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
  • B41C1/1025—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 using materials comprising a polymeric matrix containing a polymeric particulate material, e.g. hydrophobic heat coalescing particles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
  • B41N3/00—Preparing for use and conserving printing surfaces
  • B41N3/03—Chemical or electrical pretreatment
  • B41N3/036—Chemical or electrical pretreatment characterised by the presence of a polymeric hydrophilic coating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
  • B41N3/00—Preparing for use and conserving printing surfaces
  • B41N3/08—Damping; Neutralising or similar differentiation treatments for lithographic printing formes; Gumming or finishing solutions, fountain solutions, correction or deletion fluids, or on-press development
• • 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
  • 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

• the present invention relates to a method for making a lithographic printing plate. More in particular, the present invention relates to a method wherein the lithographic printing plate precursor is coated with a hydrophilic protective layer after image-wise recording and before developing.
• a so-called printing master such as a printing plate is mounted on a cylinder of the printing press.
• the master carries a lithographic image on its surface and a printed copy is obtained by applying ink to said image and then transferring the ink from the master onto a receiver material, which is typically paper.
• ink as well as an aqueous fountain solution (also called dampening liquid) are supplied to the lithographic image which consists of oleophilic (or hydrophobic, i.e. ink-accepting, water-repelling) areas as well as hydrophilic (or oleophobic, i.e. water-accepting, ink-repelling) areas.
• driographic the lithographic image consists of ink-accepting and ink-abhesive (ink-repelling) areas and during driographic printing, only ink is supplied to the master.
• Printing masters are generally obtained by the 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.
• CtF computer-to-film
• 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 '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 plate precursor by means of a so-called plate-setter.
• thermal plates sensitive to heat or infrared light
• thermal materials may be exposed directly to heat, e.g. by means of a thermal head, but preferably comprise a compound that converts absorbed light into heat and are therefore suitable for exposure by lasers, especially infrared laser diodes.
• the heat which is generated on image-wise exposure, triggers a (physico-)chemical process, such as ablation, polymerization, insolubilization by cross-linking of a polymer, decomposition, or particle coagulation of a thermoplastic polymer latex, and after optional processing, a lithographic image is obtained.
• Many thermal plate materials are based on heat-induced coagulation of thermoplastic polymer particles.
• EP-A 1 065 049 discloses a heat-sensitive material for making lithographic printing plates comprising on a lithographic support an image-forming layer comprising a hydrophilic binder, a cross-linking agent for a hydrophilic binder and dispersed hydrophobic thermoplatic polymer particles, and a covering layer comprising an organic compound comprising cationic groups.
• EP-A 770 494 discloses a method wherein an imaging material comprising an image-recording layer of a hydrophilic binder, a compound capable of converting light to heat and hydrophobic thermoplastic polymer particles, is image-wise exposed, thereby inducing coalescence of the polymer particles and converting the exposed areas into an hydrophobic phase which defines the printing areas of the printing master.
• the press run can be started immediately after exposure without any additional treatment because the layer is developed by interaction with the fountain and ink that are supplied to the cylinder during the press run.
• the non-exposed areas are removed from the support and thereby define the non-printing areas of the plate.
• This on-press processing method provides only a rapid clean-out (i.e.
• US 6,387,595 discloses a lithographic printing plate wherein a photosensitive layer capable of hardening or solubilization upon exposure to actinic radiation and an overcoat with a covarage of from 0.001 to 0.150 g/m 2 which is soluble or dispersible in ink and/or fountain solution.
• the image-wise exposed material is on-press developable and the incorporation of this ultrathin overcoat provides excellent white light stability, high contrast, excellent ink receptivity and fast on-press development.
• the presence of such a thin overcoat of a water-soluble polymer, applied on the precursor of the present invention before image-wise exposing has the drawback of reducing the sensitivity on heat-mode recording.
• EP-A 816 070 discloses a heat sensitive imaging element comprising on a hydrophilic surface of a lithographic base an image forming layer including at least hydrophobic thermoplastic polymer particles and a compound capable of converting light into heat, and wherein, on the image forming layer, a covering layer is present having a thickness between 0.1 and 3 ⁇ m.
• a method wherein the covering layer is applied on the image forming layer after the exposure step and before processing the material is not limited to the covering layer after the exposure step and before processing the material.
• EP-A 1 342 568 discloses a method of making a lithographic printing plate wherein an imaging material comprising an image-recording layer of a hydrophilic binder, a compound capable of converting light to heat and hydrophobic thermoplastic polymer particles, is image-wise exposed, thereby inducing coalescence of the polymer particles.
• the image-wise exposed material is processed by applying a gum solution to the image-recording layer, thereby removing non-exposed areas of the coating from the support.
• This object is realized by the method as defined in claim 1 wherein a hydrophilic protective layer is applied on the coating of the precursor after the image-wise exposing step and before the on-press processing step.
• this hydrophilic protective layer on the coating of the precursor is carried out by coating and drying of a hydrophilic protective coating solution in such a way that on top of the precursor a hydrophilic layer is present.
• This hydrophilic layer is able to improve the clean-out, more particularly, those parts of the non-image areas which are contaminated by ink are removed by the on-press processing within a short time. The efficiency of the clean-out may depend on the method of coating this hydrophilic protective coating solution.
• said hydrophilic protective layer is preferably applied by coating a hydrophilic protective coating solution by means of a spray nozzle or a jet nozzle. These coating methods are preferred because there is no substantial mixing of the coating with the hydrophilic protective layer.
• An example of a spray nozzle which can be used in the present invention is an air assisted spray nozzle of the type SUJ1, commercially available at Spraying Systems Belgium, Brussels.
• the spray nozzle may be mounted on a distance of 50 mm to 200 mm between nozzle and receiving substrate.
• the flow rate of the spray solution may be set to 7 ml/min.
• an air pressure in the range of 4.80x10 5 Pa may be used on the spray head. This layer may be dried during the spraying process and/or after the spraying process.
• Typical examples of jet nozzles are ink-jet nozzles and valve-jet nozzles.
• the drying of the plate is preferably carried-out as fast as possible in order to prevent mixing of the layers as much as possible.
• the drying can be carried-out by means of a drying section of the plate processing machine or by means of a hot air device.
• said hydrophilic protective layer has preferably a layer thickness of at least 0.2 g/m 2 , more preferably of at least 0.3 g/m 2 , most preferably of at least 0.4 g/m 2 . There is no specific maximum thickness for this layer but typically the layer thickness is not higher than 2 g/m 2 or even 1.5 g/m 2 .
• said hydrophilic protective coating solution comprises preferably a hydrophilic polymer and/or a surfactant.
• hydrophilic polymers are polymers comprising ionic or ionisable groups or containing polyethyleneoxide groups.
• ionic or ionisable groups are acid groups or salts thereof such as carboxylic acid group, sulphonic acid, phosphoric acid or phosphonic acid.
• the acid groups in the polymer may be neutralized with an organic amine (e.g. ammonia, triethylamine, tributylamine, dimethylethanolamine, diisopropanolamine, morpholine, diethanolamine or triethanolamine) or an alkali metal (e.g. lithium, sodium or potassium).
• the polymer may be composed of a monomer comprising an anionic group.
• the polymer may also be composed of two or more different types of monomers comprising anionic and/or non-ionic groups.
• monomers comprising anionic groups are (meth)acrylic acid, crotonic acid, (meth)acrylic acid, propyl(meth)acrylic acid, isopropyl(meth)acrylic acid, itaconic acid, fumaric acid, sulfoethyl(meth)acrylate, butyl(meth)acrylamidesulfonic acid and phosphoethyl(meth)acrylate.
• the number average molecular weight of the polymer is preferably in the range of about 1,000 to 3,000,000 g/mol.
• hydrophilic polymers are gum arabic, alginic acid, pullulan, cellulose derivatives such as carboxymethylcellulose, carboxyethylcellulose or methylcellulose, (cycle)dextrin, poly(vinyl alcohol), polystyrene sulphonic acid and salts thereof such as sodium, potassium or ammonium salt, poly(vinyl pyrrolidone), polysaccharide, homo- and copolymers of acrylic acid, methacrylic acid or acrylamide, a copolymer of vinyl methyl ether and maleic anhydride, a copolymer of vinyl acetate and maleic anhydride or a copolymer of styrene and maleic anhydride.
• Highly preferred polymers are homo- or copolymers of monomers containing carboxylic, sulfonic or phosphonic groups or the salts thereof, e.g. (meth)acrylic acid, vinyl acetate, styrene sulfonic acid, vinyl sulfonic acid, vinyl phosphonic acid or acrylamidopropane sulfonic acid.
• Other examples of hydrophilic polymers are those typically known in gumming solutions.
• Said surfactant is preferably an ionic surfactant or non-ionic surfactant.
• anionic surfactants include aliphates, abietates, hydroxyalkanesulfonates, alkanesulfonates, dialkylsulfosuccinates, straight-chain alkylbenzenesulfonates, branched alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylphenoxypolyoxyethylenepropylsulfonates, salts of polyoxyethylene alkylsulfophenyl ethers, sodium N-methyl-N-oleyltaurates, monoamide disodium N-alkylsulfosuccinates, petroleum sulfonates, sulfated castor oil, sulfated tallow oil, salts of sulfuric esters of aliphatic alkylesters, salts of alkylsulfuric esters, sulfuric esters of polyoxyethylenealkylethers, salts of sulfuric esters of aliphatic monoglycer
• anionic surfactants are dialkylsulfosuccinates, salts of alkylsulfuric esters and alkylnaphthalenesulfonates.
• suitable anionic surfactants include sodium dodecylphenoxybenzene disulfonate, the sodium salt of alkylated naphthalenesulfonate, disodium methylene-dinaphtalene-disulfonate, sodium dodecyl-benzenesulfonate, sulfonated alkyl-diphenyloxide, ammonium or potassium perfluoroalkylsulfonate and sodium dioctyl-sulfosuccinate.
• the non-ionic surfactant comprises preferably ethylene-oxide groups and/or propylene-oxide groups.
• specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxypropylene block polymers, partial esters of glycerinaliphatic acids, partial esters of sorbitanaliphatic acid, partial esters of pentaerythritolaliphatic acid, propyleneglycolmonoaliphatic esters, partial esters of sucrosealiphatic acids, partial esters of polyoxyethylenesorbitanaliphatic acid, partial esters of polyoxyethylenesorbitolaliphatic acids, polyethyleneglycolaliphatic esters, partial esters of poly-glycerinaliphatic acids, polyoxyethylenated castor oils, partial esters of polyoxyethylene
• non-ionic and anionic surfactants according to the present invention are:
• Two or more surfactants selected from anionic and/or non-ionic surfactants, may be used in combination.
• a combination of two or more different anionic surfactants or a combination of an anionic surfactant and a nonionic surfactant may be preferred.
• Said hydrophilic protective coating solution may further comprise an aqueous liquid.
• aqueous liquids include water and mixtures of water with water- miscible organic solvents such as alcohols e.g. methanol, ethanol, 2-propanol, butanol, iso-amyl alcohol, octanol, cetyl alcohol etc; glycols e.g. ethylene glycol; glycerine; N-methyl pyrrolidone; methoxypropanol; and ketones e.g. 2-propanone and 2-butanone etc.
• alcohols e.g. methanol, ethanol, 2-propanol, butanol, iso-amyl alcohol, octanol, cetyl alcohol etc
• glycols e.g. ethylene glycol; glycerine; N-methyl pyrrolidone; methoxypropanol
• ketones e.g. 2-propanone and 2-butanone etc.
• Said protective coating solution may further comprise a mineral acid, an organic acid or an inorganic salt.
• the mineral acids include nitric acid, sulfuric acid, phosphoric acid and metaphosphoric acid.
• the organic acids include carboxylic acids, sulfonic acids, phosphonic acids or salts thereof, e.g. succinates, phosphates, phosphonates, sulfates and sulfonates.
• Specific examples of the organic acid include citric acid, acetic acid, oxalic acid, malonic acid, p-toluenesulfonic acid, tartaric acid, malic acid, lactic acid, levulinic acid, phytic acid and organic phosphonic acid.
• inorganic salt examples include magnesium nitrate, monobasic sodium phosphate, dibasic sodium phosphate, nickel sulfate, sodium hexametaphosphate and sodium tripolyphosphate.
• Other inorganic salts can be used as corrosion inhibiting agents, e.g. magnesium sulfate or zinc nitrate.
• the mineral acid, organic acid or inorganic salt may be used singly or in combination with one or more thereof.
• the hydrophilic protective coating solution may further comprise a wetting agent such as ethylene glycol, propylene glycol, triethylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylol propane and diglycerin.
• a wetting agent such as ethylene glycol, propylene glycol, triethylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylol propane and diglycerin.
• the wetting agent may be used singly or in combination with one or more thereof.
• the foregoing wetting agent is preferably used in an amount of from 1 to 25 wt.% of the coating solution of the contrast layer.
• a chelate compound may be present in the hydrophilic protective coating solution.
• Calcium ion and other impurities contained in the diluting water can have adverse effects on printing and thus cause the contamination of printed matter. This problem can be eliminated by adding a chelate compound to the diluting water.
• Preferred examples of such a chelate compound include organic phosphonic acids or phosphonoalkanetricarboxylic acids.
• organic amine salts are useful.
• the preferred amount of such a chelating agent to be added is from 0.001 to 1.0 wt.% relative to the contrast coating solution.
• an antiseptic and an anti-foaming agent may be present in the hydrophilic protective coating solution.
• an antiseptic include phenol, derivatives thereof, formalin, imidazole derivatives, sodium dehydroacetate, 4-isothiazoline-3-one derivatives, benzoisothiazoline-3-one, benztriazole derivatives, amidineguanidine derivatives, quaternary ammonium salts, pyridine derivatives, quinoline derivatives, guanidine derivatives, diazine, triazole derivatives, oxazole and oxazine derivatives.
• the preferred amount of such an antiseptic to be added is such that it can exert a stable effect on bacteria, fungi, yeast or the like.
• the anti-foaming agent is preferably silicone anti-foaming agents.
• an emulsion dispersion type or solubilized type anti-foaming agent may be used.
• the proper amount of such an anti-foaming agent to be added is from 0.001 to 1.0 wt.% relative to the contrast coating solution.
• an ink receptivity agent may be present in the hydrophilic protective coating solution if desired.
• examples of such an ink receptivity agent include turpentine oil, xylene, toluene, low heptane, solvent naphtha, kerosine, mineral spirit, hydrocarbons such as petroleum fraction having a boiling point of about 120°C to about 250°C, diester phthalates (e.g., dibutyl phthalate, diheptyl phthalate, di-n-octyl phthalate, di(2-ethylhexyl) phthalate, dinonyl phthalate, didecyl phthalate, dilauryl phthalate, butylbenzyl phthalate), aliphatic dibasic esters (e.g., dioctyl adipate, butylglycol adipate, dioctyl azelate, dibutyl sebacate, di(
• solvents which can be used in combination with these solvents include ketones (e.g., cyclohexanone), halogenated hydrocarbons (e.g., ethylene dichloride), ethylene glycol ethers (e.g., ethylene glycol monomethyl ether, ethylene glycol monophenyl ether, ethylene glycol monobutyl ether), aliphatic acids (e.g., caproic acid, enathic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanic acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, heptacosanoic acid, montanic acid, melissic acid, lacceric acid, isovaleric acid) and unsaturated
• the ink receptivity agent is an aliphatic acid which is liquid at a temperature of 50°C, more preferably has from 5 to 25 carbon atoms, most preferably has from 8 to 21 carbon atoms.
• the ink receptivity agent may be used singly or in combination with one or more thereof.
• the ink receptivity agent is preferably used in an amount of from 0.01 to 10 wt.%, more preferably from 0.05 to 5 wt.%.
• the foregoing ink receptivity agent may be present as an oil-in-water emulsion or may be solubilized with the aid of a solubilizing agent.
• the viscosity of the hydrophilic protective coating solution can be adjusted to a value of e.g. between 1.5 and 5 mPa.s, by adding viscosity increasing compounds, such as poly(ethylene oxide), e.g. having a molecular weight between 10 5 and 10 7 g/mol. Such compounds can be present in a concentration of 0.01 to 10 g/l.
• viscosity increasing compounds such as poly(ethylene oxide), e.g. having a molecular weight between 10 5 and 10 7 g/mol.
• Such compounds can be present in a concentration of 0.01 to 10 g/l.
• the lithographic printing plate precursor used in the method of the present invention is negative-working and develops a lithographic image consisting of hydrophobic and hydrophilic areas at the exposed and non-exposed areas respectively.
• the hydrophilic areas are defined by the support which has a hydrophilic surface or is provided with a hydrophilic layer.
• the 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.
• the support is a metal support such as aluminum or stainless steel.
• a particularly preferred lithographic support is an electrochemically grained and anodized aluminum support.
• the anodized aluminum support may be treated to improve the hydrophilic properties of its surface.
• the aluminum support may be silicated by treating its surface with a sodium silicate solution at elevated temperature, e.g. 95°C.
• a phosphate treatment may be applied which involves treating the aluminum oxide surface with a phosphate solution that may further contain an inorganic fluoride.
• the aluminum oxide surface may be rinsed with a citric acid or citrate solution. This treatment may be carried out at room temperature or may be carried out at a slightly elevated temperature of about 30 to 50°C.
• a further interesting treatment involves rinsing the aluminum oxide surface with a bicarbonate solution.
• the aluminum oxide surface may be treated with polyvinylphosphonic acid, polyvinylmethylphosphonic acid, phosphoric acid esters of polyvinyl alcohol, polyvinylsulfonic acid, polyvinylbenzenesulfonic acid, sulfuric acid esters of polyvinyl alcohol, and acetals of polyvinyl alcohols formed by reaction with a sulfonated aliphatic aldehyde It is further evident that one or more of these post treatments may be carried out alone or in combination.
• the support can also be a flexible support, which may be provided with a hydrophilic layer, hereinafter called 'base layer'.
• the flexible support is e.g. paper, plastic film or aluminum.
• plastic film are polyethylene terephthalate film, polyethylene naphthalate film, cellulose acetate film, polystyrene film, polycarbonate film, etc.
• the plastic film support may be opaque or transparent.
• the base layer is preferably a cross-linked hydrophilic layer obtained from a hydrophilic binder cross-linked with a hardening agent such as formaldehyde, glyoxal, polyisocyanate or a hydrolyzed tetra-alkylorthosilicate.
• a hardening agent such as formaldehyde, glyoxal, polyisocyanate or a hydrolyzed tetra-alkylorthosilicate.
• the thickness of the hydrophilic base layer may vary in the range of 0.2 to 25 ⁇ m and is preferably 1 to 10 ⁇ m. More details of preferred embodiments of the base layer can be found in e.g. EP-A 1 025 992.
• the coating provided on the support contains particles comprising hydrophobic thermoplastic polymers.
• suitable hydrophobic thermoplastic polymers are e.g. polyethylene, poly(vinyl chloride), poly(methyl (meth)acrylate), poly(ethyl (meth)acrylate), poly(vinylidene chloride), poly(meth)acrylonitrile, poly(vinyl carbazole), polystyrene or copolymers thereof.
• Polystyrene and poly(meth)acrylonitrile or their derivatives are highly preferred embodiments.
• the thermoplastic polymer comprises at least 50 wt.% of polystyrene, and more preferably at least 60 wt.% of polystyrene.
• the thermoplastic polymer preferably comprises at least 5 wt.%, more preferably at least 30 wt.% of nitrogen containing monomeric units or of units which correspond to monomers that are characterized by a solubility parameter larger than 20, such as (meth)acrylonitrile.
• nitrogen containing monomeric units are disclosed in European Patent Application no. 01000657, filed on 23.11.2001.
• the hydrophobic thermoplastic polymer is a copolymer consisting of styrene and acrylonitrile units in a weight ratio between 1:1 and 5:1 (styrene:acrylonitrile), e.g. in a 2:1 ratio.
• the weight average molecular weight of the hydrophobic thermoplastic polymers may range from 5,000 to 1,000,000 g/mol.
• the hydrophobic thermoplastic polymer particles preferably have a number average particle diameter below 200 nm, more preferably between 10 and 100 nm.
• the amount of hydrophobic thermoplastic polymer particles contained in the coating is preferably between 20 wt.% and 65 wt.% and more preferably between 25 wt.% and 55 wt.% and most preferably between 30 wt.% and 45 wt.%.
• the hydrophobic thermoplastic polymer particles may be present as a dispersion in an aqueous coating liquid and may be prepared by the methods disclosed in US 3,476,937. Another method especially suitable for preparing an aqueous dispersion of the thermoplastic polymer particles comprises:
• the coating preferably comprises a hydrophilic binder.
• the hydrophilic binders are preferably polymers which do not comprise cationic groups.
• the most preferred hydrophilic binders are polymers comprising anionic or non-ionic groups.
• suitable hydrophilic polymers are homopolymers and copolymers of vinyl alcohol, acrylamide, methylol acrylamide, methylol methacrylamide, acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate or maleic anhydride/vinylmethylether copolymers.
• the hydrophilicity of the (co)polymer or (co)polymer mixture used is preferably the same as or higher than the hydrophilicity of polyvinyl acetate hydrolyzed to at least an extent of 60 percent by weight, preferably 80 percent by weight.
• the coating may also contain other ingredients such as additional binders, development inhibitors or accelerators, and especially one or more compounds that are capable of converting infrared light into heat.
• additional binders such as development inhibitors or accelerators, and especially one or more compounds that are capable of converting infrared light into heat.
• Particularly useful light-to-heat converting compounds are for example infrared dyes.
• the coating comprising a hydrophilic binder and hydrophobic thermoplastic polymer particles, is preferably not or only slightly cross-linked.
• the printing plate precursors used in the method of the present invention are exposed to heat or to infrared light, e.g. by means of a thermal head, LEDs or an infrared laser.
• a laser emitting near infrared light having a wavelength in the range from about 700 to about 1500 nm is used, e.g. a semiconductor laser diode, a Nd:YAG or a Nd:YLF laser.
• the required laser power depends on the sensitivity of the image-recording layer, the pixel dwell time of the laser beam, which is determined by the spot diameter (typical value of modern plate-setters at 1/e 2 of maximum intensity : 10-25 ⁇ m), the scan speed and the resolution of the exposure apparatus (i.e.
• ITD plate-setters for thermal plates are typically characterized by a very high scan speed up to 500 m/sec and may require a laser power of several Watts.
• the hydrophobic thermoplastic polymer particles fuse or coagulate so as to form a hydrophobic phase which corresponds to the printing areas of the printing plate. Coagulation may result from heat-induced coalescence, softening or melting of the thermoplastic polymer particles.
• the coagulation temperature of the thermoplastic hydrophobic polymer particles there is no specific upper limit to the coagulation temperature of the thermoplastic hydrophobic polymer particles, however the temperature should be sufficiently below the decomposition temperature of the polymer particles.
• the coagulation temperature is at least 10°C below the temperature at which the decomposition of the polymer particles occurs.
• the coagulation temperature is preferably higher than 50°C, more preferably above 100°C.
• the printing plate precursor is mounted on a printing press and consecutively on the press the image recording step by laser exposure, the coating of the protective layer by spraying or jetting the protective coating solution, the drying step of the coated protective layer and the developing step with the dampening liquid and ink may be carried out, followed by the (long run) printing process.
• a 0.30 mm thick aluminum foil was degreased by immersing the foil in an aqueous solution containing 40 g/l of sodium hydroxide at 60°C for 8 seconds and rinsed with demineralized water for 2 seconds.
• the foil was then electrochemically grained during 15 seconds using an alternating current in an aqueous solution containing 12 g/l of hydrochloric acid and 38 g/l of aluminum sulfate (18-hydrate) at a temperature of 33°C and a current density of 90 A/dm 2 , After rinsing with demineralized water for 2 seconds, the aluminum foil was then desmutted by etching with an aqueous solution containing 155 g/l of sulfuric acid at 70°C for 4 seconds and rinsed with demineralized water at 25°C for 2 seconds.
• the foil was subsequently subjected to anodic oxidation during 13 seconds in an aqueous solution containing 155 g/l of sulfuric acid at a temperature of 45°C and a current density of 30 A/dm 2 , then washed with demineralized water for 2 seconds and post-treated for 10 seconds with a solution containing 4 g/l of polyvinylphosphonic acid at 40°C, rinsed with demineralized water at 20°C during 2 seconds and dried.
• the support thus obtained was characterized by a surface roughness Ra of 0.22 ⁇ m and had an anodic weight of 4.0 g/m 2 of Al 2 O 3 .
• an image-recording layer was coated from an aqueous coating solution at a wet thickness of 30 g/m 2 .
• the layer consisted of 600 mg/m 2 of a copolymer of styrene and acrylonitrile (weight ratio 60/40) having an average particle size of 65 nm, stabilized with an anionic wetting agent, 60 mg/m 2 of infrared absorbing Dye-1 and 120 mg/m 2 of polyacrylic acid (Glascol E15 from Allied Colloids).
• the plate precursor thus obtained was exposed with a CREO TRENDSETTER 3244 TH957, a plate-setter available from CREO, Burnaby, Canada), having the following specifications: power-output of the laser head 40 Watt, wavelength 830 nm, drum diameter 286 mm, number of beams 192,spotsize 10.6 x 2.5 micron (slowscan x fastscan), operating at 275 mJ/cm 2 and 150 rpm and with a resolution of 2400 dpi.
• the plate was mounted on a GTO 46 printing press (available from Heidelberger Druckmaschinen AG), and the on-press processing was started by supplying fountain liquid, namely 4% Combifix XL with 10% isopropanol, and ink, namely K+E 800.
• fountain liquid namely 4% Combifix XL with 10% isopropanol
• ink namely K+E 800.
• the ik rollers were brought in contact with the plate during press stilstand for 1 minute, so that ink stripes wereleft on the plate, in order to simulate contamination by ink.
• the dampening rollers were brought in contact with the plate during 5 revolutions and subsequently the ink rollers were also brought in contact with the plate during 5 revolutions. Subsequently the clean-out was observed during the roll-up: the ink roller stripes disappear after 50 à 100 printed sheets.
• the same printing plate precursor on the same support as described in the Comparative example 1 was exposed and on-press processed in the same way as described in the Comparative example 1, with the exception that, after imaging exposure and before the on-press processing step, the coating of the plate precursor was sprayed with the RC520 solution, commercially available from AGFA, in an amount of 5.5 ml/m 2 for the INVENTION EXAMPLE 1 and 11 ml/m 2 for the INVENTION EXAMPLE 2.
• the RC520 solution is an aqueous solution of the surfactant DOWFAX 3B2 in a concentration of 39.3 g/l, citric acid.1aq in a concentration of 9.8 g/l, and trisodium citrate.2aq in a concentration of 32.6 g/l, and the RC520 solution has a pH-value of about 5.
• the plate was dried by means of the heating element of the Heights Clean Out Unit of the press.
• the same method as described in the Comparative Example 1 was carried out for the on-press processing of the plate. We observed that the ink roller stripes disappear more quickly, namely after 30 printed sheets in the INVENTION EXAMPLE 1 and after 15 printed sheets in the INVENTION EXAMPLE 2.

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• Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Thermal Sciences (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Printing Plates And Materials Therefor (AREA)
• Materials For Photolithography (AREA)
• Manufacture Or Reproduction Of Printing Formes (AREA)

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• 2004
  • 2004-09-27 EP EP20040104688 patent/EP1524113B1/fr not_active Expired - Fee Related

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