WO2007057409A1 - Procede de fabrication d'une plaque d'impression lithographique - Google Patents

Procede de fabrication d'une plaque d'impression lithographique Download PDF

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Publication number
WO2007057409A1
WO2007057409A1 PCT/EP2006/068487 EP2006068487W WO2007057409A1 WO 2007057409 A1 WO2007057409 A1 WO 2007057409A1 EP 2006068487 W EP2006068487 W EP 2006068487W WO 2007057409 A1 WO2007057409 A1 WO 2007057409A1
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Prior art keywords
layer
precursor
compound
coating
mol
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PCT/EP2006/068487
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English (en)
Inventor
Alexander Williamson
Original Assignee
Agfa Graphics Nv
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Priority claimed from EP05111012A external-priority patent/EP1788448B1/fr
Application filed by Agfa Graphics Nv filed Critical Agfa Graphics Nv
Publication of WO2007057409A1 publication Critical patent/WO2007057409A1/fr

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Classifications

    • 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
    • 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
    • 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
    • G03F7/085—Photosensitive compositions characterised by adhesion-promoting non-macromolecular additives
    • 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
    • B41C2210/04—Negative working, i.e. the non-exposed (non-imaged) areas are removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/08—Developable by water or the fountain 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

Definitions

  • Printing masters are generally obtained by the so-called computer-to-film (CtF) method, wherein various pre-press steps such as typeface selection, scanning, color separation, screening, trapping, layout and imposition are accomplished digitally and each color selection is transferred to graphic arts film using an imagesetter.
  • the film can be used as a mask for the exposure of an imaging material called plate precursor and after plate processing, a printing plate is obtained which can be used as a master.
  • the so-called x computer-to-plate' (CtP) method has gained a lot of interest.
  • This method also called 'direct-to-plate' , bypasses the creation of film because the digital document is transferred directly to a printing plate precursor by means of a so-called plate-setter.
  • a printing plate precursor for CtP is often called a digital plate.
  • Photopolymers can be sensitized for blue, green or red light (i.e. wavelength range between 450 and 750 nm) , for violet light (i.e. wavelength range between 350 and 450 nm) or for infrared light (i.e. wavelength range between 750 and 1500 nm) .
  • Laser sources have been increasingly used to expose a printing plate precursor which is sensitized to a corresponding laser wavelength.
  • an Ar laser (488 nm) or a FD-YAG laser (532 nm) can be used for exposing a visible light sensitized photopolymer plate.
  • the wide-scale availability of low cost blue or violet laser diodes, originally developed for data storage by means of DVD, has enabled the production of plate- setters operating at shorter wavelength.
  • semiconductor lasers emitting from 350 to 450 nm have been realized using an InGaN material.
  • An infrared laser diode emitting around 830 nm or a Nd-YAG laser emitting around 1060 nm can also be used.
  • a photopolymer plate is processed in alkaline developer having a pH > 10 and subsequently gummed to protect the plate from contamination, e.g. by oxidation, fingerprints, fats, oil or dust, or from damaging, e.g. by scratches during handling of the plate .
  • Photopolymer plates are also described in the literature wherein the wet processing and gumming steps are replaced by an on- press processing whereby the imaged precursor is mounted on a press and processed on-press by applying ink and fountain to remove the unexposed areas from the support.
  • a compound for increasing the adhesion between the photopolymer coating and the support can also added to the printing plate precursor for increasing the resistance of the exposed areas during the processing step and for improving the durability of the plate in the printing process as disclosed in EP 851 299, EP 1 091 251, US 2004/214105, EP 1 491 356, US 2005/39620, EP 1 495 866, EP 1 500 498, EP 1 520 694 and EP 1 557 262.
  • the binder for the photopolymerisable layer may be selected from a broad list of polymers without limitations including linear organic polymers having film- forming properties or having crosslinkable functional groups.
  • polymers having hydrophilic groups include acrylic resins, methacrylic resins, polystyrene resins, novolac type resins, polyester resins, synthetic rubbers, natural rubber, and polymers having ethylenically unsaturated bonds.
  • Polymers having hydrophilic groups are preferred and specific examples of such hydrophilic polymers are listed in the literature.
  • Specific examples of such hydrophilic polymers are poly (meth) acrylic acid and salts thereof, polyvinyl alcohol, hydrolyzed polyvinyl acetate having a degree of hydrolysis of 60 % by weight or higher, preferably 80 % by weight or higher, polyvinylpyrrolidone and copolymers of polyvinylpyrrolidone.
  • hydrophilic polymers as binder in lithographic printing plate precursors is an insufficient clean-out of the non-exposed areas by means of fountain and ink in an on-press processing step, even after printing a high number of sheets .
  • This object is realized by the method of claim 1, having the specific feature that the photopolymerizable layer comprises a polyvinyl acetate binder having a hydrolysis degree of less than 60 mol %.
  • the precursor further comprises a compound capable of interacting with the support, hereinafter also referred to as "adhesion promoting compound", which is present in the photopolymerizable layer or in an intermediate layer between the photopolymerizable layer and the support.
  • a method of making a lithographic printing plate comprising the steps of: (a) providing a lithographic printing plate precursor comprising
  • the aluminum oxide surface may be treated with polyvinylphosphonic acid, polyvinylmethylphosphonic acid, phosphoric acid esters of polyvinyl alcohol, polyvinylsulfonic acid, polyvinylbenzenesulfonic acid, sulfuric acid esters of polyvinyl alcohol, and acetals of polyvinyl alcohols formed by reaction with a sulfonated 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 ALLIED COLLOIDS.
  • 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 ALLIED COLLOIDS.
  • the grained and anodized aluminum support 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 .
  • 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 . The latter is particularly preferred.
  • 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 adhesion promoting compound may be selected from at least one of the low molecular weight compounds or polymeric compounds as described in EP-A 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.
  • 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.
  • the photopolymerizable composition according to the present invention comprises a hexaaryl-bisimidazole (HABI; dimer of triaryl -imidazole) compound as a photopolymerization initiator alone or in combination with further photoinitiators .
  • HABI hexaaryl-bisimidazole
  • a procedure for the preparation of hexaarylbisimidazoles is described in DE 1470 154 and their use in photopolymerizable compositions is documented in EP 24 629, EP 107 792, US 4 410 621, EP 215 453 and DE 3 211 312.
  • Preferred derivatives are e. g.
  • a very high sensitivity can be obtained in the context of the present invention by the combination of an optical brightener as sensitizer and a hexaarylbisimidazole as photoinitiator.
  • Suitable classes of photoinitiators other than hexaarylbisimidazole compounds include aromatic ketones, aromatic onium salts, organic peroxides, thio compounds, ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds and compounds having a carbon-halogen bond, but preferably the composition comprises a non-boron comprising photopolymerization initiator and particularly preferred the photopolymerization initiator comprises no boron comopound.
  • Many specific examples of photoinitiators suitable for the present invention can be found in EP-A 1 091 247. Other preferred initiators are trihalo methyl sulphones.
  • hexaarylbisimidazole compounds and/or metallocene compounds are used alone or in combination with other suitable photoinitiators, in particular with aromatic ketones, aromatic onium salts, organic peroxides, thio compounds, ketoxime ester compounds, azinium compounds, active ester compounds or compounds having a carbon halogen bond.
  • the hexaarylbisimidazole compounds make more than 50 mol-%, preferably at least 80 mol-% and particularly preferred at least 90 mol-% of all the photoinitiators used in the photopolymerizable composition of the present invention.
  • said polymerizable monomer or oligomer may be a combination of a monomer or oligomer comprising at least one epoxy or vinyl ether functional group and a polymerizable ethylenically unsaturated compound, having at least one terminal ethylenic group
  • said initiator may be a combination of a cationic initiator and a free-radical initiator.
  • a monomer or oligomer comprising at least one epoxy or vinyl ether functional group and a polymerizable ethylenically unsaturated compound, having at least one terminal ethylenic group can be the same compound wherein the compound contains both ethylenic group and epoxy or vinyl ether group.
  • Examples of such compounds include epoxy functional acrylic monomers, such as glycidyl acrylate.
  • the free radical initiator and the cationic initiator can be the same compound if the compound is capable of generating both free radical and free acid.
  • Examples of such compounds include various onium salts such as diaryliodonium hexafluoroantimonate and s-triazines such as 2 , 4-bis (trichloromethyl) -6- [ (4-ethoxyethylenoxy) -phen-1-yl] - s-triazine which are capable of generating both free radical and free acid in the presence of a sensitizer.
  • the photopolymerizable layer may also comprise a multifunctional monomer.
  • This monomer contains at least two functional groups selected from an ethylenically unsaturated group and/or an epoxy or vinyl ether group.
  • Particular multifunctional monomers for use in the photopolymer coating are disclosed in US 6,410,205 , US 5,049,479 , EP 1079276 , EP 1369232 , EP 1369231 EP 1341040 , US 2003/0124460 , EP 1241002 , EP 1288720 and in the reference book including the cited refences : Chemistry & Technology UV & EB formulation for coatings, inks & paints - Volume 2 - Prepolymers andReactive Diluents for UV and EB Curable Formulations by N.
  • the photopolymerizable layer may also comprise a co- initiator .
  • a co-initiator is used in combination with a free radical initiator and/or cationic initator.
  • the photopolymerizable layer may also comprise an inhibitor.
  • Particular inhibitors for use in the photopolymer coating are disclosed in US 6,410,205, EP 1288720 and the unpublished patent application EP-A 04101955, filed on 6/5/2004.
  • the binder of the photopolymerizable layer in the present invention is a polyvinyl acetate having a hydrolysis degree of less than 60 mol %, preferably having a hydrolysis degree of at most 58 mol% and at least 20 mol, most preferably having a hydrolysis degree of at most 56 mol% and at least 40 mol%.
  • a copolymer of vinyl acetate and vinyl alcohol is obtained.
  • the coating comprising this partially hydrolysed polyvinyl acetate in the photopolymerizable layer exhibits an excellent clean- out of the non-exposed areas after a few number of printed sheets in the on-press processing step.
  • POL-02 ALCOTEX 55-002H, a polyvinyl acetate with a hydrolysis degree of 54.0-57.0 mol %, commercially available from SYNTHOMER Limited, UK.
  • POL-03 ALCOTEX WDlOO, a polyvinyl acetate with a hydrolysis degree of 42.0-45.0 mol %, commercially available from SYNTHOMER
  • POL-04 ALCOTEX WD200, a polyvinyl acetate with a hydrolysis degree of 42.0-45.0 mol %, commercially available from SYNTHOMER Limited, UK.
  • POL- 05 ALCOTEX WD30, a polyvinyl acetate with a hydrolysis degree of 48.5 mol %, commercially available from SYNTHOMER Limited, UK.
  • POL- 06 POLYVIOL W45/450, a polyvinyl acetate with a hydrolysis degree of 42.0-50.0 mol %, commercially available from WACKER.
  • POL- 07 Gohsefimer LL02, a polyvinyl acetate with a hydrolysis degree of 45.0-51.0 mol %, commercially available from Nippon Gohsei .
  • the photopolymerizable layer may also further comprise an other binder in admixture with the partially hydrolysed polyvinylacetate of the present invention.
  • the additional binder can be selected from a wide series of organic polymers. Compositions of different binders can also be used.
  • Useful additional binders include for example chlorinated polyalkylene (in particular chlorinated polyethylene and chlorinated polypropylene) , polymethacrylic acid alkyl esters or alkenyl esters (in particular polymethyl (meth) acrylate, polyethyl (meth) acrylate, polybutyl (meth) acrylate, polyisobutyl (meth) acrylate, polyhexyl (meth) acrylate, poly (2-ethylhexyl) (meth) acrylate and polyalkyl (meth) acrylate copolymers of (meth) acrylic acid alkyl esters or alkenyl esters with other copolymerizable monomers (in particular with (met) acrylonitrile, vinyl chloride, vinylidene chloride, styrene and/or butadiene), polyvinyl chloride (PVC, vinylchloride/ (meth) acrylonitrile copolymers, polyvinyliden
  • Particulary preferred binders are polymers having vinylcaprolactam, vinylpyrrolidone or alkylated vinylpyrrolidone as monomeric units.
  • Alkylated vinylpyrrolidone polymers can be obtained by grafting alfa-olefines onto the vinylpyrrolidone polymer backbone. Typical examples of such products are the Agrimer AL Graft polymers commercially available from ISP.
  • the length of the alkylation group may vary from C 4 to C 30 .
  • binders containing carboxyl groups are binders containing carboxyl groups, in particular copolymers containing monomeric units of a, ⁇ -unsaturated carboxylic acids or monomeric units of ⁇ , ⁇ -unsaturated dicarboxylic acids (preferably acrylic acid, methacrylic acid, crotonic acid, vinylacetic acid, maleic acid or itaconic acid) .
  • copolymers are to be understood in the context of the present invention as polymers containing units of at least 2 different monomers, thus also terpolymers and higher mixed polymers.
  • copolymers containing units of maleic anhydride and styrene, unsaturated ethers or esters or unsaturated aliphatic hydrocarbons and the esterification products obtained from such copolymers are, for example, copolymers containing units of maleic anhydride and styrene, unsaturated ethers or esters or unsaturated aliphatic hydrocarbons and the esterification products obtained from such copolymers.
  • Further suitable binders are products obtainable from the conversion of hydroxyl-containing polymers with intramolecular dicarboxylic anhydrides.
  • Further useful binders are polymers in which groups with acid hydrogen atoms are present, some or all of which are converted with activated isocyanates. Examples of these polymers are products obtained by conversion of hydroxyl -containing polymers with aliphatic or aromatic sulfonyl isocyanates or phosphinic acid isocyanates.
  • polymers with s aliphatic or aromatic hydroxyl groups for example copolymers containing units of hydroxyalkyl (meth) acrylates, allyl alcohol, hydroxystyrene or vinyl alcohol, as well as epoxy resins, provided they carry a sufficient number of free OH groups.
  • Particular useful binder and particular useful reactive binders are disclosed in EP 1 o 369 232, EP 1 369 231, EP 1 341 040, US 2003/0124460, EP 1 241 002, EP 1 288 720, US 6,027,857, US 6,171,735 and US 6,420,089.
  • the polymeric binder may also comprise a hydrophobic backbone, and pendant groups including for example a hydrophilic poly (alkylene oxide) segment.
  • the polymeric binder may also include pendant cyano groups attached to the hydrophobic backbone.
  • a combination of such binders may also be employed.
  • the polymeric binder is a 0 solid at room temperature, and is typically a non-elastomeric thermoplastic.
  • the polymeric binder comprises both hydrophilic and hydrophobic regions, which is thought to be important for enhancing differentiation of the exposed and unexposed areas by facilitating developability .
  • the polymeric binder is characterized by a 5 number average molecular weight (Mn) in the range from about 10.000 to 250.000, more commonly in the range from about 25.000 to 200.000.
  • the polymerizable composition may comprise discrete particles of the polymeric binder.
  • the discrete particles are particles of the polymeric binder which are suspended in the polymerizable 0 composition. The presence of discrete particles tends to promote developability of the unexposed areas.
  • Specific examples of the polymeric binders according to this embodiment are described in US 6.899.994, 2004/0260050, US2005/0003285 , US2005/0170286 and US2005/0123853.
  • the imageable layer may optionally comprise one or more co-binders.
  • Printing plate precursors the imageable layer of which comprises a binder and optionally a co-binder according this embodiment and described in more detail in US2004/0260050, US2005/0003285 and US2005/0123853 , optionally comprises a topcoat and an interlayer.
  • Nonionic surfactants are preferred.
  • Preferred nonionic surfactants are polymers and oligomers containing one or more polyether (such as polyethylene glycol, polypropylene glycol, and copolymer of ethylene glycol and propylene glycol) segments.
  • nonionic surfactants are block copolymers of propylene glycol and ethylene glycol (also called block copolymer of propylene oxide and ethylene oxide) ; ethoxylated or propoxylated acrylate oligomers; and polyethoxylated alkylphenols and polyethoxylated fatty alcohols.
  • the nonionic surfactant is preferably added in an amount ranging between 0.1 and 30% by weight of the coating, more preferably between 0.5 and 20%, and most preferably between 1 and 15%.
  • the photocurable composition may also comprise a sensitizer.
  • a sensitizer are violet light absorbing sensitizers, having an absorption spectrum between 350 nm and 450 ran, preferably between 370 nm and 420 nm, more preferably between 390 nm and 415 nm.
  • Particular preferred sensitizers are disclosed in EP 1 349 006 paragraph [0007] to [0009], EP-A-3103499, filed on 22/03/2003, and WO2004/047930 , including the cited references in these patent applications.
  • sensitizers are infrared light absorbing dyes, having an absorption spectrum between 750 nm and 1300 nm, preferably between 780 nm and 1200 nm, more preferably between 800 nm and 1100 nm.
  • Particular preferred sensitizers are heptamethinecyane dyes, specially the dyes disclosed in EP 1 359 008 paragraph [0030] to [0032] .
  • Other preferred sensitizers are blue, green or red light absorbing sensitizers, having an absorption spectrum between 450 nm and 750 nm.
  • Useful sensitizers can be selected from the sensitizing dyes disclosed in US 6,410,205, US 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 and EP 1 288 720.
  • the pigments have a particle size which is preferably less than 10 ⁇ m, more preferably less than 5 ⁇ m and especially preferably less 5 than 3 ⁇ m.
  • the method for dispersing the pigments may be any known dispersion method which is used for the production of ink or toner or the like. Dispersing machines include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a dispenser, a KD mill, a colloid mill, a dynatron, a o three-roll mill and a press kneader. Details thereof are described in " Latest Pigment Applied Technology" (CMC Publications, published in 1986) .
  • the colorant can also be a dye.
  • Any known dyes such as commercially available dyes or dyes described in, for example, "Dye Handbook" (edited by the Organic Synthetic Chemistry Association, published in 1970) which are colored for the human eye, can be used as colorant in the photopolymerizable coating.
  • Specific examples 0 thereof include azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalacyanine dyes, carbionium dyes, quinonimine dyes, methine dyes, and the like. Phthalocyanine dyes are preferrred.
  • Suitable dyes are salt-forming organic dyes and may be selected from oil -soluble dyes and basic dyes. Specific examples 5 thereof are (herein is CI an abbreviation for Color Index) : Oil
  • the coating may comprise a top layer which acts as an oxygen barrier layer, hereinafter also referred to as "overcoat layer” or “overcoat” .
  • Preferred binders which can be used in the top layer are polyvinyl alcohol and the polymers disclosed in EP-A-3103498, filed on 22/03/2003, US 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 an hydrolysis degree ranging between 74 mol % and 99 mol %.
  • the toplayer has a coating thickness
  • the top layer may also comprise a component selected from the compounds of a gum solution as disclosed in the unpublished PCT Application PCT/EP 2005/052298, filed on 18 May 2005, from lines 1 on page 5 to line 35 on page 11.
  • the exposed, optionally exposed and preheated, precursor is processed on-press, i.e. while the precursor is mounted on the plate cylinder of a lithographic printing press, by rotating said plate cylinder while feeding dampening liquid and/or ink to the coating of the precursor.
  • dampening liquid is supplied to the plate during start-up of the press.
  • the ink supply is switched on.
  • supply of dampening liquid and ink can be started simultaneously or only ink can be supplied during a number of revolutions before switching on the supply of dampening liquid.
  • the precursor may be exposed and processed on-press, i.e. after step (a) and before step (b) , an additional step (a' ) is provided wherein the precursor is mounted on a plate cylinder of a lithographic printing press, and wherein step (d) is not present; optionally, after step (b) and before step (e) , an additional pre-heat step (c') is provided.
  • the foil was subsequently subjected to anodic oxidation during 10 seconds in an aqueous solution containing 145 g/1 of sulfuric acid at a temperature of 57 0 C and a current density of 33 A/dm , then washed with demineralized water for 7 seconds and post-treated for 4 seconds by spraying a solution containing 2.2 g/1 of polyvinylphosphonic acid at 7O 0 C, rinsed with demineralized water for 3.5 seconds and dried at 120 0 C for 7 seconds.
  • a 0.3 mm thick aluminum foil was degreased by spraying with an aqueous solution containing 34 g/1 of NaOH at 70 0 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/1 of HCl, 15 g/1 of SO 4 ions and 5 g/1 of Al ions at a temperature of 37°C and a current density of about 120-130 A/dm .
  • the aluminum foil was desmutted by etching with an aqueous solution containing 145 g/1 of sulfuric acid at 8O 0 C for 5 seconds and rinsed with demineralized water for 4 seconds.
  • This support is carried out in the same way as described for support S-4 with the exception that the polyvinyl phosphonic acid layer is partially removed by treatment with PD91, a water-based alkaline developer solution, commercially available from Agfa-Gevaert , followed by washing with water.
  • PD91 a water-based alkaline developer solution, commercially available from Agfa-Gevaert , followed by washing with water.
  • intermediate layers 1-1 to 1-6 The coating compositions for the intermediate layers 1-1 to 1-6 were prepared by mixing the ingredients as specified in Table 1. The resulting solutions were coated with a bar-coater on a support. After coating, the plate was dried for 1 minute at 120 0 C in a circulation oven.
  • Table 1 Compositions of the intermediate layer solutions and thickness of dried layer.
  • Sipomer PAM 100 is a phosphate functional speciality methacrylate monomer, obtained from RHODIA. This compound was treated by extraction with methyl -tert-butylether, collection of the lower phase, and subsequent addition of 250 ppm (parts per million) of para-methoxyphenol .
  • Dowanol PM is propylene glycol monomethylether, trade mark of Dow Chemical Company.
  • the coating compositions for the photosensitive layers P-I to P-6 were prepared by mixing the ingredients as specified in Table 2. The resulting solutions were coated with a bar-coater on a support or on an intermediate layer. After coating, the plate was dried for 1 minute at 12O 0 C in a circulation oven. The resulting applied 2 2 amount is 0.75 g/m for photosensitive layer P-2 and 1.50 g/m for the other photosensitive layers.
  • Alcotex 552P is a 40% by weight solution in water of polyvinylalcohol having a hydrolysis degree of 55 mol%, commercially available from Synthomer
  • Mowiol 4/88 is a polyvinylalcohol having a hydrolysis degree of 88 mol%, commercially available from Clariant
  • Mowiol 6/98 is a polyvinylalcohol having a hydrolysis degree of 98 mol%, commercially available from Clariant
  • OTos represents a tosylate anion
  • TBMPS is tri-bromo-methylphenyl-sulphone
  • FST 426R is a solution in 2-butanone containing 88.2 wt . % of a reaction product from 1 mole of 2 , 2 , 4-trimethyl- hexamethylenediisocyanate and 2 moles of hydroxy- ethylmethacrylate (viscosity 3.30 mm 2 /s at 25 0 C)
  • Lupasol P is a solution of 50% by weight of a polyethylene imine in water, commercially available from BASF
  • the plates were imaged with a Creo Trendsetter IR laser (830 nm) at different energies varying between 100 mJ/cm and 300 mJ/cm .
  • the plates were mounted on a GTO46 printing press (available from Heidelberger Druckmaschinen AG) , and a print job was started using K + E Novavit 800 Skinnex ink (trademark of BASF Drucksysteme GmbH) and 3% FSlOl (trademark of AGFA) in 10% isopropanol as fountain liquid, compressible blanket and by using offset paper.
  • the clean-out is defined by the number of sheets needed to obtain on the non-exposed areas on optical density of 0.0 while on the full exposed areas (or the 100 % dot areas of a screen) the optical density is at least 1.5, indicating an excellent ink- acceptance.
  • the indication ⁇ 5 means that a full clean-out is obtained after printing 2, 3 or 4 sheets; >1000 means that no clean- out is obtained after printing 1000 sheets.
  • Geniosil GF31 is 3-methacryloxypropyl-tri-methoxy-silane

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

Abstract

L'invention concerne un procédé de fabrication d'une plaque d'impression lithographique qui comprend les étapes consistant: a) à produire un précurseur de plaque d'impression lithographique comportant (i) un support à surface hydrophile ou qui est revêtu d'une couche hydrophile, (ii) un revêtement placé sur celui-ci, comportant une couche photopolymérisable, et éventuellement, une couche intermédiaire entre la couche polymérisable et le support, cette couche photopolymérisable contenant un composé polymérisable, un initiateur de polymérisation, et un acétate de polyvinyle partiellement hydrolysé, et dans lequel un composé favorisant l'adhésion est présent dans la couche intermédiaire ou la couche photopolymérisable, ce composé consistant en un composé pouvant interagir avec le support, b) à exposer ce revêtement à l'image, c) à éventuellement chauffer le précurseur dans une unité de préchauffage, d) à monter le précurseur exposé sur un cylindre porte-plaque d'une presse lithographique, e) à développer par rotation le cylindre porte-plaque tout en alimentant le revêtement en liquide d'amortissement et/ou en encre, éliminant ainsi les zones non exposées du revêtement, caractérisées en ce que l'acétate de polyvinyle possède un degré d'hydrolyse inférieur à 60 mol %.
PCT/EP2006/068487 2005-11-21 2006-11-15 Procede de fabrication d'une plaque d'impression lithographique WO2007057409A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP05111012.0 2005-11-21
EP05111012A EP1788448B1 (fr) 2005-11-21 2005-11-21 Procédé de fabrication d'une plaque d'impression lithographique
US74952605P 2005-12-12 2005-12-12
US60/749,526 2005-12-12

Publications (1)

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WO2007057409A1 true WO2007057409A1 (fr) 2007-05-24

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009063024A1 (fr) * 2007-11-16 2009-05-22 Agfa Graphics Nv Procédé de fabrication d'une plaque d'impression lithographique
WO2010027415A1 (fr) * 2008-09-04 2010-03-11 Eastman Kodak Company Élément de travail sur négatif pouvant être imagé et procédé d'utilisation

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1557262A2 (fr) * 2004-01-23 2005-07-27 Fuji Photo Film Co., Ltd. Précurseur de plaque d'impression lithographique et méthode pour l'impression lithographique.

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1557262A2 (fr) * 2004-01-23 2005-07-27 Fuji Photo Film Co., Ltd. Précurseur de plaque d'impression lithographique et méthode pour l'impression lithographique.

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009063024A1 (fr) * 2007-11-16 2009-05-22 Agfa Graphics Nv Procédé de fabrication d'une plaque d'impression lithographique
US8415087B2 (en) 2007-11-16 2013-04-09 Agfa Graphics Nv Method of making a lithographic printing plate
WO2010027415A1 (fr) * 2008-09-04 2010-03-11 Eastman Kodak Company Élément de travail sur négatif pouvant être imagé et procédé d'utilisation
US8304170B2 (en) 2008-09-04 2012-11-06 Eastman Kodak Company Negative-working imageable element and method of use
CN102143843B (zh) * 2008-09-04 2013-01-02 伊斯曼柯达公司 负性工作可成像元件和使用方法

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