophenyl)-4-methylphenylsulfonium bis (4-chlorophenyl)-4-methylphenylsulfonium, tris (4-chlorophenyl) sulfonium, tris 2,4-dichlorophenyl) sulfonium, bis (2,4-dichlorophenyl) phenyl sulfonium and bis (2,4-dichlorophenyl) 4-methoxyphenyl sulfonium.
  • the counter ion of the onium salts is selected from hexafluorophosphate (PF 6 ⁇ ), SbF 6 ⁇ or AsF 6 ⁇ .
  • the onium salts are preferably present in the coating in an amount between at least 1% wt and 25% wt, more preferably in an amount between at least 5% wt and 20% wt, most preferably in an amount between at least 10% wt and 15% wt, all based on the total dry weight of the photopolymerisable and/or crosslinkable layer.
  • the colour difference between the exposed and non-exposed areas of the coating calculated from the L*a*b* values of the exposed areas of the image areas (exposed areas) of the coating and the L*a*b* values of non-image areas (non-exposed areas) of the coating is denoted as ⁇ E.
  • ⁇ E is the CIE 1976 colour distance Delta E that is defined by the pair wise Euclidean distance of the CIE L*a*b* colour coordinates.
  • CIE L*a*b* colour coordinates are obtained from reflection measurement in 45/0 geometry (non-polarized), using CIE 2° observer and D50 as illuminant. More details are described in CIE S 014-4/E: 2007 Colourimetry—Part 4: CIE 1976 L*a*b* Colour Spaces and CIE publications and CIE S 014-1/E:2006, CIE Standard Colourimetric Observers.
  • the CIE 1976 colour system is described in e.g. “Colorimetry, CIE 116-1995: Industrial Colour Difference Evaluation”, or in “Measuring Colour” by R. W. G. Hunt, second edition, edited in 1992 by Ellis Horwood Limited, England.
  • the L*, a* and b* coordinates are enhanced due to absorption in the visual wavelength range whereby a clear print-out image is formed.
  • the print-out image is visible due to the contrast of the image which is defined as the colour difference between the exposed areas and the non-exposed areas. This contrast is preferably as high as possible and enables the end-user to establish immediately after imaging whether or not the precursor has already been exposed, to distinguish the different colour selections and to inspect the quality of the image on the plate precursor.
  • the optionally substituted aryl herein is preferably an optionally substituted phenyl, benzyl, tolyl or an ortho-meta- or para-xylyl, naphtyl, anthracenyl, phenanthrenyl, and/or combinations thereof.
  • the heteroaryl group is preferably a monocyclic or polycyclic aromatic ring comprising carbon atoms and one or more heteroatoms in the ring structure, preferably, 1 to 4 heteroatoms, independently selected from nitrogen, oxygen, selenium and sulphur.
  • Preferred examples thereof include an optionally substituted furyl, pyridinyl, pyrimidyl, pyrazoyl, imidazoyl, oxazoyl, isoxazoyl, thienyl, tetrazoyl, thiazoyl, (1,2,3)triazoyl, (1,2,4)triazoyl, thiadiazoyl, thiofenyl group and/or combinations thereof and the optionally substituted heteroaryl is preferably a five- or six-membered ring substituted by one, two or three oxygen atoms, nitrogen atoms, sulphur atoms, selenium atoms or combinations thereof.
  • Examples thereof include furan, thiophene, pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, oxazole, isoxazole, thiazole, isothiazole, thiadiazole, oxadiazole, pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine or 1,2,3-triazine, benzofuran, benzothiophene, indole, indazole, benzoxazole, quinoline, quinazoline, benzimidazole or benztriazole.
  • alkyl herein means all variants possible for each number of carbon atoms in the alkyl group i.e. methyl, ethyl, for three carbon atoms: n-propyl and isopropyl; for four carbon atoms: n-butyl, isobutyl and tertiary-butyl; for five carbon atoms: n-pentyl, 1,1-dimethyl-propyl, 2,2-dimethylpropyl and 2-methyl-butyl, etc.
  • the alkyl group is a C 1 to C 20 -alkyl group; more preferably the alkyl group is a C 1 to C 6 -alkyl group.
  • alkyl is a methyl group.
  • Cycloalkyls include for example, substituted or unsubstituted cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, and cyclooctyl groups.
  • substituted in e.g. substituted alkyl group means that the alkyl group may be substituted by other atoms than the atoms normally present in such a group, i.e. carbon and hydrogen.
  • a substituted alkyl group may include a halogen atom or a thiol group.
  • An unsubstituted alkyl group contains only carbon and hydrogen atoms.
  • the optional substituents represent an alkyl, cycloalkyl, alkenyl or cyclo alkenyl group, an alkynyl group, an aryl or heteroaryl group, an alkylaryl or arylalkyl group, an alkoxy group such as methoxy, ethoxy, iso-propoxy, t-butoxy, (2-hydroxytetradecyl)oxy, and various other linear and branched alkyleneoxyalkoxy groups; an aryloxy group, a thio alkyl, thio aryl or thio heteroaryl group, a hydroxyl group, —SH, a carboxylic acid group or an alkyl ester thereof, a sulphonic acid group or an alkyl ester thereof, a phosphonic acid group or an alkyl ester thereof, a phosphoric acid group or an alkyl ester thereof, an amino group, a sulphonamide group, an amide group, a nitro group, a
  • a suitable alkenyl group herein is preferably a C 2 to C 6 -alkenyl group such as an ethenyl, n-propenyl, n-butenyl, n-pentenyl, n-hexenyl, iso-propenyl, iso-butenyl, iso-pentenyl, neo-pentenyl, 1-methylbutenyl, iso-hexenyl, cyclopentenyl, cyclohexenyl and methylcyclohexenyl group.
  • a suitable alkynyl group herein is preferably a C 2 to C 6 -alkynyl group; a suitable aralkyl group is preferably a phenyl group or naphthyl group including one, two, three or more C 1 to C 6 -alkyl groups; a suitable alkaryl group is preferably a C 1 to C 6 -alkyl group including an aryl group, preferably a phenyl group or naphthyl group.
  • a cyclic group or cyclic structure herein includes at least one ring structure and may be a monocyclic- or polycyclic group, meaning one or more rings fused together.
  • the lithographic printing plate precursor according to the present invention is negative-working, i.e. after exposure and development the non-exposed areas of the coating are removed from the support and define hydrophilic (non-printing) areas, whereas the exposed coating is not removed from the support and defines oleophilic (printing) areas.
  • the hydrophilic areas are defined by the support which has a hydrophilic surface or is provided with a hydrophilic layer.
  • the hydrophobic areas are defined by the coating, hardened upon exposing, optionally followed by a heating step. Areas having hydrophilic properties means areas having a higher affinity for an aqueous solution than for an oleophilic ink; areas having hydrophobic properties means areas having a higher affinity for an oleophilic ink than for an aqueous solution.
  • Hardened means that the coating becomes insoluble or non-dispersible for the developing solution and may be achieved through polymerization and/or crosslinking of the photosensitive coating, optionally followed by a heating step to enhance or to speed-up the polymerization and/or crosslinking reaction.
  • this optional heating step hereinafter also referred to as “pre-heat”, the plate precursor is heated, preferably at a temperature of about 80° C. to 150° C. and preferably during a dwell time of about 5 seconds to 1 minute.
  • the coating includes at least one layer including a photopolymerisable and/or crosslinkable composition.
  • the layer including the mainly photopolymerisable composition is also referred to as the “photopolymerisable layer”, the layer including the mainly crosslinkable composition is also referred to as the “crosslinkable layer”.
  • the coating may include an intermediate layer, located between the support and the photopolymerisable and/or crosslinkable layer.
  • the lithographic printing precursors can be multi-layer imageable elements.
  • the lithographic printing plate precursor can be prepared by applying on a support the coating as described below and drying the precursor.
  • the printing plate of the present invention is preferably exposed with UV radiation having an energy density comprised between 10 mJ/cm 2 and 150 mJ/cm 2 ; preferably between 15 mJ/cm 2 and 120 mJ/cm 2 ; most preferably between 20 mJ/cm 2 and 100 mJ/cm 2 .
  • the printing plate precursor of the present invention has the specific feature that it is not sensitive to the portion of the electromagnetic spectrum starting from about 500 nm and higher. In other words, the printing plate of the present invention is stable for at least five minutes in office light (i.e. for example 800 lux). Stable means that the quality of the printing plate precursor remains high and that the precursor does not have an increased tendency to toning and/or formation of defects in the coating after such light exposure.
  • the sensitivity of the plate precursor does not reduce after such light exposure.
  • the quality of the printing plate remains high i.e. no/limited loss of sensitivity, no/limited formation of defects in the coating, and/or no/limited tendency of toning after exposure to office light up to five minutes.
  • the lithographic printing plate used in the present invention comprises a support which has a hydrophilic surface or which is provided with a hydrophilic layer.
  • the support is preferably a grained and anodized aluminum support, well known in the art. Suitable supports are for example disclosed in EP 1 843 203 (paragraphs [0066] to [0075]).
  • the surface roughness, obtained after the graining step, 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.
  • an Al 2 O 3 layer is formed and the anodic weight (g/m 2 Al 2 O 3 formed on the aluminum surface) varies between 1 and 8 g/m 2 .
  • the anodic weight is preferably ⁇ 3 g/m 2 , more preferably ⁇ 3.5 g/m 2 and most preferably ⁇ 4.0 g/m 2
  • the grained and anodized aluminum support may be subjected to so-called post-anodic treatments, for example a treatment with polyvinylphosphonic acid or derivatives thereof, a treatment with polyacrylic acid, a treatment with potassium fluorozirconate or a phosphate, a treatment with an alkali metal silicate, or combinations thereof.
  • the support may be treated with an adhesion promoting compound such as those described in EP 1 788 434 in [0010] and in WO 2013/182328.
  • an adhesion promoting compound such as those described in EP 1 788 434 in [0010] and in WO 2013/182328.
  • a plastic support for example a polyester support, provided with one or more hydrophilic layers as disclosed in for example EP 1 025 992 may also be used.
  • the photopolymerisable layer includes, besides the sensitizer and the onium salt discussed above, a polymerisable compound, optionally a binder and a polymerization initiator capable of hardening said polymerisable compound in the exposed areas.
  • the photopolymerisable layer has a coating thickness preferably ranging between 0.2 and 5.0 g/m 2 , more preferably between 0.4 and 3.0 g/m 2 , most preferably between 0.6 and 2.2 g/m 2 .
  • the polymerisable compound is preferably a monomer or oligomer including at least one epoxy or vinyl ether functional group and the polymerisation initiator is a Brönsted acid generator capable of generating free acid, optionally in the presence of a sensitizer, upon exposure, hereinafter the Brönsted acid generator is also referred to as “cationic photoinitiator” or “cationic initiator”.
  • Suitable polyfunctional epoxy monomers include, for example, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, bis-(3,4-epoxycyclohexymethyl) adipate, difunctional bisphenol A-epichlorohydrin epoxy resin and multifunctional epichlorohydrintetraphenylol ethane epoxy resin.
  • Suitable cationic photoinitiators include, for example, triarylsulfonium hexafluoroantimonate, triarylsulfonium hexafluorophosphate, diaryliodonium hexafluoroantimonate, and haloalkyl substituted s-triazine. It is noted that most cationic initiators are also free radical initiators because, in addition to generating Brönsted acid, they also generate free radicals during photo or thermal decomposition.
  • the further polymerisable compound is a polymerisable monomer or oligomer including at least one terminal ethylenic group, hereinafter also referred to as “free-radical polymerisable monomer”, and the polymerisation initiator is a compound capable of generating free radicals upon exposure, optionally in the presence of a sensitizer, hereinafter said initiator is referred to as “free radical initiator”.
  • the polymerisation involves the linking together of the free-radical polymerisable monomers.
  • Suitable free-radical polymerisable monomers include, for example, multifunctional (meth)acrylate monomers (such as (meth)acrylate esters of ethylene glycol, trimethylolpropane, pentaerythritol, ethoxylated ethylene glycol and ethoxylated trimethylolpropane, multifunctional urethanated (meth)acrylate, and epoxylated (meth)acrylate), and oligomeric amine diacrylates.
  • the (meth)acrylic monomers may also have other double bond or epoxide group, in addition to (meth)acrylate group.
  • the (meth)acrylate monomers may also contain an acidic (such as carboxylic acid) or basic (such as amine) functionality.
  • Suitable free-radical polymerisable monomers are disclosed in [0042] and [0050] of EP 2 916 171 and are incorporated herein by reference.
  • the coating contains a free radical initiator capable of generating free radicals upon exposure directly and/or in the presence of a sensitizer.
  • Suitable free-radical initiators are described in WO 2005/111727 from page 15 line 17 to page 16 line 11 and EP 1 091 247 and may include for example hexaaryl-bisimidazole compound (HABI; dimer of triaryl-imidazole), aromatic ketones, aromatic onium salts, organic peroxides, thio compounds, ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds and further compounds having a carbon-halogen bond.
  • HABI hexaaryl-bisimidazole compound
  • the photopolymerisable layer may also comprise a co-initiator.
  • a co-initiator is used in combination with a free radical initiator.
  • Suitable co-initiators for use in the photopolymer coating are disclosed in U.S. Pat. Nos. 6,410,205; 5,049,479; EP 1 079 276, EP 1 369 232, EP 1 369 231, EP 1 341 040, US 2003/0124460, EP 1 241 002, EP 1 288 720 and in the reference book including the cited refences: Chemistry & Technology UV & EB formulation for coatings, inks & paints—Volume 3—Photoinitiators for Free Radical and Cationic Polymerisation by K. K.
  • the photopolymerisable layer preferably includes a binder.
  • the binder can be selected from a wide series of organic polymers. Compositions of different binders can also be used. Useful binders are described in WO2005/111727 page 17 line 21 to page 19 line 30, EP 1 043 627 in paragraph [0013] and in WO2005/029187 page 16 line 26 to page 18 line 11.
  • the photopolymerisable layer may also comprise particles which increase the resistance of the coating against manual or mechanical damage.
  • the particles may be inorganic particles, organic particles or fillers such as described in for example U.S. Pat. No. 7,108,956. More details of suitable spacer particles described in EP 2 916 171 [0053] to [0056] are incorporated herein by reference.
  • the photopolymerisable layer may also comprise an inhibitor. Particular inhibitors for use in the photopolymer coating are disclosed in U.S. Pat. No. 6,410,205, EP 1 288 720 and EP 1 749 240.
  • the photopolymerisable layer may further comprise an adhesion promoting compound.
  • the adhesion promoting compound is a compound capable of interacting with the support, preferably a compound having an addition-polymerisable ethylenically unsaturated bond and a functional group capable of interacting with the support.
  • interacting each type of physical and/or chemical reaction or process whereby, between the functional group and the support, a bond is formed which can be a covalent bond, an ionic bond, a complex bond, a coordinate bond or a hydrogen-bond, and which can be formed by an adsorption process, a chemical reaction, an acid-base reaction, a complex-forming reaction or a reaction of a chelating group or a ligand.
  • the adhesion promoting compound may be selected from at least one of the low molecular weight compounds or polymeric compounds as described in EPA 851 299 from lines 22 on page 3 to line 1 on page 4, EP-A 1 500 498 from paragraph [0023] on page 7 to paragraph [0052] on page 20, EP-A 1 495 866 paragraph [0030] on page 5 to paragraph [0049] on page 11, EP-A 1 091 251 from paragraph [0014] on page 3 to paragraph [0018] on page 20, and EP-A 1 520 694 from paragraph [0023] on page 6 to paragraph [0060] on page 19.
  • Preferred compounds are those compounds which comprise a phosphate or phosphonate group as functional group capable of adsorbing on the aluminum support and which comprise an addition-polymerisable ethylenic double bond reactive group, especially those described in EP-A 851 299 from lines 22 on page 3 to line 1 on page 4 and EP-A 1 500 498 from paragraph [0023] on page 7 to paragraph [0052] on page 20.
  • tri-alkyl-oxy silane groups hereinafter also referred to as “trialkoxy silane” groups, wherein the alkyl is preferably methyl or ethyl, or wherein the trialkyloxy silane groups are at least partially hydrolysed to silanol groups, as functional group capable of adsorbing on the support, especially silane coupling agents having an addition-polymerisable ethylenic double bond reactive group as described in EP-A 1 557 262 paragraph [0279] on page 49 and EP-A 1 495 866 paragraph [0030] on page 5 to paragraph [0049] on page 11. Also the adhesion promoting compounds described in EP 2 916 171 [0058] are incorporated herein by reference.
  • the adhesion promoting compound may be present in the photopolymerisable layer in an amount ranging between 1 and 50 wt %, preferably between 3 and 30 wt %, more preferably between 5 and 20 wt % of the non-volatile components of the composition.
  • the adhesion promoting compound may be present in an optional intermediate layer in an amount of at least 25 wt %, preferably at least 50 wt %, more preferably at least 75 wt %, of the non-volatile components of the composition.
  • the intermediate layer may consist of the adhesion promoting compound.
  • surfactants may be added into the photopolymerisable layer to allow or enhance the developability of the precursor; especially developing with a gum solution.
  • Both polymeric and small molecule surfactants for example nonionic surfactants are preferred. More details are described in EP 2 916 171 [0059] and are incorporated herein by reference.
  • the crosslinkable layer may include a diazonium compound and preferably a binder.
  • Diazonium compounds are preferably characterized by the generic structure A-N 2 + X ⁇ , wherein A is an aromatic or heterocyclic residue and X is the anion of an acid.
  • Specific examples of light sensitive diazonium coatings include higher molecular weight compositions obtained, for example, by the condensation of certain aromatic diazonium salts in an acid condensation medium with active carbonyl compounds such as formaldehyde, as disclosed for example in U.S. Pat. Nos. 2,063,631 and 2,667,415.
  • Suitable examples include condensation products of diazonium salts of p-amino-diphenylamines, such as diphenylamine-4-diazonium chloride or diphenylamine-4-diazonium bromide or diphenyl-amine-4-diazonium phosphate, with formaldehyde in phosphoric acid of high concentration.
  • phosphoric acid also includes pyrophosphoric acid, metaphosphoric acid, and poly-phosphoric acid.
  • diazonium compounds Another preferred class of diazonium compounds is described in U.S. Pat. No. 3,849,392.
  • the compounds are the polycondensation product of 3-methoxy-4-diazo-diphenyl amine sulfate and 4, 4′-bis-methoxy methyl-diphenyl ether, precipitated as mesitylene sulfonate, as taught in U.S. Pat. No. 3,849,392.
  • the most preferred diazonium salt is benzenediazonium, 2-methoxy-4-(phenylamino), 2,4,6-trimethylbenzenesulfonate (1:1), polymer with 1,1′-oxybis[4-(methoxymethyl)benzene].
  • the preparation of this diazonium salt is disclosed in DE 2024244A.
  • Other diazonium salts disclosed in this document are suitable to be contained in the crosslinkable layer.
  • the diazonium salt is preferably present in the coating composition in an amount of from about 20% to about 100% by weight of the solid composition components. A more preferred range is from about 25% to 50% and most preferably from about 30% to 45%.
  • the binder may be added to the diazonium compound to improve mechanical resistance of the crosslinkable layer and/or the processing behaviour of the plate.
  • Suitable binders are polyvinyl acetates, epoxy resins based on bis-phenol-A-epichlorohydrin, p-(vinyl butyral-co-,vinyl acetate-co-vinyl alcohol), unplasticized urea resin of an approximate acid number of 2 (Resamin 106 F), Recinene-modified alkyd resin, Resins comprising a polyvinyl acetate resin and a styrene/maleic acid half ester copolymer,
  • Suitable polyvinyl acetate resins have a weight average molecular weight in the range of from about 40.000 to less than 800.000.
  • a preferred weight average molecular weight maximum is about 700.000; more preferably 680.000.
  • the most preferred average molecular weight is in the range of about 80.000 to 200,000.
  • Preferred binders are the butyl semi-ester of the maleic acid anhydride/styrene copolymers (such as Scripset® 540, available from Monsanto) and the styrene/maleic acid half ester copolymers as disclosed in U.S. Pat. No. 4,511,640A.
  • a more preferred binder is obtained by reacting p-[vinylbutyral-co-vinyl alcohol-co-vinyl acetate] such as Mowital B30T or Mowital B60T (from Kuraray Europe GmbH) with maleic acid anhydride to a half-ester and half acid, with the OH of the polyvinylalcohol as disclosed in Preparation Example 5 in U.S. Pat. No. 5,695,905.
  • the binder is preferably present in the coating composition in an amount of from about 8% to about 60% by weight of the solid composition components. A more preferred range is from about 12% to 50% and most preferably from about 18% to 45%.
  • the weight ratio of binder to diazonium compound does not exceed 20, preferably equal to or less than 10, more preferably between 0.8 and 1.2.
  • the coverage of the crosslinkable layer is preferably between 0.1 and 1.2 g/m 2 , more preferably between 0.5 and 0.8 g/m 2 .
  • the crosslinkable layer may further comprise additives, such as for example acid stabilizers including phosphoric, citric, tartaric and p-toluene sulfonic acids.
  • the acid stabilizer may be present in the coating composition in an amount of from about 1.5% to about 4.5% by weight of the solid composition components, a more preferably from about 2.0% to 4.0% and most preferably from about 2.5% to 3.5%.
  • Exposure indicators including para phenyl azo diphenyl amine, Calcozine Fuchine dyes and Crystal Violet and Methylene Blue dyes may be present in an amount from about 0.05% to about 0.35% by weight of the solid composition components. A more preferred range is from about 0.10% to 0.30% and most preferably from about 0.15% to 0.25%.
  • Suitable solvents which may be used as a medium to combine the ingredients of the coating include Methyl Cellosolve, ethylene glycol ethers, butyrolactone, alcohols as ethyl alcohol and n-propanol, and ketones such as methyl ethyl ketone.
  • the crosslinkable layer may include an o-quinonediazide compound and preferably a binder.
  • o-quinonediazide compounds are well-known and are for example described in Light-Sensitive Systems written by J. Kosar (Published by John Wiley & Sons. Inc.) pp. 339-352.
  • Suitable o-quinonediazide compounds are for example o-naphthoquinonediazide sulfonic acid esters of aromatic hydroxyl compounds, o-naphthoquinonediazide carboxylic acid esters of aromatic hydroxy compounds, o naphthoquinonediazide sulfonic acid amides of aromatic amino compounds and o-naphthoquinonediazide carboxylic acid amides of aromatic amino compounds.
  • Preferred binders are alkali-soluble resins include novolak resins such as for examples phenol-formaldehyde resins, cresol-formaldehyde resins, p-tert-butylphenol-formaldehyde resins, phenol modified xylene resins, i.e., a formaldehyde condensate of phenol and xylene, and phenol modified xylene mesitylene resins, i.e., a formaldehyde condensate of phenol, xylene and mesitylene.
  • Other useful alkali-soluble resins include polyhydroxystyrene, polyhalogenated hydroxystyrene, and copolymers of acrylic acid or methacrylic acid and other vinyl compounds (for example, methyl methacrylate).
  • the amount of o-quinonediazide compounds in coating composition is preferably from 10 to 50% by weight, preferably from 20 to 40% by weight, based on the total solid composition components.
  • the amount of the alkali-soluble resins added is preferably between 90 and 50% by weight, preferably between 80 and 60% by weight, based on the total solid weight.
  • the coating may include on the photopolymerisable or on the crosslinkable layer, a toplayer or protective overcoat layer which acts as an oxygen barrier layer including water-soluble or water-swellable binders.
  • Printing plate precursors which do not contain a toplayer or protective overcoat layer are also referred to as overcoat-free printing plate precursors.
  • a toplayer should be easily removable during development, adhere sufficiently to the photopolymerisable layer or optional other layers of the coating and should preferably not inhibit the transmission of light during exposure.
  • Preferred binders which can be used in the toplayer are polyvinyl alcohol and the polymers disclosed in WO 2005/029190; U.S. Pat. No. 6,410,205 and EP 1 288 720, including the cited references in these patents and patent applications.
  • the most preferred binder for the toplayer is polyvinylalcohol.
  • the polyvinylalcohol has preferably a hydrolysis degree ranging between 74 mol % and 99 mol %, more preferably between 88-98%.
  • the weight average molecular weight of the polyvinylalcohol can be measured by the viscosity of an aqueous solution, 4% by weight, at 20° C. as defined in DIN 53 015, and this viscosity number ranges preferably between 1 and 26, more preferably between 2 and 15, most preferably between 2 and 10.
  • the overcoat layer may optionally include other ingredients such as inorganic or organic acids, matting agents or wetting agents as disclosed in EP 2 916 171 and are incorporated herein by reference.
  • the coating thickness of the optional toplayer is preferably between 0.25 and 1.75 g/m 2 , more preferably between 0.25 and 1.3 g/m 2 , most preferably between 0.25 and 1.0 g/m 2 .
  • the optional toplayer has a coating thickness between 0.25 and 1.75 g/m 2 and comprises a polyvinylalcohol having a hydrolysis degree ranging between 74 mol % and 99 mol % and a viscosity number as defined above ranging between 1 and 26.
  • the photopolymerisable or the crosslinkable layer does not contain an overcoat layer.
  • a method for making a negative-working lithographic printing plate comprising the steps of imagewise exposing a printing plate precursor followed by developing the imagewise exposed precursor so that the non-exposed areas are dissolved in the developer solution.
  • a heating step is carried out to enhance or to speed-up the polymerization and/or crosslinking reaction.
  • the lithographic printing plate precursor can be prepared by (i) applying on a support the coating as described above and (ii) drying the precursor.
  • the image-wise exposing step is carried out off-press in a platesetter, i.e. an exposure apparatus suitable for image-wise exposing the precursor with a laser such as a laser diode, for example emitting around 405 nm, or by a conventional exposure in contact with a mask.
  • a laser such as a laser diode
  • the precursor is image-wise exposed by a laser emitting UV-light.
  • the printing plate precursor is preferably image wise exposed with UV-light and/or light in the short wavelength region of the visible light spectrum.
  • the light source preferably emits light having a wavelength between 360 and 420 nm.
  • the light source is built in an exposure head. Different modes can be used to expose the lithographic printing plate precursor, one where the plate is immobile and the exposure head moves back and forth such is in image setters having an internal drum, one where the plate is mounted onto a drum which rotates at high speed while the exposure head moves from one side of the drum to the other side of the drum.
  • the light source can be a bulb or lamp such as mercury vapour bulbs.
  • lasers are used due to the high energy density achievable, such as fibre-coupled laser diodes emitting at 405 nm. This high energy density makes it possible to achieve high plate throughput during the exposure step.
  • the image wise exposure via a laser is done by digital modulation of the current and or voltage.
  • the image wise exposure may be achieved by means of modulation of the light emitted from the light source. This modulation can be done by means of digital mirror devices, also called DMD imaging.
  • UV setters which are suitable to digitally modulate the light source are available from Lüscher AG and Basysprint from Xeikon International B.V. The digital information is obtained from a digital image which is made available to the UV setter.
  • the precursor may be pre-heated in a preheating unit, preferably at a temperature of about 80° C. to 150° C. and preferably during a dwell time of about 5 seconds to 1 minute.
  • This preheating unit may comprise a heating element, preferably an IR-lamp, an UV-lamp, heated air or a heated roll.
  • a preheat step can be used for printing plate precursors comprising a photopolymerisable composition to enhance or to speed-up the polymerization and/or crosslinking reaction.
  • the plate precursor may be processed (developed).
  • a pre-rinse step might be carried out especially for the negative-working lithographic printing precursors having a protective oxygen barrier or topcoat.
  • This pre-rinse step can be carried out in a stand-alone apparatus or by manually rinsing the imaged precursor with water or the pre-rinse step can be carried out in a washing unit that is integrated in a processor used for developing the imaged precursor.
  • the washing liquid is preferably water, more preferably tap water. More details concerning the wash step are described in EP 1 788 434 in [0026].
  • the non-exposed areas of the image-recording layer are at least partially removed without essentially removing the exposed areas.
  • the processing liquid also referred to as developer
  • the processing liquid can be applied to the plate e.g. by rubbing with an impregnated pad, by dipping, immersing, coating, spincoating, spraying, pouring-on, either by hand or in an automatic processing apparatus.
  • the treatment with a processing liquid may be combined with mechanical rubbing, e.g. by a rotating brush.
  • any water-soluble protective layer present is preferably also removed.
  • the development is preferably carried out at temperatures between 20 and 40° C. in automated processing units.
  • the processing liquid may be an alkaline developer or solvent-based developer.
  • Suitable alkaline developers have been described in US2005/0162505.
  • An alkaline developer is an aqueous solution which has a pH of at least 11, more typically at least 12, preferably from 12 to 14.
  • Alkaline developers typically contain alkaline agents to obtain high pH values can be inorganic or organic alkaline agents.
  • the developers can comprise anionic, non-ionic and amphoteric surfactants (up to 3% on the total composition weight); biocides (antimicrobial and/or antifungal agents), antifoaming agents or chelating agents (such as alkali gluconates), and thickening agents (water soluble or water dispersible polyhydroxy compounds such as glycerine or polyethylene glycol).
  • the processing liquid is a gum solution whereby during the development step the non-exposed areas of the photopolymerisable layer are removed from the support and the plate is gummed in a single step.
  • the development with a gum solution has the additional benefit that, due to the remaining gum on the plate in the non-exposed areas, an additional gumming step is not required to protect the surface of the support in the non-printing areas.
  • the precursor is processed and gummed in one single step which involves a less complex developing apparatus than a developing apparatus comprising a developer tank, a rinsing section and a gumming section.
  • the gumming section may comprise at least one gumming unit or may comprise two or more gumming units.
  • These gumming units may have the configuration of a cascade system, i.e. the gum solution, used in the second gumming unit and present in the second tank, overflows from the second tank to the first tank when gum replenishing solution is added in the second gumming unit or when the gum solution in the second gumming unit is used once-only, i.e. only starting gum solution is used to develop the precursor in this second gumming unit by preferably a spraying or jetting technique. More details concerning such gum development is described in EP1 788 444.
  • a gum solution is typically an aqueous liquid which comprises one or more surface protective compounds that are capable of protecting the lithographic image of a printing plate against contamination, e.g. by oxidation, fingerprints, fats, oils or dust, or damaging, e.g. by scratches during handling of the plate.
  • Suitable examples of such surface protective compounds are film-forming hydrophilic polymers or surfactants.
  • the layer that remains on the plate after treatment with the gum solution preferably comprises between 0.005 and 20 g/m 2 of the surface protective compound, more preferably between 0.010 and 10 g/m 2 , most preferably between 0.020 and 5 g/m 2 . More details concerning the surface protective compounds in the gum solution can be found in WO 2007/057348 page 9 line 3 to page 11 line 6.
  • the gum solution preferably has a pH value between 3 and 11, more preferably between 4 and 10, even more preferably between 5 and 9, and most preferably between 6 and 8.
  • a suitable gum solution is described in for example EP 1 342 568 in [0008] to [0022] and WO2005/111727.
  • the gum solution may further comprise an inorganic salt, an anionic surfactant, a wetting agent, a chelate compound, an antiseptic compound, an anti-foaming compound and/or an ink receptivity agent and/or combinations thereof. More details about these additional ingredients are described in WO 2007/057348 page 11 line 22 to page 14 line 19.
  • the plate may be dried in a drying unit.
  • the plate is dried by heating the plate in the drying unit which may contain at least one heating element selected from an IR-lamp, an UV-lamp, a heated metal roller or heated air.
  • the plate After drying the plate can optionally be heated in a baking unit. More details concerning the heating in a baking unit can be found in WO 2007/057348 page 44 line 26 to page 45 line 20.
  • the printing plate thus obtained can be used for conventional, so-called wet offset printing, in which ink and an aqueous dampening liquid is supplied to the plate.
  • Another suitable printing method uses a so-called single-fluid ink without a dampening liquid.
  • Suitable single-fluid inks have been described in U.S. Pat. Nos. 4,045,232; 4,981,517 and 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.
  • a 0.3 mm thick aluminum foil was degreased by spraying with an aqueous solution containing 26 g/l NaOH at 65° C. for 2 seconds and rinsed with demineralised water for 1.5 seconds.
  • the foil was then electrochemically grained during 10 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+ ions at a temperature of 37° C. and a current density of about 100 A/dm 2 .
  • the aluminum foil was then desmutted by etching with an aqueous solution containing 5.5 g/l of NaOH at 36° C. for 2 seconds and rinsed with demineralised water for 2 seconds.
  • the foil was subsequently subjected to anodic oxidation during 15 seconds in an aqueous solution containing 145 g/l of sulfuric acid at a temperature of 50° C. and a current density of 17 A/dm 2 , then washed with demineralised water for 11 seconds and dried at 120° C. for 5 seconds.
  • the support thus obtained was characterized by a surface roughness Ra of 0.35-0.4 ⁇ m (measured with interferometer NT1100) and had an oxide weight of 3.0 g/m 2 .
  • the printing plate precursor PPP-00 to PPP-06 were prepared by coating onto the above described support S-01 the components as defined in Table 1 dissolved in a mixture of 35% by volume of MEK and 65% by volume of Dowanol PM (1-methoxy-2-propanol, commercially available from DOW CHEMICAL Company).
  • the coating solution was applied at a wet coating thickness of 30 ⁇ m and then dried at 120° C. for 1 minute in a circulation oven. Dry coating weight 1,295 g/m 2
  • Tegoglide 410 is a surfactant commercially available from Evonik Tego Chemie GmbH; 3) CN 104 is an epoxy acrylate oligomer commercially available from Arkema; 4) CN-UVE 151M is an epoxy diacrylate monomer commercially available from Sartomer 5) Mono Z1620 is a solution in MEK containing 30 wt % of a reaction product from 1 mole of 2-hydroxyethylmethacrylate and 0.5 mole of 2-(2-hydroxyethyl-piperidine); 6) Disperbyk 182 is commercially available from BYK Chemie GmbH.; 7) HABI 1-2 is a photoinitiator, commercially available from Hodogaya Chemical; 8) MBT is 2-mercapto-benzimidazool; 9) Sipomer PAM 100 is a methacrylate phosphonic ester commercially available from Rhodia; 10) Albritect
  • a solution in water with the composition as defined in Table 2 was coated (40 ⁇ m) on the printing plate precursors, and dried at 120° C. for 2 minutes.
  • the so-formed protective top layer OC-1 has a dry thickness or dry coating weight of 1.35 g/m 2 .
  • Mowiol 4-88 is a partially hydrolyzed polyvinylalcohol from Kuraray.
  • Mowiol 4-98 is a fully hydrolyzed polyvinylalcohol from Kuraray;
  • Ebotec MB-SF is a biocide commercially available from Bode Chemie Hamburg GmbH;
  • Advantage S is a dewetting agent commercially available from; ISP;
  • Lutensol A8 is a surface active agent commercially available from BASF.
  • Exposure was carried out on a Lücher Expose plate-setter, a UV contact frame with band filters to select the 405 nm region or a 395 nm UV LED firejet 200 of Phoseon, at an energy density of 25 mJ/cm 2 .
  • ⁇ E was calculated from the L*, a* and b* values of the plate precursor before and after imaging.
  • the total colour difference ⁇ E is a single value that takes into account the difference between the L*, a* and b* values of the image areas and the non-image areas:
  • ⁇ E ⁇ square root over ( ⁇ L 2 + ⁇ a 2 + ⁇ b 2 ) ⁇
  • a solid pattern was imaged on the printing plate precursors PPP-00 to PPP-06 and the L*a*b* values of both the non-image areas and the solid imaged area were measured and the respective delta E ( ⁇ E) values were calculated.
  • Table 3 Print plate precursors PPP-00 to PPP-06 with an overcoat layer
  • Table 4 Print plate precursors PPP-00 to PPP-06 without an overcoat layer
  • Tables 3 and 4 show that at an exposure energy of 25 mJ/cm 2 a good visual contrast ⁇ E ⁇ 5 is obtained for the inventive printing plate precursors including a coating including the combination of PF 6 ⁇ counter ion as part of an onium structure and fluomix.
  • the onium salt is preferably iodonium salt.
  • the printing plate precursor PPP-07 to PPP-12 were prepared by coating onto the above described support S-01 the components as defined in Table 5 dissolved in a mixture of 35% by volume of MEK and 65% by volume of Dowanol PM (1-methoxy-2-propanol, commercially available from DOW CHEMICAL Company).
  • the coating solution was applied at a wet coating thickness of 30 ⁇ m and then dried at 120° C. for 1 minute in a circulation oven.
  • a solution in water with the composition as defined in Table 2 above was coated (40 ⁇ m) on the printing plate precursors, and dried at 120° C. for 2 minutes.
  • the so-formed protective top layer OC-1 has a dry thickness or dry coating weight of 1.35 g/m 2 .
  • Exposure was carried out on a Lücher Expose plate-setter, a UV contact frame with band filters to select the 405 nm region or a 395 nm UV LED firejet 200 of Phoseon, at an energy density of 25 mJ/cm 2 .
  • ⁇ E was measured before and after imaging following the method as described in Example 1.
  • the printing plate precursor PPP-14 to PPP-16 were prepared by coating onto the above described support S-01 the components as defined in Table 7 dissolved in a mixture of 22% by volume of MeOH and 77% by volume of Dowanol PM (1-methoxy-2-propanol, commercially available from DOW CHEMICAL Company) and 1% by volume monoethylene glycol.
  • the coating solution was applied at a wet coating thickness of 26 ⁇ m and then dried at 120° C. for 1 minute in a circulation oven.
  • Exposure was carried out on a Lücher Expose plate-setter, a UV contact frame with band filters to select the 405 nm region or a 395 nm UV LED firejet 200 of Phoseon, at an energy density of 70 mJ/cm 2 .
  • ⁇ E was measured before and after imaging following the method as described in Example 1.
  • the printing plate precursor PPP-17 to PPP-19 were prepared by coating onto the above described support S-01 the components as defined in Table 9 dissolved in a mixture of 35% by volume of MEK and 65% by volume of Dowanol PM (1-methoxy-2-propanol, commercially available from DOW CHEMICAL Company).
  • the coating solution was applied at a wet coating thickness of 30 ⁇ m and then dried at 120° C. for 1 minute in a circulation oven.
  • Exposure was carried out on a Lücher Expose plate-setter, a UV contact frame with band filters to select the 405 nm region or a 395 nm UV LED firejet 200 of Phoseon, at an energy density of 25 mJ/cm 2 .
  • Printing plates PP-17 to PP-19 were evaluated for development on-press.
  • the printing plates were mounted on a Heidelberg GTO52 dalhgren press using K+E Skinnex 800 SPEED IK black ink (trademark of BASF Druckmaschine GmbH) and 4 wt % Prima FS303 SF (trademark of Agfa Graphics) and 8% isopropanol in water as fountain solution.
  • a compressible blanket was used and printing was performed on non-coated offset paper. Prior to paper feeding, 10 press revolution with only the dampening system followed by 5 revolutions with only the inking rollers was performed. Up to 500 sheets were printed and visual assessment of every 10 sheets was performed to evaluate toning (i.e. accepting ink) in the non-image areas.
  • Toning behaviour of the on-press developed printing plates was visually assessed every 10 printed sheets. The results are given in Table 10.

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