Title of Invention	METHOD FOR MAKING A LITHOGRAPHIC PRINTING PLATE
Abstract	1. Method for making a lithographic printing plate comprising the steps of; (i) providing a negative-working, heat-sensitive lithographic printing plate precursor comprising; - a support having a hydrophilic surface or which is provided with a hydrophilic layer and - a coating provided thereon, said coating comprising an image-recording layer which comprises hydrophobic thermoplastic polymer particles, a binder and an infrared absorbing dye characterised in that; - said hydrophobic thermoplastic polymer particles have an average particle diameter, measured by Photon Correlation Spectroscopy, of more than 10 rati and less than 40 nm; - the amount of said IR-dye, without taking into account an optional counter ion, is more than 0.70 mg per m2 of the total surface of said thermoplastic polymer particles, measured by Hydrodynamic Fractionation; and - the amount of hydrophobic thermoplastic polymer particles relative to the total weight of the ingredients of the imaging layer is at least 60 %. (ii) exposing said precursor to infrared light; (iii) developing said exposed precursor in an alkaline aqueous solution.

Title of Invention

METHOD FOR MAKING A LITHOGRAPHIC PRINTING PLATE

Abstract

1. Method for making a lithographic printing plate comprising the steps of; (i) providing a negative-working, heat-sensitive lithographic printing plate precursor comprising; - a support having a hydrophilic surface or which is provided with a hydrophilic layer and - a coating provided thereon, said coating comprising an image-recording layer which comprises hydrophobic thermoplastic polymer particles, a binder and an infrared absorbing dye characterised in that; - said hydrophobic thermoplastic polymer particles have an average particle diameter, measured by Photon Correlation Spectroscopy, of more than 10 rati and less than 40 nm; - the amount of said IR-dye, without taking into account an optional counter ion, is more than 0.70 mg per m2 of the total surface of said thermoplastic polymer particles, measured by Hydrodynamic Fractionation; and - the amount of hydrophobic thermoplastic polymer particles relative to the total weight of the ingredients of the imaging layer is at least 60 %. (ii) exposing said precursor to infrared light; (iii) developing said exposed precursor in an alkaline aqueous solution.

Full Text	METHOD FOR MAKING A LITHOGRAPHIC PRINTING PLATE. [DESCRIPTION] FIELD OF THE INVENTION The present invention relates to a method for making a lithographic printing plate. BACKGROUND OF THE INVENTION Lithographic printing presses use a so-called printing master such as a printing plate which is mounted on a cylinder of the printing press. The master carries a lithographic image on its surface and a print is obtained by applying ink to said image and then transferring the ink from the master onto a receiver material, which is typically paper. In conventional, so-called "wet" lithographic printing, ink as well as an aqueous fountain solution (also called dampening liquid) are supplied to the lithographic image which consists of oleophilic for hydrophobic, i.e. ink-accepting, water-repelling) areas as well as hydrophilic {or oleophobic, i.e. water-accepting, ink-repelling) areas. In so-called driographic printing, the lithographic image consists of ink-accepting and ink-abhesive (ink-repelling) areas and during driographic printing, only ink is supplied to the master. Printing masters are generally obtained by the image-wise exposure and processing of an imaging material called plats precursor. In addition to the well-known photosensitive, so-called pre-sensitized plates, which are suitable for UV contact exposure through a film mask, also heat-sensitive printing plate precursors have become very popular in the late 1990s. Such thermal materials offer the advantage of daylight stability and are especially used in the so-called computer-to-plate method wherein the plate precursor is directly exposed, i.e. without the use of a film mask. The material is exposed to heat or to infrared light and the generated heat triggers a (physico-)chemical process, such as ablation, polymerization, insoluhiiizatior. by cross linking of a polymer, heat-induced solubilization, or particle coagulation of a thermoplastic polymer latex. The most popular thermal plates form an image by a heat-induced solubility difference in an alkaline developer between exposed and non-exposed areas of the coating. The coating typically comprises an oleophilic binder, e.g. a phenolic resin, of which the rate of dissolution in the developer is either reduced (negative working) or increased (positive working), by the image-wise exposure. During processing, the solubility differential leads to the removal of the non-image (non-printing) areas of the coating, thereby revealing the hydrophilic support, while the image (printing) areas of the coating remain on the support. Typical examples of such plates are described in e.g. EP-As 625 728, 823 327, 825 927, 864 420, 894 622 and 901 902. Negative working embodiments of such thermal materials often require a pre-heat step between exposure and development as described in e.g. EP-A 625 728. Negative working plate precursors which do not require a pre¬heat step may contain an image-recording layer that works by heat-induced particle coalescence of a thermoplastic polymer latex, as described in e.g. EP-As 770 454, 770 495, 770 496 and 770 497. These patents disclose a method for making a lithographic printing plate comprising the steps of (1) image-wise exposing an imaging element comprising hydrophobic thermoplastic polymer particles dispersed in a hydrophilic binder and a compound capable of converting light into heat and (2) developing the image-wise exposed element by applying fountain and/or ink. EP-A 849 091 discloses a printing plate precursor comprising hydrophobic thermoplastic particles having an average particles size of 40 nm to 150 nm and a polydispersity of less than 0.2. EP-A 1 342 568 describes a method of making a lithographic printing plate comprising the steps of (1) image-wise exposing an imaging element comprising hydrophobic thermoplastic polymer particles dispersed in a hydrophilic binder and a compound capable of converting light into heat and (2) developing the image-wise exposed element by applying a gum solution, thereby removing non- 5xposecl areas cf the coating from the support. WO2006/C37"?16 describes a method for preparing a lithographic printing plate which comprises the steps of (1) image-wise exposing an imaging element comprising hydrophobic thermoplastic polymer particles dispersed in a r.ydropr.ilic binder and a compound capable Df converting light into heat ar.d (2) developing the image-wise exposed element; by applying a gum solution, thereby removing nor.-Bxposed areas of the coating from the support and characterised by an average particle size of the thermoplastic polymer particles between 40 nm and 63 nm and wherein the amount of the hydrophobic thermoplastic polymer particles is more than 70 % and less than S5 °s oy weight, relative to the image recording layer. The amount of infrared absorbing dye, hereinafter referred to as IR dye, used in this invention is preferably more then 6 % by weight relative to the image recording layer. EP-A 1 614 538 describes a negative working lithographic printing plate precursor which comprises a support having a hydrophilic surface or which is provided with a hydrophilic layer and a coating provided thereon, the coating comprising an image-recording layer which comprises hydrophobic thermoplastic polymer particles and a hydrophilic binder, characterised in that the hydrophobic thermoplastic polymer particles have an average particle size in the range from 4 5 nm to 63 nm, and that the amount of the hydrophobic thermoplastic polymer particles in the image-recording layer is at least 70 % by weight relative to the image-recording layer. The amount of IB dye used in this invention is preferably more then 6 %, most preferably more then 8 %, by weight relative to the image recording layer. EP-A 1 614 539 and EP-A 1 614 540 describes a method of making a lithographic printing plate comprising the steps of (1) image-wise exposing an imaging element disclosed in EP-A 1 614 538 and (2) developing the image-wise exposed element by applying an aqueous, alkaline solution. EP-A 1 564 020 describes a printing plate comprising a hydrophilic support and provided thereon, an image formation layer containing thermoplastic resin particles in an amount form 60 to 100 % by weight, the thermoplastic particles having a glass transition point (Tg) and an average particle size of from O.Cl -c 2 um, more preferably from 0.1 to 2 um. As thermoplastic particles, polyester resins are preferred. EP 1 564 C20 discloses printing plate precursors comprising polyester thermoplastic particles, cf which the particle size is 160 nm. The unpublished EP-A 06 111 322 (filed 2006-03-17) describes a negative working lithographic printing plate precursor which comprises a support having a hydrophilic surface or which is provided with a hydrophilic layer and a coating provided thereon, said coating comprising an image-recording layer which comprises hydrophobic thermoplastic polymer particles and a hydrophilic binder, characterised in that said hydrophobic thermoplastic polymer particles comprise a polyester and have an average particle diameter from 18 nm to 50 nm. A first problem associated with negative-working printing plates that work according to the mechanism of heat-induced latex-coalescence is the complete removal of the non-exposed areas during the development step (i.e. clean-out). An insufficient clean-out may result in toning on the press, i.e. an undesirable increased tendency of ink-acceptance in the non-image areas. This clean-out problem tends to become worse when the particle size of the thermoplastic particles used in the printing plate precursor decreases, as mentioned in EP-As 1 614 538, 1 614 539, 1 614 540 and WO2006/037716. A decrease of the particle diameter of the hydrophobic thermoplastic particles in the imaging layer may however further increase the sensitivity of the printing plate precursor. According to the unpublished European Application 06 111 322 (filed 2006-03-17) a good clean out is obtained, even with particle sizes from 18 nm to 50 nm, when the hydrophobic thermoplastic polymer particles comprise a polyester. The sensitivity of the lithographic printing plate precursors comprising said thermoplastic polymer particles remains however rather low. The rather low sensitivity of negative-working printing plates that work according to the mechanism of heat-induced latex- coalescence is £ second problem to be solved. A printing piar.e precursor characterised by a low sensitivity needs a longer exposure time and therefore results in a lower throughput (i.e. lower number of printing plate precursors that can be exposed in a given time interval;. SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for making a lithographic printing plate, that work according to the mechanism of heat-induced latex-coalescence, having a high sensitivity and excellent printing properties with reduced or without toning. This object is realized with a method for making a lithographic printing plate comprising the steps of; (i) providing a negative-working, heat-sensitive lithographic printing plate precursor comprising; - a support having a hydrophilic surface or which is provided with a hydrophilic layer and - a coating provided thereon, said coating comprising an image-recording layer which comprises hydrophobic thermoplastic polymer particles, a binder and an infrared absorbing dye characterised in that; - said hydrophobic thermoplastic polymer particles have an average particle diameter, measured by Photon Correlation Spectroscopy, of more than 10 nm and less than 40 nm and - the amount of said IR-dye, without taking into account an optional counter ion, is more than 0.70 mg per nr of the total surface of said thermoplastic polymer particles, measured by Hydrodynamic Fractionation, and - the amount of hydrophobic thermoplastic polymer particles relative to the total weight of the ingredients of the imaging layer is at least 60 %. (ii) exposing said precursor to infrared light; (iii) developing said exposed precursor in an alkaline aqueous solution. Preferred embodiments of the present invention are defined in the dependent claims. DETAILED DESCRIPTION OF THS INVENTION The printing plate precursor, used in the method for making a printing plate, comprises a coating on a hydrophilic support. The coating may comprise one or mors layer(s). The layer of said coating comprising the hydrophobic thermoplastic particles is referred to herein as the image-recording layer. Hydrophobic thermoplastic particles The hydrophobic particles have an average particle diameter of more than 10 nm and less than 4 0 nrn, preferably of more than 15 nm and less than 38 nm, more preferably of more than 20 and less than 36 nm. The average particle diameter referred to in the claims and the description of this application is meant to be the average particle diameter measured by Photon Correlation Spectrometry (0?Cs) , also known as Quasi-Elastic or Dynamic Light-Scattering, unless otherwise specified. The measurements were performed according the ISO 13321 procedure (first edition, 1996-07-01) with a Brookhaven BI-9G analyzer, commercially available from Brookhaven Instrument Company, Holtsville, NY, USA. An alternative method to measure the average particle diameter is based on hydrodynamic fractionation. With this technique a volume distribution of the particles is obtained from which a volume average particle diameter is calculated (0V). In the examples the volume average particle diameter, measured according to this technique, is obtained with a PL-PSDA apparatus (Polymer Laboratories Particle Size Diameter Analyser) from Polymer Laboratories Ltd, Church Stretton, Shropshire, UK. From the volume distribution, obtained with the PL-PSDA apparatus, the total surface of the hydrophobic particles .expressed as square metrs per gram hydrophobic particles, itr/g) can be calculated. In these calculations the density ig/cnr) of the -hermoplastic particles has :o be taken into accour.. The density of different polymers can be found for example in the handbook 'Properties of polymers, their estimation and correlation with chemical structures' by D.w. Van Krevelen, from Elsevier Scientific Publishing Company, second edition, pages 574 to 581). The density may also be measured. For particles or lattices, the so-called skeletal (definition according to ASTM D3766 standard) density may be measured according to the gas displacement method. The amount of hydrophobic thermoplastic polymer particles is at least 60, preferably at least 65, more preferably at least 70 percent by weight relative to the weight of all the ingredients in the image-recording layer. The hydrophobic thermoplastic polymer particles which are present in the coating are preferably selected from polyethylene, poly-(vinyl)chloride, polymethyl(meth)acrylate, polyethyl (methj acrylate, polyvinylidene chloride, poly(meth)acrylonitrile, polyvinyl-carbazole, polystyrene or copolymers thereof. According to a preferred embodiment, the thermoplastic polymer particles comprise polystyrene or derivatives thereof, mixtures comprising polystyrene and poly(meth)acrylonitrile or derivatives thereof, or copolymers comprising polystyrene and poly(meth)-acrylonitrile or derivatives thereof. The latter copolymers may comprise at least 50 wt.% of polystyrene, more preferably at least 65 wt.% of polystyrene. In order to obtain sufficient resistivity towards organic chem." caIs such as hydrocarbons used in e.g. plate cleaners, the thermoplastic polymer particles preferably comprise at least 5 wt.%, more preferably at least 30 wt.%, of nitrogen containing units, such as (meth)acrylonitrile, as described in Ep-A 1 219 416. According to the most preferred embodiment, the thermoplastic polymer particles consist essentially of styrene and acrylonitrile units in a weight ratio between 1:1 and 5:1 (styrene:acrylonitrile), e.g. in a 2:1 ratio. In a preferred embodiment the hydrophobic thermoplastic particles do not consist of polyester. The weight average m^lecuiiir weight of the n he miopias tic polymer particles may range from 5,000 to 1,000,000 g/mol. The hydrophobic thermoplastic polymer particles can be prepared by addition polymerization or by condensation polymerization. They ere preferably applied onto the lithographic base in the form of a dispersion in an aqueous coaling liquid. These water based dispersions can he prepared by polymerization in a water-cased system e.g. by free-radical emulsion polymerization as described in US 3 476 937 cr EP-A 1 217 010 or by means of dispersing techniques of che water-insoluble polymers into water. Another method for preparing an aqueous dispersion of the thermoplastic polymer particles comprises (1) dissolving the hydrophobic thermoplastic polymer in an organic water immiscible solvent, (2) dispersing the thus obtained solution in water or in an aqueous medium and (3) removing the organic solvent by evaporation. Emulsion polymerization is typically carried out through controlled addition of several components - i.e. vinyl monomers, surfactants (dispersion aids], initiators and optionally other components such as buffers or protective colloids - to a continuous medium, usually water. The resulting polymer is a dispersion of discrete particles in water. The surfactants or dispersion aids which are present in the reaction medium have a multiple role in the emulsion polymerization: (1) they reduce the interfacial tension between the monomers and the aqueous phase, (2) they provide reaction sites through micelle formation in which the polymerization occurs and (3) they stabilize the growing polymer particles and ultimately the latex emulsion. The surfactants are absorbed at the water/polymer interface and thereby prevent coagulation of the fine polymer particles. Non-ionic, cationic and anionic surfactants may be used in emulsion polymerization. Preferably non-ionic or anionic surfactants are used. Most preferably the hydrophobic thermoplastic particles are stabilized with ar. anionic dispersion aid. Specific examples of suitable anionic dispersion aids include sodium lauryl sulphate, sodium lauryl ether sulphate, sodium dodecyl sulphate, sodium dodecyl benzene sulphonate and sodiuro lauryl phosphate; suitable non-ionic dispersion aids are for example ethoxylated lauryi aleonol anc ethoxylatSG octylphenol. IP. absorbing compounds The coating contains a dye which absorbs infrared (IR) light and converts the absorbed energy into heat. Preferred IR absorbing dyes are cyanine, merocyanine, indoaniline, oxonol, pyrilium and squsrilium dyes. Examples of suitable IR absorbers are described in e.g. EP-As S23 327, 973 376, 1 C29 667, 1 053 S68 and 1 093 934 and WOs 97/39894 and 00/29214. Other preferred IR-dyes are described in EP 1 614 541 (page 20 line 25 to page 44 line 29] and the unpublished EP-A 05 105 440 (filed 2005-06-21). IR-dyes, preferably used in this invention, are water compatible, most preferably, water soluble. In the prior art, e.g. in EP-A 1 614 538, the IR-dye amount is preferably at least 6 %, more preferably at least 8 %, by weight relative to the image recording layer, irrespective of the average particle diameter of the hydrophobic thermoplastic particles used. According to EP-A 1 614 538 lithographic printing plates comprising hydrophobic thermoplastic particles with a particle size less then 40 nm have inferior lithographic properties, i.e. a bad clean-out (e.g. comparative in example 1, average particle diameter = 36 nm). It has surprisingly been found that lithographic printing plates comprising hydrophobic thermoplastic particles with a particle size of more then 10 nm and less then 40 nm, characterised by a good clean-out and a high sensitivity, are obtained by adjusting the amount of IR-dye in relation to the amount and the average particle diameter of said thermoplastic particles. As a result of this investigation it has been found that by adjusting the amount of IR-dye in relation to the total surface of the hydrophobic thermoplastic particles present in the image-recording layer, printing plate precursors with optimum lithographic properties are obtained. The total surface of the hydrophobic thermoplastic particles is calculated as described above and in the examples. A possible explanation of this phenomenon may be that all or part of the IR-ayes adsorb on the surface of the hydrophobic particles and render the particles more dispersible in aqueous solutions (e.g. developer) resulting in an improved clean-out behavior. Since it is believed that optional counter ions of the IR-dyes (i.e. when the IR-dyes are used as salts) do not have an essential contribution to the invention, the amount of IR-dye used according to this invention is meant to be the amount of IR-dye without taking into account an optional counter ion. A good clean-out and superior sensitivity with lithographic printing plates comprising hydrophobic thermoplastic particles with a particle diameter of more than 10 nm and size less than 40 nm, is obtained when the amount of IR-dye, without taking into account an optional counter ion, is more than 0.70 mg, preferably more than 0.85 mg, more preferably more than 1.00 mg per ITT of the total surface of said thermoplastic polymer particles. These findings imply that when the average particle diameter of the hydrophobic thermoplastic particles decreases (and the amount of particles (g/m2) in the imaging layer remains constant) the amount of IR dye in the imaging layer must be increased to maintain good lithographic properties. Referring to the comparative example of EP-A 1 614 538 mentioned above, the amount of IR-dye, without taking into account the counter ion, used therein is less then 0.70 rag per m2 of the total surface of the thermoplastic polymer particles, having an average particle diameter of 36 nm. There is no particular upper limit for the amount of IR-dye. However, when the total infrared optical density (e.g. at 830 nm) of the coating becomes too high, the IR-light emitted from the exposure source, may not reach the lower part of the imaging layer, resulting in a poor coalescence of the thermoplastic polymer particles at the part of the imaging layer that makes contact with the support. This may be overcome with a higher energy exposure, but results in a lower throughput (numbers of printing plate precursors that can be exposed in a given time interval). The maximum optical density at 830 nm of the coating, obtained from diffuse reflectance spectra, measured with a Shimadzu UV-3101 PC/ISR-3100 spectrophotometer, is preferably less then 2.00, more preferably less then 1.50, most preferably less then 1.25. Binder The image-recording layei may further comprise a hydrophilic binder. Examples of suitaole hydrophilic binders are horriopolymers and copolymers of vinyl alcohol, imeth)acryiamide. methyloi imeth)acryiamide, imeth)acrylic acid, hydroxyethyl (meth)acrylate, naleic anhydride/vmylmethyiether copolymers, copolymers of imeth)acrylic acid or vinylalcohol with styrene sulphonic acid. Preferably, the hydrophilic binder comprises polyvinylalcohcl or polyacrylic acid. The amount of hydrophilic binder may be between 2.5 and 50 wt.%, preferably between 3 and 20 wt.3, more preferably between 4 and 10 wt.% relative to the total weight of all ingredients of the image-recording layer. The amount of the hydrophobic thermoplastic polymer particles relative to the amount of the binder is preferably between 8 and 20, more preferably between 10 and 18, most preferably between 12 and 16. Contrast Dyes Colorants, such as dyes or pigments, which provide a visible color to the coating and remain in the exposed areas of the coating after the processing step may be added to the coating. The image-areas, which are not removed during the processing step, form a visible image on the printing plate and examination of the lithographic image on the developed printing plate becomes feasible. Typical examples of such contrast dyes are the ammo-substituted tri- or diarylmethane dyes, e.g. crystal violet, methyl violet, victoria pure blue, flexoblau 630, basonylblau 640, auraraine and malachite green. Also the dyes which are discussed in depth in the detailed description of EP-A 40C 706 are suitable contrast dyes. Dyes which, combined with specific additives, only slightly color the coating but which become intensively "Glared after exposure, as described in for example WO2006/0C5686 are also of interest. Other ingredients. Optionally, the coating may further contain additional ingredients. These ingredients may be present in the image-recording layer or in an optional other layer. For example, additional binders, polymer particles such as matting agents and spacers, surfactants such as perfluoro-surfactants, silicon or titanium dioxide particles, development inhibitors, development accelerators, colorants, metal complexing agents are well-known components of lithographic coatings. Preferably the image-recording layer comprises an organic compound, characterised in that said organic compound comprises at least one phosphonic acid group or at least one phosphoric acid group or a salt thereof, as described in the unpublished European Patent Application 05 109 781 (filed 2005-10-20). In a particularly preferred embodiment the image-recording layer comprises an organic compound as represented by formtla I: Compounds according tc formula I may be present i- the image-recording layer in an amount between 0.05 and 15 wt.%, preferablv between 0.5 and 1C wz.%, more preferably between 1 and 5 w-.= relative tc the total weight of the ingredients of the image-reccrding layer. Other layers cf the coating To protect the surface cf the coating, in particular from mechanical damage, a protective layer may optionally be applied on the image-recording layer. The protective layer generally comprises at least one water-soluble polymeric binder, such as polyvinyl alcohol, polyvinylpyrrolidone, partially hydrolyzed polyvinyl acetates, gelatin, carbohydrates or hydroxyethylcellulose. The protective layer may contain small amounts, i.e. less then 5 % by weight, of organic solvents. The thickness of the protective layer is not particularly limited but preferably is up to 5.0 um, more preferably from 0.05 to 3.0 um, particularly preferably from 0.10 to 1.0 um. The coating may further contain other additional layer(s) such as for example an adhesion-improving layer located between the image-recording layer and the support. Support The support of the lithographic printing plate precursor 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. In one embodiment of the invention the support is a metal support such as aluminum or stainless steel. The support can also be a laminate comprising an aluminum foil and a plastic layer, e.g. polyester film. A particularly preferred lithographic support is an aluminum support. Any known and widely used aluminum materials can be used. The aluminum support: has a thickness of about 0.1-0.6 mm. However, this thickness can be changed appropriately depending on the size of the printing plate used and the plate-setters on which the printing place precursors jie exposed. To optimize the lithographic properties, the aluminum support is subjected to several treatments well known in the art such as for example: decrease, surface roughening, etching, anodizaeion, sealing, surface treatment. In between such treatments, a neutralization treatment is often carried out. A detailed description of these treatments can be found in e.g. EP-As 1 142 707, 1 564 020 and 1 614 533. A preferred aluminum substrate, characterized by an arithmetical mean center-line roughness Ra less then 0.45 u is described in EP 1 356 926. Optimizing the pore diameter and distribution thereof of the grained and anodized aluminum surface as described in EP 1 142 707 and US 6 692 890 may enhance the press life of the printing plate and may improve the toning behaviour. Avoiding large and deep pores as described in US 6 912 956 may also improve the toning behaviour of the printing plate. An optimal ratio between pore diameter of the surface of the aluminum support and the average particle size of the hydrophobic thermoplastic particles may enhance the press run length of the plate and may improve the toning behaviour of the prints. This ratio of the average pore diameter of the surface of the aluminum support to the average particle size of the thermoplastic particles present in the image-recording layer of the coating, preferably ranges from 0.05:1 to 0.8:1, more preferably from 0.10:1 to 0.35:1. Alternative supports for the plate precursor can also be used, such as amorphous metallic alloys (metallic glasses). Such amorphous metallic alloys can be used as such or joined with other non-amorphous metals such as aluminum. Examples of amorphous metallic alloys are described in US 5 288 344, US 5 368 659, US 5 618 359, US 5 735 975, US 5 250 124, US 5 032 196, US 6 325 868, and US 6 818 078. The following references describe the science of amorphous metals in much more detail and sre incorporated as references: Introduceion to rhe Theory of Amorphous Metals, N.P. Kovalenkc sc al.i200ii; Atomic Ordering in Liquid and Amorphous Metals, S.I. Popel, et al; Physics of Amorphous Metals, N.P. Kovalenko su al (2 001;. According to another embodiment, "he support can also be a flexible support, which is provided with a hydrophilic layer. The flexible support is e.g. paper, plastic film, thin aluminum or a laminare thereof. Preferred examples of plastic film are poly¬ethylene "cerephthalate film, polyethylene naphthalate film, cellulose acetate film, polystyrene film, polycarbonate film, etc. The plastic film support may be opaque or transparent. Particular examples of suitable hydrophilic layers that may be supplied to a flexible support for use in accordance with the present invention are disclosed in EP-A 601 240, GB 1 419 512, FR 2 300 354, US 3 971 660, US 4 284 705, EP 1 614 538, EP 1 564 020 and US 2006/0019196. Exposure The printing plate precursor is exposed with infrared light, preferably near infrared light. The infrared light is converted into heat by an IR-dye as discussed above. The heat-sensitive lithographic printing plate precursor of the present invention is preferably not sensitive to visible light. Host preferably, the coating is not sensitive to ambient daylight, i.e. visible (400-750 nm] and near UV light (300-400 nm) at an intensity and exposure time corresponding to normal working conditions so that the material can be handled without the need for a safe light environment. The printing plate precursors of the present invention can be exposed to infrared light by means of e.g. LEDs or an infrared laser. Preferably lasers, emitting near infrared light having a wavelength in the range from about 700 to about 1500 nm, e.g. a semiconductor laser diode, a Kd:YAG or a Nd:YLF laser, are used. Most preferably, a laser emitting in the range between 780 and 830 nm is used. The required laser power depends on the sensitivity of cne image-recording layer, the pixel dwell rime of rhe laser bsaiu, which is determined by the spot diameter (typical value of modern plate-setters at 1/e- of maximum intensity : 10-25 urn) , the scar, speed and the resolution of the exposure apparatus (i.e. the number of addressable pixels per unit cf linear distance, often expressed in dots per inch or dpi; typical value : 1000-4000 dpi). In a preferred embodiment of this invention a useful lithographic image is obtained upon image-wise exposure of the printing plate precursor with IR-light having an energy density, measured at the surface of said precursor, of 200 mj/cnr" or less, more preferably of 180 mJ/cm^ or less, most preferably of 160 mJ/cnr or less. With a useful lithographic image on the printing plate, 2 % dots (at 200 lpi) are perfectly visible on at least 1 000 prints on paper. Two types of laser-exposure apparatuses are commonly used: internal (ITD) and external drum (XTD) plate-setters. ITD plate-setters for thermal plates are typically characterized by a very high scan speed up to 1500 m/sec and may require a laser power of several Watts. The Agfa Galileo T (trademark of Agfa Gevaert W.V.) is a typical example of a plate-setter using the ITD-technology. XTD plate-setters for thermal plates having a typical laser power from about 20 mW to about 500 mW operate at a lower scan speed, e.g. from 0.1 to 20 m/sec. The Agfa Xcalibur, Accento and Avalon plate-setter families (trademark of Agfa Gevaert N.V.] make use of the XTD-technology. Due to the heat generated during the exposure step, the hydrophobic thermoplastic polymer particles may fuse cr 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. 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. Preferably the coagulation temperature is at least 10 °C below the temperature at which the decomposition of the polymer particles occurs. The coagulation temperature is pr&ierably higner than 50 °C, more preferably above 100 °C. Development Afrer exposure, the material can be developed by supplying to the coating an aqueous alkaline solution whereby the non-image areas of the coating are removed. This developing step with an aqueous alkaline developer solution may be combined with mechanical rubbing, e.g. by a rotating brush. During the development step, any water-soluble protective layer present is preferably also removed. A preferred developer solution is a developer with a pH of at least 9, preferably at least 10, more preferably at least 11, most preferably at least 12. The developer comprises an alkaline agent. In a preferred embodiment said alkaline agent comprises an alkaline silicate or metasilicate. The alkaline silicate or metasilicate exhibits an alkalinity when dissolved in water, and examples thereof include an alkali metal silicate and alkali metal metasilicate such as sodium silicate, sodium metasilicate, potassium silicate and lithium silicate, and ammonium silicate. Said alkaline silicate may be used alone, or in combination with another alkaline agent. The development performance of the alkaline aqueous solution may be easily modulated by adjusting the molar ratio of alkaline silicates and alkali metal hydroxides, represented by silicon oxide (Si02) and an alkali oxide (M2O, wherein M represents an alkali metal or an ammonium group). The alkaline aqueous solution has preferably a molar ratio Si02/M20 from 0.5 to 3.0, more preferably from 1.0 to 2.0, most preferably of 1.0. The concentration of alkaline silicate in the developer ranges generally from 1 to 14% by weight, preferably from 3 to 14% by weight, and more preferably from 4 to 14% by weight. In another embodiment, the aqueous alkaline solution may comprise a nonreducing sugar. The nonreducing sugar denotes sugars r.sviric n: reductive property due tc ~he aosence of a free aldehyde group cr a free Ketone group. Said nonreducing sugar is classified into trehalose-^ype oligosaccharides wherein a reductive group and another reductive group make a linkage; glycosides wherein a reductive group in a sugar is linked o a non-sugar compound; and sugar alcohols which are produced by reducing a sugar with hydrogenation. Said trehalose-type oligosaccharides include sucrose and trehalose, and said glycosides include alkyl glycosides, phenol glycosides, mustard oil glycosices and the like. Said sugar alcohols include D,L-arabitol, ribitoi, xylitol, D,L-sorbitol, D,L-mannitol, D,L-iditol, talitol, dulcitol, allodulcitol and the like. Further, maltitol obtained hy hydrogenation of disaccharide, a reduced material obtained by hydrogenation of oligosaccharide (a reduced starch syrup) and the like are preferably used. Pentaerythritol car. also be used in the developing solution. Of the above mentioned nonreducing sugars, preferred are sugar alcohols and sucrose, and particularly preferred are D-sorbitol, sucrose and a reduced starch syrup, since they have buffering action in appropriate pH range. In addition to alkali metal silicates and/or nonreducing sugars, the developer may optionally contain further components, such as buffer substances, complexing agents, antifoams, organic solvents in small amounts, corrosion inhibitors, dyes, surfactants and/or hydrotropic agents as known in the art. Development is preferably carried out at temperatures of from 20 to 40 °C in automated processing units as customary in the art. For replenishment (also called regeneration) purposes, alka i metal silicate solutions having alkali metal contents of from 0.6 to 2.0 mol/1 can suitably be used. These solutions may have the same silica/alkali metal oxide ratio as the developer and optionally contain further additives. Replenishment may be tailored to the developing apparatuses used, daily plate throughputs, image areas, etc. and are in general from 1 to 50 ml per square meter of plate precursor. Addition of replenisher can be regulated, for example, by measuring the conductivity of the developer as described in EP-A 0 556 690. protective compounds that are capable of protecting the lithographic image cf a printing plate against contamination or damaging. Scitabie examples of such compounds are film-forming r_ydropb.il 2. c polymers or surfactants. The plate precursor can, i: required, be post-treated with a suitable correcting agent or preservative as known in the art. To increase the resistance of the finished printing plate and hence to extend the run length, the layer can be briefly heated to elevated temperatures ("baking"!. The plate can be dried before baking or is dried during the baking process itself. During the baking step, the plate can be heated at a temperature which is higher than the glass transition temperature of the thermoplastic particles, e.g. between 100 °C and 230 °C for a period of 40 minutes to 5 minutes. A preferred baking temperature is above 60 °C. For example, the exposed and developed plates can be baked at a temperature of 230 °C for 5 minutes, at a temperature of 15C "C for 10 minutes or at a temperature of 120 °C for 30 nunutes. Baking can be done in conventional hot air ovens or by irradiation with lamps emitting in the infrared or ultraviolet spectrum. As a result of this baking step, the resistance of the printing plate to plate cleaners, correction agents and UV-curable printing inks increases. Such a thermal post-treatment is described in e.g. DE 1 447 963 and GB 1 154 749. 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 so-called single-fluid ink without a dampening liquid. Suitable single-fluid inks have been described in US 4 045 232; US 4 981 517 and US 6 140 392. In a most preferred embodiment, the single-fluid ink comprises an ink phase, also called the hydrophobic or oleophilic phase, and a polyol phase as described in JVO 00/32705. Ir_ another preferred emboaj.mer.r., development cff p_ess »:;-r. e.g. a developing solution, where-in r.he non-exposed areas of the image recording layer are parrialiy removed, may be combined with a development or. press, wherein a complete removal cf -he non-exposed is realised. EXAMPLES Preparation hydrophobic Ehermoplastic parr-ides (LX-01 to LX-G2) Preparation of LX-01: The polymer emulsion was prepared by means of a 'semi-continuous emulsion' polymerization wherein all monomers (styrene and acrylonitrile) are added to the reactor. All surfactant (3 wt. "a relative to the monomer amount! is present in the reactor before the monomer addition was started. In a 2 1 double-jacketed reactor, 10.8 g of sodium dodecyl sulphate (Texapon K12 from Cognis) and 1243.9 g of" demineralised water was added. The reactor was flushed with nitrogen and heated until 80 °C. When the reactor content reached a temperature of 80 °C, 12 g of a 5% solution of sodium persulphate in water was added. The reactor was subsequently heated for 15 min. at 80 °C. Then the monomer mixture (238.5 g of styrene and 121.5 g of acrylonitrile) was dosed during 180 min. Simultaneously with the monomer addition, an additional amount of an aqueous persulphate solution was added [24 g of a 5% aqueous Na2S2Oe solution). After the monomer addition was finished the reactor was heated for 30 min. at 80 °C. To reduce the amount of residual monomer, a redox-initiation system was added: 1.55 g sodium formaldehyde sulphoxylate dihydrate (SFS) dissolved in 120 g water and 2.57 g of a 70 wt.% t-butyl hydro peroxide (TBHP) diluted with 22.5 g of water. The aqueous solutions of SFS and TBHP were added separately during 80 min. The reactor was then heated for another 10 min. and was subsequently cooled to room temperature. 800 g of a 5 wt.% aqueous solution of 5-bromo-5-nitro-1,3-dioxane was added as biocide and the latex was filtered using a zoarse tiller paper. This resulted in the lacex dispersion 1X-01 with a solid content of 20.64 wt.% and a pH cf 3.71. Preparation of LX-02: The polymer ernulsior. was prepared by means of a 'semi-continuous emulsion' polymerization wherein all monomers (styrene and acrylonitrile) are added to the reactor. All surfactant (2.15 wt.i towards the monomer amount) is present in the reactor before the monomer addition is started. In a 400 1 double-jacks ted reactor, 17.2 kg cf a 10 wt.% aqueous solution of sodium dodecyl sulphate (Texapon K12 from Cognis) and 265 kg of demineralised water was added. The reactor was brought under inert atmosphere by 3 times vacuum/nitrogen exchange. The reactor content was stirred at 100 rpm and heated until 82 °C. When the reactor content reached a temperature of 82 °C, 6.67 kg of a 2% of sodium persulphate in water was added. The reactor was subsequently heated for 15 min. at 82 °C. Then the monomer mixture (53.04 kg of styrene and 27.0 kg Of acrylonitrile) was dosed during 3 hours. Simultaneously with the monomer addition an aqueous persulphate solution was added (13.34 kg of s 2% aqueous Na^SjOe solution) during 3 hours. The monomer flask was flushed with 5 1 of demineralised water. After the monomer addition the reactor was heated during 60 min. at 82 DC. To reduce the amount of residual monomer a redox-initiation system was added (340 g of sodium formaldehyde sulphoxylate dihydrate (SFS) dissolved in 22.81 kg water and 570 g of a 70 wt.% t-butyl hydro peroxide (TBHP) diluted with 4.8 kg of water. The aqueous solutions of SFS and TBHP were added separately during 2 hours, and 20 min. The reaction was then heated for another 10 min. at 82 °C and was subsequently cooled to room temperature. 800 g of a 5 wt.% aqueous solution of 5-bromo-5-nitro-l,3-dioxane was added as biocide and the latex was filtered using a 5 micron filter. This resulted in the latex dispersion LX-02 with a solid content of 19.92 wt.% and a pH of 3.2. Particle size and surface of t-he hydrophobic thermoplastic particles Two techniques were used :c measure the particle diameter of the hydrophobic thermoplastic particles, as described in the detailed description: 0,.-s : is the particle diameter obtained by Photon Correlation Spectroscopy. The measurements were performed according the ISO 13321 procedure (first edition, 1996-07-01) with a Brookhaven BI-90 analyzer from Brookhaven Instrument Company, Holt5vilie, NY, USA. 0-,- : is the volume average particle diameter obtained with hydrodynamic fractionation obtained with a PL-PSDA apparatus (Polymer Laboratories Particle Size Diameter Analyzer) from Polymeric Labs. From the volume particle size distribution, obtained with the PL-PSDA apparatus, the total surface of the hydrophobic thermo¬plastic particles [Surface (m2/g)) is calculated. These calculations have been performed with a density (p, (g/cm3) ) of the particles of 1.10 g/cmJ. Since all particles LX-01 to LX-02 have the same composition, they all have the same density. The density of the particles LX-01 to LX-02 (skeletal density according to ASTM D3766 standard) has been measured using the gas displacement method on a Accupyc 1330 helium-pycnometer (from Micromeritics). The calculations are based on the following formulas: p = Density (g/cm3) V = Volume of 1 g particles N = Number of particles in 1 g S = total Surface of 1 g of particles (m2/g) 0V = Volume particle diameter (nm) A 0.2 mm thick aluminum io.. I was degreased by spraying with ar. aqueous solution containing 34 g/1 NaOH at 70 °C for 6 seconds and rinsed with dsmmeralised water for 3.6 seconds. The foil was tner. electrochemically grained during 6 seconds using an alternating current in an aqueous solution containing 15 g/1 HC1, 15 g/1 SCV ions and 5 g/1 AT"" ions at a temperature of 37 °C and a current density of about 100 A/dm" {charge density cf about SCO C/dfir). Afterwards, the aluminum foil was desmutted by etching with an aqueous solution containing 145 g/1 of sulphuric acid at 80 °c for 5 seconds and rinsed with demineralised water for 4 seconds. The foil was subsequently subjected to anodic oxidation during 10 seconds in an aqueous solution containing 145 g/i of sulphuric acid at a temperature of 57 °C and a current density of 33 A/dm" (charge density of 330 C/dm2) , then washed with demineralised water for 7 seconds and post-treated for 4 seconds (by spray) with a solution containing 2.2 g/1 PVPA at 70 °C, rinsed with demineralised water for 3.5 seconds and dried at 120 °C for 7 seconds. The support thus obtained is characterised by a surface roughness Ra of 0.35-0.4 um (measured with interferometer NT1100] and have an anodic weight of about 4 . 0 g/rrr ingredients used in the preparation of the printing plate precursors PAA: Polyacrylic acid from Ciba Specialty Chemicals. PAA was added to the coating solutions as a 5 wt% aqueous solution IR-1: Chemical formula see table 2. IR-1 was added to the coating solutions as a 1 wt% aqueous solution IR-2: Chemical formula see table 2. IR-2 was added to the coating solutions as a 1 wt% aqueous solution IR-3: Chemical formula see table 2. IR-3 was added to the coating solutions as a solid. :-iSDP: 1-hydroxyethylidene-l, 1-diphcsphonic acid from Solutia. HE.D? was added to ;.ie coaling solutions as a 10 w:-t aqueous solution FSO ICO : Zonyl FSO 100, a flucr surfactant from Dupont CD-01 : 5 % aqueous dispersion of a modified Cu-phthaiocyanine IJX 883 from Cabot Corporation. CD-02 : 20 ". aqueous dispersion of a phthalocyanine Heliogsn 'Biau D7490 from BASF. The dispersion is stabilized with an anionic surf actar.i. CD-03 : 20 % aqueous dispersion of PV Fast Violet RL from Clariant. The dispersion is stabilized with an anionic surfactant. Example 1: Printing plate precursors PPP-1 to 6 Preparation of the coating solutions The coating solutions for the printing plate precursors 1 to 6 were prepared using the solutions or dispersions as described above. The latex dispersions (LX) were added to demineralised water followed by stirring for 10 minutes and addition of the IB-dye. After SO minutes of stirring the poly acrylic acid (PAA) solution was added followed by stirring during 10 minutes and addition of the HEDP solution. Subsequently after another 10 minutes of stirring the surfactant solution was added and the coating dispersion was stirred for another 30 minutes. Subsequently the pH was adjusted to a value of 3.6 with a diluted ammonia solution (ca 3%). Preparation of the printing plate precursors PPP-1 to PPP-6 The printing plate precursor coating solutions were subsequently coated on the aluminum substrate, as described above, with a coating knife at a wet thickness of 30 urn. The coatings were dried at 60°C. Table 3 lists the resulting dry coating weight of the different components of the printing plate precursors. Exposure, development and printing of the printing plate precursors The printing plate precursors were exposed on a Creo Trend-Setter 3244 40W fast head IR-laser plate-setter at 300 - 250 - 200 -150 - 100 mj/cm£ at 150 rotations per minute (rpm) with a 200 line per inch (lpi) screen and an addressability of 2400 dpi. After exposure the printing plate precursors were developed in a VA-98 processor (from Agfa Gevaert NV] with a TD1000 developer (from Agfa-Gevaert NV) followed by gumming using a gum solution prepared as follows: To 700 ml demineralized water 11.3 ml Dowfax 3B2 (commercially available from Dow Chemical) 32.6 g of trisodium citrate dihydrate 9.8 g citric acid monohydrate were added whilst stirring demineralized water was further added to obtain LOCO g gurn solution. After development and gumrp.ing the printing plates were mounted zr. a GT046 printing press. A compressible blanket was used and printing was done with the fountain Agfa Prima FS101 (trademark of Agfa) and K+E SZO clack ink (trademark: of K£E; . The following start¬up procedure was used : first 5 revolutions with the dampening form rollers engaged, then 5 revolutions with both the dampening and ink form rollers engaged, then printing started. 1000 prints were made on 80 g offset paper. Evaluation of the printing plate precursors PPp-1 to PPP-6 The printing plate precursors are evaluated by the following characteristics: Sensitivity 1 : Plate sensitivity (2% dot) (mj/crrr) ; the lowest exposure energy density at which 2% dots are perfectly visible (by means of a 5x magnifying glass) on the one-thousandth print on paper. Sensitivity 2 : Plate sensitivity (B-25 2%) (rnJ/cm2) : is the interpolated energy density value where the surface coverage (calculated from the measured optical density of the one-thousandth print on paper) of a B-25 2% dot patch equals 55%. A B-25 2% dot patch consists of 2% ABS (200 lpi, 2400 dpi) dots, but the total surface coverage of these dots is 25%. ABS dots are generated with the Agfa Balanced Screening methodology. Clean-out: After 750 prints, the paper sheet size is shortened and printing is continued for another 250 prints. After 1 OQC prints, a few more prints are generated on the normal paper size. If any staining should occur, this will result in an accumulation of ink on the blanket, while printing is performed with the shortened paper size. This accumulated ink will tier, oe transferred to the paper when the normal paper size is used again, after 1 000 prints. This method allows for a very precise evaluation of the stain level. A value of 5.0 indicates that no stain is observed after 1 000 prints. A value of 4.0 would be barely acceptable. A value of 3.0 would be totally unacceptable for high quality print jobs. The optical densities referred to above are all measured with a Gretag Macbeth densitometer Type D19C. In table 4 the lithographic properties are given together with the following characteristics of the lithographic printing plate precursors: 0KS, 0V, Surface (rrrVg) {see above) and IR-dye/Surf. : amount of IR-dye (mg), without taken into account the counter ion, per m~ of the total surface of the particles (mg/nrS. Latex wt. % : amount of Latex relative to the total amount of ingredients in the imaging layer (wt.%). Latex/PAA : amount of Latex relative to the amount of the polyacrylic acid (PAA) binder. Dry Coating Weight. : total amount of all ingredients of the dried image-recording layer (g/m2) . Table 4: lithographic evaluation of PPP-1 to ppp-6 From the results shown in cable 4 can be concluded: When the average particle diameter of the hydrophobic particles is less than 40 ran and the amount of IR-dye \|mg\|, without taken into account the counter ion, per nr of total surface of said particles is less than 0.70 mg/nr a bad clean out is observed (comparative example 3, 6). When the average particle diameter of the hydrophobic particles is less than 40 nm and the amount of IR-dye (mg) , without taken into account the counter ion, per m^ of total surface of said particles is more than 0.70 mg/m2 a good clean out is observed (all invention examples). When the average particle diameter of the hydrophobic particles is less than 40 nm and the amount of IR-dye (mg), without taken into account the counter ion, per m' of total surface of said particles is more than 0.70 mg/m2 a higher sensitivity is obtained compared to hydrophobic particles with an average particle size of more than 40 nm (comparative example 1 and all invention examples). Method for making a lithographic printing plate comprising the steps of; (i's providing a negative-working, heat-sensitive lithographic printing plate precursor comprising; - a support having a hydrophilic surface or which is provided with a hydrcphiiic layer and - a coating provided thereon, said coating comprising an image-recording layer which comprises hydrophobic thermoplastic polymer particles, a binder and an infrared absorbing dye characterized in that; - said hydrophobic thermoplastic polymer particles have an average particle diameter, measured by Photon Correlation Spectroscopy, of more than 10 nm and less than 40 nm and - the amount of said IR-dye, without taking into account an optional counter ion, is more than 0.70 mg per rrr of the total surface of said thermoplastic polymer particles, measured by Hydrodynamic Fractionation, and - the amount of hydrophobic thermoplastic polymer particles relative tc the total weight of the ingredients of the imaging layer is at least 60 %. (ii) exposing said precursor to infrared light; (iii) developing said exposed precursor in an alkaline aqueous solution. [CLAIMS] 1. Method for making a lithographic printing plate comprising the steps of; (i) providing a negative-working, heat-sensitive lithographic printing plate precursor comprising; - a support having a hydrophilic surface or which is provided with a hydrophilic layer and - a coating provided thereon, said coating comprising an image-recording layer which comprises hydrophobic thermoplastic polymer particles, a binder and an infrared absorbing dye characterised in that; - said hydrophobic thermoplastic polymer particles have an average particle diameter, measured by Photon Correlation Spectroscopy, of more than 10 rati and less than 40 nm; - the amount of said IR-dye, without taking into account an optional counter ion, is more than 0.70 mg per m2 of the total surface of said thermoplastic polymer particles, measured by Hydrodynamic Fractionation; and - the amount of hydrophobic thermoplastic polymer particles relative to the total weight of the ingredients of the imaging layer is at least 60 %. (ii) exposing said precursor to infrared light; (iii) developing said exposed precursor in an alkaline aqueous solution. 2. A method for making a lithographic printing plate according to claim 1 wherein said hydrophobic thermoplastic polymer particles have an average particle diameter of more than 20 nm and less than 36 nm. 7,. A method for making a lithographic printing plate according- to any or the preceding claims wherein the amount of said IR-dye, without taking into account an optional counter ion, is mors than 1.00 mg per m of the total surfacs of said thermoplastic polymer particles 4. A method for making a lithographic printing plate according to any of Lhe preceding claims wherein the amount of said hydrophobic thermoplastic polymer particles relative to the total amount of ingredients of the image-recording layer is at least 70 %. 5. A method for making a lithographic printing plate according to any of the preceding claims wherein the amount of said hydrophobic thermoplastic polymer particles relative to the amount of said binder is at least 8. 6. A method for making a lithographic printing plate according to any of the preceding claims wherein the image-recording layer further comprises an organic compound comprising at least one phosphonic acid group or at least one .phosphoric acid group or a salt thereof. 7. A method for making a lithographic printing plate according to any of the preceding claims wherein the IR-light used to expose the printing plate precursor has an energy density, measured on the surface of the precursor, of 200 mJ/cnr or less. 3. A method for making a lithographic printing plate according to any of the preceding claims wherein the alkaline aqueous solution has a pH of > 10.0. 9. A method of lithographic printing comprising the steps of: - supplying ink and fountain to a printing plate obtained by method i tD 8 on a printing press; transferring the ink to paper.

Full Text

METHOD FOR MAKING A LITHOGRAPHIC PRINTING PLATE. [DESCRIPTION]
FIELD OF THE INVENTION
The present invention relates to a method for making a lithographic printing plate.
BACKGROUND OF THE INVENTION
Lithographic printing presses use a so-called printing master such as a printing plate which is mounted on a cylinder of the printing press. The master carries a lithographic image on its surface and a print is obtained by applying ink to said image and then transferring the ink from the master onto a receiver material, which is typically paper. In conventional, so-called "wet" lithographic printing, ink as well as an aqueous fountain solution (also called dampening liquid) are supplied to the lithographic image which consists of oleophilic for hydrophobic, i.e. ink-accepting, water-repelling) areas as well as hydrophilic {or oleophobic, i.e. water-accepting, ink-repelling) areas. In so-called driographic printing, the lithographic image consists of ink-accepting and ink-abhesive (ink-repelling) areas and during driographic printing, only ink is supplied to the master.
Printing masters are generally obtained by the image-wise exposure and processing of an imaging material called plats precursor. In addition to the well-known photosensitive, so-called pre-sensitized plates, which are suitable for UV contact exposure through a film mask, also heat-sensitive printing plate precursors have become very popular in the late 1990s. Such thermal materials offer the advantage of daylight stability and are especially used in the so-called computer-to-plate method wherein the plate precursor is directly exposed, i.e. without the use of a film mask. The material is exposed to heat or to infrared light and the generated heat triggers a (physico-)chemical process, such as ablation,

polymerization, insoluhiiizatior. by cross linking of a polymer, heat-induced solubilization, or particle coagulation of a thermoplastic polymer latex.
The most popular thermal plates form an image by a heat-induced solubility difference in an alkaline developer between exposed and non-exposed areas of the coating. The coating typically comprises an oleophilic binder, e.g. a phenolic resin, of which the rate of dissolution in the developer is either reduced (negative working) or increased (positive working), by the image-wise exposure. During processing, the solubility differential leads to the removal of the non-image (non-printing) areas of the coating, thereby revealing the hydrophilic support, while the image (printing) areas of the coating remain on the support. Typical examples of such plates are described in e.g. EP-As 625 728, 823 327, 825 927, 864 420, 894 622 and 901 902. Negative working embodiments of such thermal materials often require a pre-heat step between exposure and development as described in e.g. EP-A 625 728.
Negative working plate precursors which do not require a pre¬heat step may contain an image-recording layer that works by heat-induced particle coalescence of a thermoplastic polymer latex, as described in e.g. EP-As 770 454, 770 495, 770 496 and 770 497. These patents disclose a method for making a lithographic printing plate comprising the steps of (1) image-wise exposing an imaging element comprising hydrophobic thermoplastic polymer particles dispersed in a hydrophilic binder and a compound capable of converting light into heat and (2) developing the image-wise exposed element by applying fountain and/or ink.
EP-A 849 091 discloses a printing plate precursor comprising hydrophobic thermoplastic particles having an average particles size of 40 nm to 150 nm and a polydispersity of less than 0.2.
EP-A 1 342 568 describes a method of making a lithographic printing plate comprising the steps of (1) image-wise exposing an imaging element comprising hydrophobic thermoplastic polymer particles dispersed in a hydrophilic binder and a compound capable of converting light into heat and (2) developing the image-wise exposed element by applying a gum solution, thereby removing non-

5xposecl areas cf the coating from the support.
WO2006/C37"?16 describes a method for preparing a lithographic printing plate which comprises the steps of (1) image-wise exposing an imaging element comprising hydrophobic thermoplastic polymer particles dispersed in a r.ydropr.ilic binder and a compound capable Df converting light into heat ar.d (2) developing the image-wise exposed element; by applying a gum solution, thereby removing nor.-Bxposed areas of the coating from the support and characterised by an average particle size of the thermoplastic polymer particles between 40 nm and 63 nm and wherein the amount of the hydrophobic thermoplastic polymer particles is more than 70 % and less than S5 °s oy weight, relative to the image recording layer. The amount of infrared absorbing dye, hereinafter referred to as IR dye, used in this invention is preferably more then 6 % by weight relative to the image recording layer.
EP-A 1 614 538 describes a negative working lithographic printing plate precursor which comprises a support having a hydrophilic surface or which is provided with a hydrophilic layer and a coating provided thereon, the coating comprising an image-recording layer which comprises hydrophobic thermoplastic polymer particles and a hydrophilic binder, characterised in that the hydrophobic thermoplastic polymer particles have an average particle size in the range from 4 5 nm to 63 nm, and that the amount of the hydrophobic thermoplastic polymer particles in the image-recording layer is at least 70 % by weight relative to the image-recording layer. The amount of IB dye used in this invention is preferably more then 6 %, most preferably more then 8 %, by weight relative to the image recording layer.
EP-A 1 614 539 and EP-A 1 614 540 describes a method of making a lithographic printing plate comprising the steps of (1) image-wise exposing an imaging element disclosed in EP-A 1 614 538 and (2) developing the image-wise exposed element by applying an aqueous, alkaline solution.
EP-A 1 564 020 describes a printing plate comprising a hydrophilic support and provided thereon, an image formation layer containing thermoplastic resin particles in an amount form 60 to 100

% by weight, the thermoplastic particles having a glass transition point (Tg) and an average particle size of from O.Cl -c 2 um, more preferably from 0.1 to 2 um. As thermoplastic particles, polyester resins are preferred. EP 1 564 C20 discloses printing plate precursors comprising polyester thermoplastic particles, cf which the particle size is 160 nm.
The unpublished EP-A 06 111 322 (filed 2006-03-17) describes a negative working lithographic printing plate precursor which comprises a support having a hydrophilic surface or which is provided with a hydrophilic layer and a coating provided thereon, said coating comprising an image-recording layer which comprises hydrophobic thermoplastic polymer particles and a hydrophilic binder, characterised in that said hydrophobic thermoplastic polymer particles comprise a polyester and have an average particle diameter from 18 nm to 50 nm.
A first problem associated with negative-working printing plates that work according to the mechanism of heat-induced latex-coalescence is the complete removal of the non-exposed areas during the development step (i.e. clean-out). An insufficient clean-out may result in toning on the press, i.e. an undesirable increased tendency of ink-acceptance in the non-image areas. This clean-out problem tends to become worse when the particle size of the thermoplastic particles used in the printing plate precursor decreases, as mentioned in EP-As 1 614 538, 1 614 539, 1 614 540 and WO2006/037716.
A decrease of the particle diameter of the hydrophobic thermoplastic particles in the imaging layer may however further increase the sensitivity of the printing plate precursor.
According to the unpublished European Application 06 111 322 (filed 2006-03-17) a good clean out is obtained, even with particle sizes from 18 nm to 50 nm, when the hydrophobic thermoplastic polymer particles comprise a polyester. The sensitivity of the lithographic printing plate precursors comprising said thermoplastic polymer particles remains however rather low.
The rather low sensitivity of negative-working printing plates that work according to the mechanism of heat-induced latex-

coalescence is £ second problem to be solved. A printing piar.e precursor characterised by a low sensitivity needs a longer exposure time and therefore results in a lower throughput (i.e. lower number of printing plate precursors that can be exposed in a given time interval;.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a method for making a lithographic printing plate, that work according to the mechanism of heat-induced latex-coalescence, having a high sensitivity and excellent printing properties with reduced or without toning.
This object is realized with a method for making a lithographic printing plate comprising the steps of;
(i) providing a negative-working, heat-sensitive lithographic printing plate precursor comprising;
- a support having a hydrophilic surface or which is provided with a hydrophilic layer and
- a coating provided thereon, said coating comprising an image-recording layer which comprises hydrophobic thermoplastic polymer particles, a binder and an infrared absorbing dye characterised in that;
- said hydrophobic thermoplastic polymer particles have an average particle diameter, measured by Photon Correlation Spectroscopy, of more than 10 nm and less than 40 nm and
- the amount of said IR-dye, without taking into account an optional counter ion, is more than 0.70 mg per nr of the total surface of said thermoplastic polymer particles, measured by Hydrodynamic Fractionation, and
- the amount of hydrophobic thermoplastic polymer particles relative to the total weight of the ingredients of the imaging layer is at least 60 %.
(ii) exposing said precursor to infrared light;
(iii) developing said exposed precursor in an alkaline aqueous
solution.

Preferred embodiments of the present invention are defined in the dependent claims.
DETAILED DESCRIPTION OF THS INVENTION
The printing plate precursor, used in the method for making a printing plate, comprises a coating on a hydrophilic support. The coating may comprise one or mors layer(s). The layer of said coating comprising the hydrophobic thermoplastic particles is referred to herein as the image-recording layer.
Hydrophobic thermoplastic particles
The hydrophobic particles have an average particle diameter of more than 10 nm and less than 4 0 nrn, preferably of more than 15 nm and less than 38 nm, more preferably of more than 20 and less than 36 nm. The average particle diameter referred to in the claims and the description of this application is meant to be the average particle diameter measured by Photon Correlation Spectrometry (0?Cs) , also known as Quasi-Elastic or Dynamic Light-Scattering, unless otherwise specified. The measurements were performed according the ISO 13321 procedure (first edition, 1996-07-01) with a Brookhaven BI-9G analyzer, commercially available from Brookhaven Instrument Company, Holtsville, NY, USA.
An alternative method to measure the average particle diameter is based on hydrodynamic fractionation. With this technique a volume distribution of the particles is obtained from which a volume average particle diameter is calculated (0V). In the examples the volume average particle diameter, measured according to this technique, is obtained with a PL-PSDA apparatus (Polymer Laboratories Particle Size Diameter Analyser) from Polymer Laboratories Ltd, Church Stretton, Shropshire, UK. From the volume distribution, obtained with the PL-PSDA apparatus, the total surface

of the hydrophobic particles .expressed as square metrs per gram hydrophobic particles, itr/g) can be calculated. In these calculations the density ig/cnr) of the -hermoplastic particles has :o be taken into accour.*. The density of different polymers can be found for example in the handbook 'Properties of polymers, their estimation and correlation with chemical structures' by D.w. Van Krevelen, from Elsevier Scientific Publishing Company, second edition, pages 574 to 581). The density may also be measured. For particles or lattices, the so-called skeletal (definition according to ASTM D3766 standard) density may be measured according to the gas displacement method.
The amount of hydrophobic thermoplastic polymer particles is at least 60, preferably at least 65, more preferably at least 70 percent by weight relative to the weight of all the ingredients in the image-recording layer.
The hydrophobic thermoplastic polymer particles which are present in the coating are preferably selected from polyethylene, poly-(vinyl)chloride, polymethyl(meth)acrylate, polyethyl (methj acrylate, polyvinylidene chloride, poly(meth)acrylonitrile, polyvinyl-carbazole, polystyrene or copolymers thereof.
According to a preferred embodiment, the thermoplastic polymer particles comprise polystyrene or derivatives thereof, mixtures comprising polystyrene and poly(meth)acrylonitrile or derivatives thereof, or copolymers comprising polystyrene and poly(meth)-acrylonitrile or derivatives thereof. The latter copolymers may comprise at least 50 wt.% of polystyrene, more preferably at least 65 wt.% of polystyrene. In order to obtain sufficient resistivity towards organic chem." caIs such as hydrocarbons used in e.g. plate cleaners, the thermoplastic polymer particles preferably comprise at least 5 wt.%, more preferably at least 30 wt.%, of nitrogen containing units, such as (meth)acrylonitrile, as described in Ep-A 1 219 416. According to the most preferred embodiment, the thermoplastic polymer particles consist essentially of styrene and acrylonitrile units in a weight ratio between 1:1 and 5:1 (styrene:acrylonitrile), e.g. in a 2:1 ratio.
In a preferred embodiment the hydrophobic thermoplastic particles do not consist of polyester.

The weight average m^lecuiiir weight of the n he miopias tic polymer particles may range from 5,000 to 1,000,000 g/mol.
The hydrophobic thermoplastic polymer particles can be prepared by addition polymerization or by condensation polymerization. They ere preferably applied onto the lithographic base in the form of a dispersion in an aqueous coaling liquid. These water based dispersions can he prepared by polymerization in a water-cased system e.g. by free-radical emulsion polymerization as described in US 3 476 937 cr EP-A 1 217 010 or by means of dispersing techniques of che water-insoluble polymers into water. Another method for preparing an aqueous dispersion of the thermoplastic polymer particles comprises (1) dissolving the hydrophobic thermoplastic polymer in an organic water immiscible solvent, (2) dispersing the thus obtained solution in water or in an aqueous medium and (3) removing the organic solvent by evaporation.
Emulsion polymerization is typically carried out through controlled addition of several components - i.e. vinyl monomers, surfactants (dispersion aids], initiators and optionally other components such as buffers or protective colloids - to a continuous medium, usually water. The resulting polymer is a dispersion of discrete particles in water. The surfactants or dispersion aids which are present in the reaction medium have a multiple role in the emulsion polymerization: (1) they reduce the interfacial tension between the monomers and the aqueous phase, (2) they provide reaction sites through micelle formation in which the polymerization occurs and (3) they stabilize the growing polymer particles and ultimately the latex emulsion. The surfactants are absorbed at the water/polymer interface and thereby prevent coagulation of the fine polymer particles. Non-ionic, cationic and anionic surfactants may be used in emulsion polymerization. Preferably non-ionic or anionic surfactants are used. Most preferably the hydrophobic thermoplastic particles are stabilized with ar. anionic dispersion aid. Specific examples of suitable anionic dispersion aids include sodium lauryl sulphate, sodium lauryl ether sulphate, sodium dodecyl sulphate, sodium dodecyl benzene sulphonate and sodiuro lauryl phosphate; suitable non-ionic dispersion aids are for example ethoxylated

lauryi aleonol anc ethoxylatSG octylphenol.
IP. absorbing compounds
The coating contains a dye which absorbs infrared (IR) light and converts the absorbed energy into heat. Preferred IR absorbing dyes are cyanine, merocyanine, indoaniline, oxonol, pyrilium and squsrilium dyes. Examples of suitable IR absorbers are described in e.g. EP-As S23 327, 973 376, 1 C29 667, 1 053 S68 and 1 093 934 and WOs 97/39894 and 00/29214.
Other preferred IR-dyes are described in EP 1 614 541 (page 20 line 25 to page 44 line 29] and the unpublished EP-A 05 105 440 (filed 2005-06-21). IR-dyes, preferably used in this invention, are water compatible, most preferably, water soluble.
In the prior art, e.g. in EP-A 1 614 538, the IR-dye amount is preferably at least 6 %, more preferably at least 8 %, by weight relative to the image recording layer, irrespective of the average particle diameter of the hydrophobic thermoplastic particles used. According to EP-A 1 614 538 lithographic printing plates comprising hydrophobic thermoplastic particles with a particle size less then 40 nm have inferior lithographic properties, i.e. a bad clean-out (e.g. comparative in example 1, average particle diameter = 36 nm).
It has surprisingly been found that lithographic printing plates comprising hydrophobic thermoplastic particles with a particle size of more then 10 nm and less then 40 nm, characterised by a good clean-out and a high sensitivity, are obtained by adjusting the amount of IR-dye in relation to the amount and the average particle diameter of said thermoplastic particles. As a result of this investigation it has been found that by adjusting the amount of IR-dye in relation to the total surface of the hydrophobic thermoplastic particles present in the image-recording layer, printing plate precursors with optimum lithographic properties are obtained. The total surface of the hydrophobic thermoplastic particles is calculated as described above and in the examples. A possible explanation of this phenomenon may be that all or part of

the IR-ayes adsorb on the surface of the hydrophobic particles and render the particles more dispersible in aqueous solutions (e.g. developer) resulting in an improved clean-out behavior. Since it is believed that optional counter ions of the IR-dyes (i.e. when the IR-dyes are used as salts) do not have an essential contribution to the invention, the amount of IR-dye used according to this invention is meant to be the amount of IR-dye without taking into account an optional counter ion. A good clean-out and superior sensitivity with lithographic printing plates comprising hydrophobic thermoplastic particles with a particle diameter of more than 10 nm and size less than 40 nm, is obtained when the amount of IR-dye, without taking into account an optional counter ion, is more than 0.70 mg, preferably more than 0.85 mg, more preferably more than 1.00 mg per ITT of the total surface of said thermoplastic polymer particles. These findings imply that when the average particle diameter of the hydrophobic thermoplastic particles decreases (and the amount of particles (g/m2) in the imaging layer remains constant) the amount of IR dye in the imaging layer must be increased to maintain good lithographic properties. Referring to the comparative example of EP-A 1 614 538 mentioned above, the amount of IR-dye, without taking into account the counter ion, used therein is less then 0.70 rag per m2 of the total surface of the thermoplastic polymer particles, having an average particle diameter of 36 nm.
There is no particular upper limit for the amount of IR-dye. However, when the total infrared optical density (e.g. at 830 nm) of the coating becomes too high, the IR-light emitted from the exposure source, may not reach the lower part of the imaging layer, resulting in a poor coalescence of the thermoplastic polymer particles at the part of the imaging layer that makes contact with the support. This may be overcome with a higher energy exposure, but results in a lower throughput (numbers of printing plate precursors that can be exposed in a given time interval). The maximum optical density at 830 nm of the coating, obtained from diffuse reflectance spectra, measured with a Shimadzu UV-3101 PC/ISR-3100 spectrophotometer, is preferably less then 2.00, more preferably less then 1.50, most preferably less then 1.25.

Binder
The image-recording layei may further comprise a hydrophilic binder. Examples of suitaole hydrophilic binders are horriopolymers and copolymers of vinyl alcohol, imeth)acryiamide. methyloi imeth)acryiamide, imeth)acrylic acid, hydroxyethyl (meth)acrylate, naleic anhydride/vmylmethyiether copolymers, copolymers of imeth)acrylic acid or vinylalcohol with styrene sulphonic acid.
Preferably, the hydrophilic binder comprises polyvinylalcohcl or polyacrylic acid.
The amount of hydrophilic binder may be between 2.5 and 50 wt.%, preferably between 3 and 20 wt.3, more preferably between 4 and 10 wt.% relative to the total weight of all ingredients of the image-recording layer.
The amount of the hydrophobic thermoplastic polymer particles relative to the amount of the binder is preferably between 8 and 20, more preferably between 10 and 18, most preferably between 12 and 16.
Contrast Dyes
Colorants, such as dyes or pigments, which provide a visible color to the coating and remain in the exposed areas of the coating after the processing step may be added to the coating. The image-areas, which are not removed during the processing step, form a visible image on the printing plate and examination of the lithographic image on the developed printing plate becomes feasible. Typical examples of such contrast dyes are the ammo-substituted tri- or diarylmethane dyes, e.g. crystal violet, methyl violet, victoria pure blue, flexoblau 630, basonylblau 640, auraraine and malachite green. Also the dyes which are discussed in depth in the detailed description of EP-A 40C 706 are suitable contrast dyes. Dyes which, combined with specific additives, only slightly color

the coating but which become intensively "Glared after exposure, as described in for example WO2006/0C5686 are also of interest.
Other ingredients.
Optionally, the coating may further contain additional ingredients. These ingredients may be present in the image-recording layer or in an optional other layer. For example, additional binders, polymer particles such as matting agents and spacers, surfactants such as perfluoro-surfactants, silicon or titanium dioxide particles, development inhibitors, development accelerators, colorants, metal complexing agents are well-known components of lithographic coatings.
Preferably the image-recording layer comprises an organic compound, characterised in that said organic compound comprises at least one phosphonic acid group or at least one phosphoric acid group or a salt thereof, as described in the unpublished European Patent Application 05 109 781 (filed 2005-10-20). In a particularly preferred embodiment the image-recording layer comprises an organic compound as represented by formtla I:

Compounds according tc formula I may be present i- the image-recording layer in an amount between 0.05 and 15 wt.%, preferablv between 0.5 and 1C wz.%, more preferably between 1 and 5 w-.= relative tc the total weight of the ingredients of the image-reccrding layer.
Other layers cf the coating
To protect the surface cf the coating, in particular from mechanical damage, a protective layer may optionally be applied on the image-recording layer. The protective layer generally comprises at least one water-soluble polymeric binder, such as polyvinyl alcohol, polyvinylpyrrolidone, partially hydrolyzed polyvinyl acetates, gelatin, carbohydrates or hydroxyethylcellulose. The protective layer may contain small amounts, i.e. less then 5 % by weight, of organic solvents. The thickness of the protective layer is not particularly limited but preferably is up to 5.0 um, more preferably from 0.05 to 3.0 um, particularly preferably from 0.10 to 1.0 um.
The coating may further contain other additional layer(s) such as for example an adhesion-improving layer located between the image-recording layer and the support.
Support
The support of the lithographic printing plate precursor 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.
In one embodiment of the invention the support is a metal support such as aluminum or stainless steel. The support can also be a laminate comprising an aluminum foil and a plastic layer, e.g. polyester film. A particularly preferred lithographic support is an

aluminum support. Any known and widely used aluminum materials can be used. The aluminum support: has a thickness of about 0.1-0.6 mm. However, this thickness can be changed appropriately depending on the size of the printing plate used and the plate-setters on which the printing place precursors jie exposed.
To optimize the lithographic properties, the aluminum support is subjected to several treatments well known in the art such as for example: decrease, surface roughening, etching, anodizaeion, sealing, surface treatment. In between such treatments, a neutralization treatment is often carried out. A detailed description of these treatments can be found in e.g. EP-As 1 142 707, 1 564 020 and 1 614 533.
A preferred aluminum substrate, characterized by an arithmetical mean center-line roughness Ra less then 0.45 u is described in EP 1 356 926.
Optimizing the pore diameter and distribution thereof of the grained and anodized aluminum surface as described in EP 1 142 707 and US 6 692 890 may enhance the press life of the printing plate and may improve the toning behaviour. Avoiding large and deep pores as described in US 6 912 956 may also improve the toning behaviour of the printing plate. An optimal ratio between pore diameter of the surface of the aluminum support and the average particle size of the hydrophobic thermoplastic particles may enhance the press run length of the plate and may improve the toning behaviour of the prints. This ratio of the average pore diameter of the surface of the aluminum support to the average particle size of the thermoplastic particles present in the image-recording layer of the coating, preferably ranges from 0.05:1 to 0.8:1, more preferably from 0.10:1 to 0.35:1.
Alternative supports for the plate precursor can also be used, such as amorphous metallic alloys (metallic glasses). Such amorphous metallic alloys can be used as such or joined with other non-amorphous metals such as aluminum. Examples of amorphous metallic alloys are described in US 5 288 344, US 5 368 659, US 5 618 359, US 5 735 975, US 5 250 124, US 5 032 196, US 6 325 868, and US 6 818 078. The following references describe the science of amorphous

metals in much more detail and sre incorporated as references: Introduceion to rhe Theory of Amorphous Metals, N.P. Kovalenkc sc al.i200ii; Atomic Ordering in Liquid and Amorphous Metals, S.I. Popel, et al; Physics of Amorphous Metals, N.P. Kovalenko su al
(2 001;.
According to another embodiment, "he support can also be a flexible support, which is provided with a hydrophilic layer. The flexible support is e.g. paper, plastic film, thin aluminum or a laminare thereof. Preferred examples of plastic film are poly¬ethylene "cerephthalate film, polyethylene naphthalate film, cellulose acetate film, polystyrene film, polycarbonate film, etc. The plastic film support may be opaque or transparent. Particular examples of suitable hydrophilic layers that may be supplied to a flexible support for use in accordance with the present invention are disclosed in EP-A 601 240, GB 1 419 512, FR 2 300 354, US 3 971 660, US 4 284 705, EP 1 614 538, EP 1 564 020 and US 2006/0019196.
Exposure
The printing plate precursor is exposed with infrared light, preferably near infrared light. The infrared light is converted into heat by an IR-dye as discussed above. The heat-sensitive lithographic printing plate precursor of the present invention is preferably not sensitive to visible light. Host preferably, the coating is not sensitive to ambient daylight, i.e. visible (400-750 nm] and near UV light (300-400 nm) at an intensity and exposure time corresponding to normal working conditions so that the material can be handled without the need for a safe light environment.
The printing plate precursors of the present invention can be exposed to infrared light by means of e.g. LEDs or an infrared laser. Preferably lasers, emitting near infrared light having a wavelength in the range from about 700 to about 1500 nm, e.g. a semiconductor laser diode, a Kd:YAG or a Nd:YLF laser, are used. Most preferably, a laser emitting in the range between 780 and 830 nm is used. The required laser power depends on the sensitivity of

cne image-recording layer, the pixel dwell rime of rhe laser bsaiu, which is determined by the spot diameter (typical value of modern plate-setters at 1/e- of maximum intensity : 10-25 urn) , the scar, speed and the resolution of the exposure apparatus (i.e. the number of addressable pixels per unit cf linear distance, often expressed in dots per inch or dpi; typical value : 1000-4000 dpi).
In a preferred embodiment of this invention a useful lithographic image is obtained upon image-wise exposure of the printing plate precursor with IR-light having an energy density, measured at the surface of said precursor, of 200 mj/cnr" or less, more preferably of 180 mJ/cm^ or less, most preferably of 160 mJ/cnr or less. With a useful lithographic image on the printing plate, 2 % dots (at 200 lpi) are perfectly visible on at least 1 000 prints on paper.
Two types of laser-exposure apparatuses are commonly used: internal (ITD) and external drum (XTD) plate-setters. ITD plate-setters for thermal plates are typically characterized by a very high scan speed up to 1500 m/sec and may require a laser power of several Watts. The Agfa Galileo T (trademark of Agfa Gevaert W.V.) is a typical example of a plate-setter using the ITD-technology. XTD plate-setters for thermal plates having a typical laser power from about 20 mW to about 500 mW operate at a lower scan speed, e.g. from 0.1 to 20 m/sec. The Agfa Xcalibur, Accento and Avalon plate-setter families (trademark of Agfa Gevaert N.V.] make use of the XTD-technology.
Due to the heat generated during the exposure step, the hydrophobic thermoplastic polymer particles may fuse cr 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. 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. Preferably the coagulation temperature is at least 10 °C below the temperature at which the decomposition of the polymer particles occurs. The

coagulation temperature is pr&ierably higner than 50 °C, more preferably above 100 °C.
Development
Afrer exposure, the material can be developed by supplying to the coating an aqueous alkaline solution whereby the non-image areas of the coating are removed. This developing step with an aqueous alkaline developer solution may be combined with mechanical rubbing, e.g. by a rotating brush. During the development step, any water-soluble protective layer present is preferably also removed. A preferred developer solution is a developer with a pH of at least 9, preferably at least 10, more preferably at least 11, most preferably at least 12.
The developer comprises an alkaline agent. In a preferred embodiment said alkaline agent comprises an alkaline silicate or metasilicate. The alkaline silicate or metasilicate exhibits an alkalinity when dissolved in water, and examples thereof include an alkali metal silicate and alkali metal metasilicate such as sodium silicate, sodium metasilicate, potassium silicate and lithium silicate, and ammonium silicate. Said alkaline silicate may be used alone, or in combination with another alkaline agent.
The development performance of the alkaline aqueous solution may be easily modulated by adjusting the molar ratio of alkaline silicates and alkali metal hydroxides, represented by silicon oxide
(Si02) and an alkali oxide (M2O, wherein M represents an alkali metal or an ammonium group). The alkaline aqueous solution has preferably a molar ratio Si02/M20 from 0.5 to 3.0, more preferably from 1.0 to 2.0, most preferably of 1.0.
The concentration of alkaline silicate in the developer ranges generally from 1 to 14% by weight, preferably from 3 to 14% by weight, and more preferably from 4 to 14% by weight.
In another embodiment, the aqueous alkaline solution may comprise a nonreducing sugar. The nonreducing sugar denotes sugars

r.sviric n: reductive property due tc ~he aosence of a free aldehyde group cr a free Ketone group. Said nonreducing sugar is classified into trehalose-^ype oligosaccharides wherein a reductive group and another reductive group make a linkage; glycosides wherein a reductive group in a sugar is linked *o a non-sugar compound; and sugar alcohols which are produced by reducing a sugar with hydrogenation. Said trehalose-type oligosaccharides include sucrose and trehalose, and said glycosides include alkyl glycosides, phenol glycosides, mustard oil glycosices and the like. Said sugar alcohols include D,L-arabitol, ribitoi, xylitol, D,L-sorbitol, D,L-mannitol, D,L-iditol, talitol, dulcitol, allodulcitol and the like. Further, maltitol obtained hy hydrogenation of disaccharide, a reduced material obtained by hydrogenation of oligosaccharide (a reduced starch syrup) and the like are preferably used. Pentaerythritol car. also be used in the developing solution.
Of the above mentioned nonreducing sugars, preferred are sugar alcohols and sucrose, and particularly preferred are D-sorbitol, sucrose and a reduced starch syrup, since they have buffering action in appropriate pH range.
In addition to alkali metal silicates and/or nonreducing sugars, the developer may optionally contain further components, such as buffer substances, complexing agents, antifoams, organic solvents in small amounts, corrosion inhibitors, dyes, surfactants and/or hydrotropic agents as known in the art.
Development is preferably carried out at temperatures of from 20 to 40 °C in automated processing units as customary in the art.
For replenishment (also called regeneration) purposes, alka i metal silicate solutions having alkali metal contents of from 0.6 to 2.0 mol/1 can suitably be used. These solutions may have the same silica/alkali metal oxide ratio as the developer and optionally contain further additives. Replenishment may be tailored to the developing apparatuses used, daily plate throughputs, image areas, etc. and are in general from 1 to 50 ml per square meter of plate precursor. Addition of replenisher can be regulated, for example, by measuring the conductivity of the developer as described in EP-A 0 556 690.

protective compounds that are capable of protecting the lithographic image cf a printing plate against contamination or damaging. Scitabie examples of such compounds are film-forming r_ydropb.il 2. c polymers or surfactants.
The plate precursor can, i: required, be post-treated with a suitable correcting agent or preservative as known in the art. To increase the resistance of the finished printing plate and hence to extend the run length, the layer can be briefly heated to elevated temperatures ("baking"!. The plate can be dried before baking or is dried during the baking process itself. During the baking step, the plate can be heated at a temperature which is higher than the glass transition temperature of the thermoplastic particles, e.g. between 100 °C and 230 °C for a period of 40 minutes to 5 minutes. A preferred baking temperature is above 60 °C. For example, the exposed and developed plates can be baked at a temperature of 230 °C for 5 minutes, at a temperature of 15C "C for 10 minutes or at a temperature of 120 °C for 30 nunutes. Baking can be done in conventional hot air ovens or by irradiation with lamps emitting in the infrared or ultraviolet spectrum. As a result of this baking step, the resistance of the printing plate to plate cleaners, correction agents and UV-curable printing inks increases. Such a thermal post-treatment is described in e.g. DE 1 447 963 and GB 1 154 749.
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 so-called single-fluid ink without a dampening liquid. Suitable single-fluid inks have been described in US 4 045 232; US 4 981 517 and US 6 140 392. In a most preferred embodiment, the single-fluid ink comprises an ink phase, also called the hydrophobic or oleophilic phase, and a polyol phase as described in JVO 00/32705.

Ir_ another preferred emboaj.mer.r., development cff p_ess »:;-r. e.g. a developing solution, where-in r.he non-exposed areas of the image recording layer are parrialiy removed, may be combined with a development or. press, wherein a complete removal cf -he non-exposed is realised.
EXAMPLES
Preparation hydrophobic Ehermoplastic parr-ides (LX-01 to LX-G2)
Preparation of LX-01:
The polymer emulsion was prepared by means of a 'semi-continuous emulsion' polymerization wherein all monomers (styrene and acrylonitrile) are added to the reactor. All surfactant (3 wt. "a relative to the monomer amount! is present in the reactor before the monomer addition was started. In a 2 1 double-jacketed reactor, 10.8 g of sodium dodecyl sulphate (Texapon K12 from Cognis) and 1243.9 g of" demineralised water was added. The reactor was flushed with nitrogen and heated until 80 °C. When the reactor content reached a temperature of 80 °C, 12 g of a 5% solution of sodium persulphate in water was added. The reactor was subsequently heated for 15 min. at 80 °C. Then the monomer mixture (238.5 g of styrene and 121.5 g of acrylonitrile) was dosed during 180 min. Simultaneously with the monomer addition, an additional amount of an aqueous persulphate solution was added [24 g of a 5% aqueous Na2S2Oe solution). After the monomer addition was finished the reactor was heated for 30 min. at 80 °C. To reduce the amount of residual monomer, a redox-initiation system was added: 1.55 g sodium formaldehyde sulphoxylate dihydrate (SFS) dissolved in 120 g water and 2.57 g of a 70 wt.% t-butyl hydro peroxide (TBHP) diluted with 22.5 g of water. The aqueous solutions of SFS and TBHP were added separately during 80 min. The reactor was then heated for another 10 min. and was subsequently cooled to room temperature. 800 g of a 5 wt.% aqueous solution of 5-bromo-5-nitro-1,3-dioxane was added as biocide and the latex was filtered using a

zoarse tiller paper.
This resulted in the lacex dispersion 1X-01 with a solid content of 20.64 wt.% and a pH cf 3.71.
Preparation of LX-02:
The polymer ernulsior. was prepared by means of a 'semi-continuous emulsion' polymerization wherein all monomers (styrene and acrylonitrile) are added to the reactor. All surfactant (2.15 wt.i towards the monomer amount) is present in the reactor before the monomer addition is started. In a 400 1 double-jacks ted reactor, 17.2 kg cf a 10 wt.% aqueous solution of sodium dodecyl sulphate
(Texapon K12 from Cognis) and 265 kg of demineralised water was added. The reactor was brought under inert atmosphere by 3 times vacuum/nitrogen exchange. The reactor content was stirred at 100 rpm and heated until 82 °C. When the reactor content reached a temperature of 82 °C, 6.67 kg of a 2% of sodium persulphate in water was added. The reactor was subsequently heated for 15 min. at 82 °C. Then the monomer mixture (53.04 kg of styrene and 27.0 kg Of acrylonitrile) was dosed during 3 hours. Simultaneously with the monomer addition an aqueous persulphate solution was added (13.34 kg of s 2% aqueous Na^SjOe solution) during 3 hours. The monomer flask was flushed with 5 1 of demineralised water. After the monomer addition the reactor was heated during 60 min. at 82 DC. To reduce the amount of residual monomer a redox-initiation system was added
(340 g of sodium formaldehyde sulphoxylate dihydrate (SFS) dissolved in 22.81 kg water and 570 g of a 70 wt.% t-butyl hydro peroxide
(TBHP) diluted with 4.8 kg of water. The aqueous solutions of SFS and TBHP were added separately during 2 hours, and 20 min. The reaction was then heated for another 10 min. at 82 °C and was subsequently cooled to room temperature. 800 g of a 5 wt.% aqueous solution of 5-bromo-5-nitro-l,3-dioxane was added as biocide and the latex was filtered using a 5 micron filter.
This resulted in the latex dispersion LX-02 with a solid content of 19.92 wt.% and a pH of 3.2.

Particle size and surface of t-he hydrophobic thermoplastic particles
Two techniques were used :c measure the particle diameter of the hydrophobic thermoplastic particles, as described in the detailed description:
0,.-s : is the particle diameter obtained by Photon Correlation
Spectroscopy. The measurements were performed according the ISO 13321 procedure (first edition, 1996-07-01) with a Brookhaven BI-90 analyzer from Brookhaven Instrument Company, Holt5vilie, NY, USA.
0-,- : is the volume average particle diameter obtained with
hydrodynamic fractionation obtained with a PL-PSDA apparatus (Polymer Laboratories Particle Size Diameter Analyzer) from Polymeric Labs.
From the volume particle size distribution, obtained with the PL-PSDA apparatus, the total surface of the hydrophobic thermo¬plastic particles [Surface (m2/g)) is calculated. These calculations have been performed with a density (p, (g/cm3) ) of the particles of 1.10 g/cmJ. Since all particles LX-01 to LX-02 have the same composition, they all have the same density. The density of the particles LX-01 to LX-02 (skeletal density according to ASTM D3766 standard) has been measured using the gas displacement method on a Accupyc 1330 helium-pycnometer (from Micromeritics).
The calculations are based on the following formulas:
p = Density (g/cm3)
V = Volume of 1 g particles
N = Number of particles in 1 g
S = total Surface of 1 g of particles (m2/g)
0V = Volume particle diameter (nm)

A 0.2 mm thick aluminum io.. I was degreased by spraying with ar. aqueous solution containing 34 g/1 NaOH at 70 °C for 6 seconds and rinsed with dsmmeralised water for 3.6 seconds. The foil was tner. electrochemically grained during 6 seconds using an alternating current in an aqueous solution containing 15 g/1 HC1, 15 g/1 SCV ions and 5 g/1 AT"" ions at a temperature of 37 °C and a current density of about 100 A/dm" {charge density cf about SCO C/dfir). Afterwards, the aluminum foil was desmutted by etching with an aqueous solution containing 145 g/1 of sulphuric acid at 80 °c for 5 seconds and rinsed with demineralised water for 4 seconds. The foil was subsequently subjected to anodic oxidation during 10 seconds in an aqueous solution containing 145 g/i of sulphuric acid at a temperature of 57 °C and a current density of 33 A/dm" (charge density of 330 C/dm2) , then washed with demineralised water for 7 seconds and post-treated for 4 seconds (by spray) with a solution containing 2.2 g/1 PVPA at 70 °C, rinsed with demineralised water for 3.5 seconds and dried at 120 °C for 7 seconds. The support thus obtained is characterised by a surface roughness Ra of 0.35-0.4 um (measured with interferometer NT1100] and have an anodic weight of about 4 . 0 g/rrr
ingredients used in the preparation of the printing plate precursors
PAA: Polyacrylic acid from Ciba Specialty Chemicals. PAA was added to the coating solutions as a 5 wt% aqueous solution
IR-1: Chemical formula see table 2. IR-1 was added to the coating solutions as a 1 wt% aqueous solution
IR-2: Chemical formula see table 2. IR-2 was added to the coating solutions as a 1 wt% aqueous solution
IR-3: Chemical formula see table 2. IR-3 was added to the coating solutions as a solid.

:-iSDP: 1-hydroxyethylidene-l, 1-diphcsphonic acid from Solutia. HE.D? was added to ;.ie coaling solutions as a 10 w:-t aqueous solution
FSO ICO : Zonyl FSO 100, a flucr surfactant from Dupont
CD-01 : 5 % aqueous dispersion of a modified Cu-phthaiocyanine
IJX 883 from Cabot Corporation. CD-02 : 20 ". aqueous dispersion of a phthalocyanine Heliogsn 'Biau
D7490 from BASF. The dispersion is stabilized with an
anionic surf actar.i. CD-03 : 20 % aqueous dispersion of PV Fast Violet RL from
Clariant. The dispersion is stabilized with an anionic
surfactant.

Example 1: Printing plate precursors PPP-1 to 6
Preparation of the coating solutions
The coating solutions for the printing plate precursors 1 to 6 were prepared using the solutions or dispersions as described above. The latex dispersions (LX) were added to demineralised water followed by stirring for 10 minutes and addition of the IB-dye. After SO minutes of stirring the poly acrylic acid (PAA) solution was added followed by stirring during 10 minutes and addition of the HEDP solution. Subsequently after another 10 minutes of stirring the surfactant solution was added and the coating dispersion was stirred for another 30 minutes. Subsequently the pH was adjusted to a value of 3.6 with a diluted ammonia solution (ca 3%).
Preparation of the printing plate precursors PPP-1 to PPP-6
The printing plate precursor coating solutions were subsequently coated on the aluminum substrate, as described above, with a coating knife at a wet thickness of 30 urn. The coatings were dried at 60°C. Table 3 lists the resulting dry coating weight of the different components of the printing plate precursors.

Exposure, development and printing of the printing plate precursors
The printing plate precursors were exposed on a Creo Trend-Setter 3244 40W fast head IR-laser plate-setter at 300 - 250 - 200 -150 - 100 mj/cm£ at 150 rotations per minute (rpm) with a 200 line per inch (lpi) screen and an addressability of 2400 dpi.
After exposure the printing plate precursors were developed in a VA-98 processor (from Agfa Gevaert NV] with a TD1000 developer (from Agfa-Gevaert NV) followed by gumming using a gum solution prepared as follows:
To 700 ml demineralized water
11.3 ml Dowfax 3B2 (commercially available from Dow Chemical)
32.6 g of trisodium citrate dihydrate
9.8 g citric acid monohydrate
were added whilst stirring

demineralized water was further added to obtain LOCO g gurn solution.
After development and gumrp.ing the printing plates were mounted zr. a GT046 printing press. A compressible blanket was used and printing was done with the fountain Agfa Prima FS101 (trademark of Agfa) and K+E SZO clack ink (trademark: of K£E; . The following start¬up procedure was used : first 5 revolutions with the dampening form rollers engaged, then 5 revolutions with both the dampening and ink form rollers engaged, then printing started. 1000 prints were made on 80 g offset paper.
Evaluation of the printing plate precursors PPp-1 to PPP-6
The printing plate precursors are evaluated by the following characteristics:
Sensitivity 1 : Plate sensitivity (2% dot) (mj/crrr) ; the lowest exposure energy density at which 2% dots are perfectly visible (by means of a 5x magnifying glass) on the one-thousandth print on paper.
Sensitivity 2 : Plate sensitivity (B-25 2%) (rnJ/cm2) : is the
interpolated energy density value where the surface coverage (calculated from the measured optical density of the one-thousandth print on paper) of a B-25 2% dot patch equals 55%. A B-25 2% dot patch consists of 2% ABS (200 lpi, 2400 dpi) dots, but the total surface coverage of these dots is 25%. ABS dots are generated with the Agfa Balanced Screening methodology.

Clean-out:

After 750 prints, the paper sheet size is shortened

and printing is continued for another 250 prints. After 1 OQC prints, a few more prints are generated on the normal paper size. If any staining should occur, this will result in an accumulation of ink on the blanket, while printing is performed with the shortened paper size. This accumulated ink will tier, oe transferred to the paper when the normal paper size is used again, after 1 000 prints. This method allows for a very precise evaluation of the stain level. A value of 5.0 indicates that no stain is observed after 1 000 prints. A value of 4.0 would be barely acceptable. A value of 3.0 would be totally unacceptable for high quality print jobs.
The optical densities referred to above are all measured with a Gretag Macbeth densitometer Type D19C.
In table 4 the lithographic properties are given together with the following characteristics of the lithographic printing plate precursors: 0KS, 0V, Surface (rrrVg) {see above) and
IR-dye/Surf. : amount of IR-dye (mg), without taken into
account the counter ion, per m~ of the total surface of the particles (mg/nrS.
Latex wt. % : amount of Latex relative to the total amount
of ingredients in the imaging layer (wt.%).
Latex/PAA : amount of Latex relative to the amount of the
polyacrylic acid (PAA) binder.
Dry Coating Weight. : total amount of all ingredients of the dried
image-recording layer (g/m2) .
Table 4: lithographic evaluation of PPP-1 to ppp-6

From the results shown in cable 4 can be concluded:
When the average particle diameter of the hydrophobic particles is less than 40 ran and the amount of IR-dye |mg|, without taken into account the counter ion, per nr of total surface of said particles is less than 0.70 mg/nr a bad clean out is observed (comparative example 3, 6).
When the average particle diameter of the hydrophobic particles is less than 40 nm and the amount of IR-dye (mg) , without taken into account the counter ion, per m^ of total surface of said particles is more than 0.70 mg/m2 a good clean out is observed (all invention examples).
When the average particle diameter of the hydrophobic particles is less than 40 nm and the amount of IR-dye (mg), without taken into account the counter ion, per m' of total surface of said particles is more than 0.70 mg/m2 a higher sensitivity is obtained compared to hydrophobic particles with an average particle size of more than 40 nm (comparative example 1 and all invention examples).

Method for making a lithographic printing plate comprising the steps of;
(i's providing a negative-working, heat-sensitive lithographic printing plate precursor comprising;
- a support having a hydrophilic surface or which is provided with a hydrcphiiic layer and
- a coating provided thereon, said coating comprising an image-recording layer which comprises hydrophobic thermoplastic polymer particles, a binder and an infrared absorbing dye characterized in that;
- said hydrophobic thermoplastic polymer particles have an average particle diameter, measured by Photon Correlation Spectroscopy, of more than 10 nm and less than 40 nm and
- the amount of said IR-dye, without taking into account an optional counter ion, is more than 0.70 mg per rrr of the total surface of said thermoplastic polymer particles, measured by Hydrodynamic Fractionation, and
- the amount of hydrophobic thermoplastic polymer particles relative tc the total weight of the ingredients of the imaging layer is at least 60 %.
(ii) exposing said precursor to infrared light;
(iii) developing said exposed precursor in an alkaline aqueous solution.

[CLAIMS]
1. Method for making a lithographic printing plate comprising the
steps of;
(i) providing a negative-working, heat-sensitive
lithographic printing plate precursor comprising;
- a support having a hydrophilic surface or which is provided with a hydrophilic layer and
- a coating provided thereon, said coating comprising an image-recording layer which comprises hydrophobic thermoplastic polymer particles, a binder and an infrared absorbing dye characterised in that;
- said hydrophobic thermoplastic polymer particles have an average particle diameter, measured by Photon Correlation Spectroscopy, of more than 10 rati and less than 40 nm;
- the amount of said IR-dye, without taking into account an optional counter ion, is more than 0.70 mg per m2 of the total surface of said thermoplastic polymer particles, measured by Hydrodynamic Fractionation; and
- the amount of hydrophobic thermoplastic polymer
particles relative to the total weight of the
ingredients of the imaging layer is at least 60 %.
(ii) exposing said precursor to infrared light;
(iii) developing said exposed precursor in an alkaline aqueous solution.
2. A method for making a lithographic printing plate according to
claim 1 wherein said hydrophobic thermoplastic polymer
particles have an average particle diameter of more than 20 nm
and less than 36 nm.

7,. A method for making a lithographic printing plate according- to any or the preceding claims wherein the amount of said IR-dye, without taking into account an optional counter ion, is mors than 1.00 mg per m of the total surfacs of said thermoplastic polymer particles
4. A method for making a lithographic printing plate according to any of Lhe preceding claims wherein the amount of said hydrophobic thermoplastic polymer particles relative to the total amount of ingredients of the image-recording layer is at least 70 %.
5. A method for making a lithographic printing plate according to any of the preceding claims wherein the amount of said hydrophobic thermoplastic polymer particles relative to the amount of said binder is at least 8.
6. A method for making a lithographic printing plate according to any of the preceding claims wherein the image-recording layer further comprises an organic compound comprising at least one phosphonic acid group or at least one .phosphoric acid group or a salt thereof.
7. A method for making a lithographic printing plate according to any of the preceding claims wherein the IR-light used to expose the printing plate precursor has an energy density, measured on the surface of the precursor, of 200 mJ/cnr or less.
3. A method for making a lithographic printing plate according to any of the preceding claims wherein the alkaline aqueous
solution has a pH of > 10.0.
9. A method of lithographic printing comprising the steps of: - supplying ink and fountain to a printing plate obtained by

method i tD 8 on a printing press; transferring the ink to paper.

Documents:

http://ipindiaonline.gov.in/patentsearch/GrantedSearch/viewdoc.aspx?id=mow9WeQeqLbdeYAwmnMu0Q==&loc=egcICQiyoj82NGgGrC5ChA==

« Previous Patent

Next Patent »

Patent Number

268488

Indian Patent Application Number

6416/CHENP/2008

PG Journal Number

36/2015

Publication Date

04-Sep-2015

Grant Date

31-Aug-2015

Date of Filing

24-Nov-2008

Name of Patentee

AGFA GRAPHICS NV

Applicant Address

SEPTESTRAAT 27, B-2640 MORTSEL

Inventors:

#	Inventor's Name	Inventor's Address
1	HUBERTUS VAN AERT	C/O AGFA GRAPHICS NV, IP DEPARTMENT 3622, SEPTESTRAAT 27, B-2640 MORTSEL
2	JOAN VERMEERSCH	C/O AGFA GRAPHICS NV, IP DEPARTMENT 3622, SEPTESTRAAT 27, B-2640 MORTSEL
3	HIERONYMUS ANDRIESSEN	C/O AGFA GRAPHICS NV, IP DEPARTMENT 3622, SEPTESTRAAT 27, B-2640 MORTSEL
4	STEVEN LEZY	C/O AGFA GRAPHICS NV, IP DEPARTMENT 3622, SEPTESTRAAT 27, B-2640 MORTSEL

PCT International Classification Number

B41C1/10

PCT International Application Number

PCT/EP2007/054917

PCT International Filing date

2007-05-22

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	US60/804,190	2006-06-08	EUROPEAN UNION
2	EP06114475.4	2006-05-24	EUROPEAN UNION