# Patent

## Title
Negative working, heat-sensitive lithographic printing plate precursor

## Abstract

A heat-sensitive negative-working lithographic printing plate precursor comprising:

    
    
        a support having a hydrophilic surface or which is provided with a hydrophilic layer; and
        an image-recording layer comprising hydrophobic thermoplastic polymer particles, an infrared light absorbing dye and a dye;

wherein said dye has a specified structure and a most bathochromic light absorption peak between 451 nm and 750 nm.

## Background
FIELD OF THE INVENTION
The present invention relates to a heat-sensitive, negative-working lithographic printing plate precursor.
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 (or 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 plate 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, insolubilization by cross linking of a polymer, heat-induced solubilization, or particle coagulation of a thermoplastic polymer latex.
The most popular thermal plates form an image by a heat-induced solubility difference in an alkaline developer between exposed and non-exposed areas of the coating. The coating typically comprises an oleophilic binder, e.g. a phenolic resin, of which the rate of dissolution in the developer is either reduced (negative working) or increased (positive working), by the image-wise exposure. 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 770 494, 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 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-exposed areas of the coating from the support.
WO2006/037716 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 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-exposed areas of the coating from the support wherein said thermoplastic polymer particles have an average particle size between 40 nm and 63 nm and wherein the amount of the hydrophobic thermoplastic polymer particles is more than 70% and less than 85% 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, wherein said hydrophobic thermoplastic polymer particles have an average particle size in the range from 45 nm to 63 nm and wherein 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.
EP-A 1 614 539 and EP-A 1 614 540 describe a method of making a lithographic printing plate comprising the steps of (1) image-wise exposing an imaging element as disclosed in EP-A 1 614 538 and (2) developing the image-wise exposed element by applying an aqueous, alkaline solution.
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 diameter of the thermoplastic particles used in the printing plate 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. The rather low sensitivity of negative-working printing plates that work according to the mechanism of heat-induced latex-coalescence is a second problem to be solved. A printing plate precursor characterized 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).
According to the unpublished EP-A 06 114 473 (filed 2006-05-24) a good clean-out is obtained, even with printing plate precursors comprising thermoplastic particles having a particle diameter of less than 40 nm, when the amount of infrared light absorbing dye, without taking into account an optional counterion, is more than 0.80 mg per m2 of the total surface of the hydrophobic particles.
According to the unpublished EP-A 06 114 475 (filed 2006-05-24) a good clean-out is obtained when said amount of the infrared light absorbing dye is more than 0.70 mg per m2 of the total surface of the hydrophobic particles, when the precursor is developed in an alkaline developer. A possible disadvantage of this invention may be a too high absorption of infrared light by the coating, due to the high amount of infrared light absorbing dye present in the image-recording layer, resulting in a low sensitivity.
To enable a visual inspection of the exposed image on the printing plate, after exposure and processing of the precursor, colorants are often added to the coating of the precursor. After removal of the non-exposed areas of said coating by the processing, the colorants in the exposed areas provide a visual image. Said colorants can be pigments or dyes. The lithographic printing plate precursor used in the method of producing a printing plate described in WO2006/037716 comprises preferably a pigment, more preferably a pigment having a hydrophilic surface. EP 1 524 112 describes a lithographic printing plate precursor comprising a contrast layer wherein said contrast layer comprises a colorant capable of providing a visible image after exposure and development of the precursor and wherein the image recording layer is substantially free of the colorant. According to the unpublished EP-A 05 109 781 (filed 2005-10-20) the lithographic printing plate precursor may comprise amino-substituted tri- or diarylmethane dyes as contrast dyes. WO2006/005688 discloses dyes which, combined with specific additives, only slightly color the coating but become intensely colored after exposure. The unpublished EP-A 05 105 440 (filed 2005-06-21) and PCT/EP2006/063327 (filed 2006-06-20) disclose infrared light absorbing dyes providing a print-out image after exposure to infrared light.
SUMMARY OF THE INVENTION
One aspect of the present invention provides a heat-sensitive negative-working lithographic printing plate precursor comprising:
a support having a hydrophilic surface or which is provided with a hydrophilic layer; and
an image-recording layer comprising hydrophobic thermoplastic polymer particles, an infrared light absorbing dye and a dye;
wherein said dye has a structure according to Formula I;




    
    
        wherein
        Q represents an optionally substituted mono-, tri- or penta methine chain;
        Z and Z′ independently represent O, NR′, S or CH═CH wherein R′ is an optionally substituted alkyl or (hetero)aryl group;
        X and X′ independently represent hydrogen, halogen, O—CH3, an optionally substituted alkyl or (hetero)aryl group, a condensed benzene ring;
        L and L′ represent a linking group; and
        G and G′ represent an acid group or salt thereof;

and wherein said dye has a most bathochromic light absorption peak at a wavelength between 451 nm and 750 nm

    
    




DETAILED DESCRIPTION OF THE INVENTION
The heat-sensitive printing plate precursor comprises a support, having a hydrophilic surface or which is provided with a hydrophilic layer, and a coating. The coating may comprise one or more layer(s). The layer of said coating comprising the hydrophobic thermoplastic particles is referred to as the image-recording layer. Said image-recording layer further comprises an infrared light absorbing dye and a dye according to formula I and having a most bathochromic absorption peak at a wavelength between 451 nm and 750 nm.
Dye
The image-recording layer of the printing plate precursor comprises a dye according to Formula I.




    
    
        wherein
        Q represents an optionally substituted mono-, tri- or penta methine chain;
        Z and Z′ independently represent O, NR′, S or CH═CH wherein R′ is an optionally substituted alkyl or (hetero)aryl group;
        X and X′ independently represent hydrogen, halogen, O—CH3, an optionally substituted alkyl or (hetero)aryl group, a condensed benzene ring;
        L and L′ represent a linking group;
        G and G′ represent an acid group or salt thereof.
    
    


The dye preferably has a structure according to Formulae II to V.




wherein X, X′, Z, Z′, L, L′, G, G′ have the same meaning as in Formula I and wherein Rm, R1 and R2 independently represent H, alkyl or aryl.
To obtain an electrically neutral molecule in Formulae I to V, monovalent positive counter ion(s) such as Li+, K+, Na+, NH4+, H3N(R′′)1+, H2N(R′′)2+, HN(R′′)3+, N(R′′)4+, wherein R′′ is an optionally substituted alkyl or (hetero)aryl group, are preferred.
Said acidic groups G and G′ in Formulae I to V are preferably selected from the list consisting of:

    
    
        a substituted sulphonamido acid group; (—SO2NHCORg, —SO2NHSO2Rg, —CONHSO2Rg)
        a carboxylic acid group (—COOH);
        a sulphonic acid group (—SO3H);
        a dithiosulphonic acid group (—SSO3H);
        a sulphuric acid group (—OSO3H);
        a phosphoric acid group (—OPO3H2);
        a phosphonic acid group (—PO3H2);

wherein Rg independently represents a hydrocarbon group which may have a substituent.

    
    


Most preferably the acidic groups G and G′ are sulphonic acid groups.
The linking group is preferably a divalent linking group. The divalent linking group is preferably an optionally substituted alkylene or (hetero)arylene group, more preferably an alkylene group. Most preferably, the linking groups L and L′ in the formulae I to V, are —(CH2)q—, wherein q is an integer ranging from 1 to 5.
In a most preferred embodiment said dye has a structure according to Formulae VI to VII:




    
    
        wherein
        p and p′ are integers ranging from 0 to 3;
        X and X′ have the same meaning as in Formula I;
        M+ is a monovalent positive counter ion.
    
    


The synthesis of cyanine dyes is described in for example “The Chemistry of heterocyclic compounds; The cyanine dyes and related compounds”, by F. M. Hamer from Wiley & Sons, 1964, page 58 and page 534.
Some examples of dyes according to the present invention are



















In centrifugation experiments with solutions containing hydrophobic thermoplastic particles (0.1 to 5.0 wt. %) and one of the dyes (D-01 to D-34) listed above, it has been observed that these dyes, at least partially, co-sediment with the hydrophobic thermoplastic particles. In these experiments, centrifugation conditions of 40 000 to 60 000 rpm for 1 to 4 hours were used, in order to achieve sedimention of all particles. As a reference experiment, a solution of the dye, without hydrophobic particles, was centrifuged under the same conditions. Comparison with UV-VIS spectroscopy of both supernatent solutions revealed that all dyes, D-01 to D-34 were, at least partially, co-sedimented with the particles.
To obtain an optimal visual contrast, the dye has a most bathochromic light absorption peak at a wavelength between 451 nm and 750 nm. One or more dye(s) may be used to optimize the visual contrast. Selecting dye(s) with specific absorption maxima between 451 nm and 750 nm, enables one to optimize the colour of the visual contrast.
A too strong absorption in the infrared wavelength region (750-1500 nm) may adversely influence the sensitivity of the lithographic printing plate precursor. If the infrared density of the image-recording layer becomes too high, a higher exposure may be necessary for inducing coalescence of the thermoplastic particles located near the support, resulting in a lower throughput, i.e. lower number of printing plate precursors that can be exposed in a given time interval.
The dyes of the present invention may be used in combination with other colorants, dyes or pigments, known in the art, e.g. derivatives of amino-substituted tri- or diarylmethane dyes.
Infrared Light Absorbing Dye
The image-recording layer comprises an infrared light absorbing dye which converts the absorbed energy into heat.
Preferred infrared light absorbing compounds are dyes such as cyanine, merocyanine, indoaniline, oxonol, pyrilium and squarilium dyes. Examples of suitable infrared light absorbing dyes are described in e.g. EP-As 823 327, 978 376, 1 029 667, 1 053 868 and 1 093 934 and WOs 97/39894 and 00/29214.
Other preferred infrared light absorbing 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) and PCT/EP2006/063327 (filed 2006-06-20). Since these infrared light absorbing dyes give rise to a print-out image upon exposure to infrared light, they may contribute to an enhanced visual contrast.
A combination of two or more infrared light absorbing dyes may be used.
The printing plate precursor comprising hydrophobic thermoplastic particles, an infrared light absorbing dye and a dye according to formula I, having a most bathochromic light absorption peak at a wavelength between 451 nm and 750 nm, in the image-recording layer is characterized by an improved clean-out, a high sensitivity and a good visual contrast after exposure and processing. A possible explanation of this phenomenon may be that all or part of the infrared light absorbing dye and said dye adsorb on the surface of the hydrophobic particles and render the particles more dispersible in aqueous solutions (e.g. the developing solution). An optimal interaction between said dye and the hydrophobic particles, resulting in an improved clean-out, may be achieved by selecting the dye as described above.
Depending on the method used to develop the exposed printing plate precursors, different amounts of the infrared light absorbing dye and said dye may be used. Since it is believed that optional counter ions of the infrared light absorbing dye and said dye (i.e. when the infrared light absorbing dye and/or said dye are used as salts) do not have an essential contribution to the invention, the amount of the infrared light absorbing dye and said dye, referred to in the description, the examples and the claims, is meant to be the amount of the infrared light absorbing dye and said dye without taking into account optional counter ions.
The sum of the amounts of the infrared light absorbing dye and said dye, without taking into account optional counter ions, is preferably more than 0.70 mg, more preferably more than 0.80 mg and most preferably more than 1.00 mg per m2 of the total surface of said thermoplastic polymer particles.
There are no particular limitations concerning the ratio between infrared light absorbing dye and said dye. However, when the amount of infrared light absorbing dye becomes too low, the sensitivity of the precursor may decrease. Therefore, the amount of infrared light absorbing dye, without taking into account optional counter ions, is preferably more than 0.25 mg, more preferably more than 0.35 mg, most preferably more than 0.45 mg per m2 of the total surface of said thermoplastic polymer particles. When the amount of the infrared light absorbing dye becomes too high, the total infrared optical density (e.g. at 830 nm) of the coating may become too high, again resulting in a possible decrease of the sensitivity. 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 than 2.00, more preferably less than 1.50, most preferably less than 1.25.
The amount of said dye may be optimized to obtain a sufficient visual contrast. The optimal amount of said dye will therefore depend on the absorption characteristics of said dye. To optimize the visual contrast, e.g. to enhance the visual contrast or to provide a visual contrast with a particular colour, more than one dye according to the present invention may be used.
Hydrophobic Thermoplastic Particles
The hydrophobic particles preferably have an average particle diameter from 15 nm to 75 nm, more preferably from 25 to 55 nm, most preferably from 35 nm to 45 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 (ØPCS), 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-90 analyzer, commercially available from Brookhaven Instrument Company, Holtsville, N.Y., USA.
A method to measure the specific surface of the hydrophobic particles is based on hydrodynamic fractionation. With this technique a volume distribution of the particles is obtained from which an volume average particle diameter is calculated (ØV). In the examples the volume average particle diameter, measured according to this technique, is obtained with a PL-PSDA apparatus (Polymeric Laboratories Particle Size Diameter Analyser) from Polymeric Labs. From the volume distribution, obtained with the PL-PSDA apparatus, the total surface of the hydrophobic particles (expressed as square metre per gram hydrophobic particles, m2/g) can be calculated. In these calculations the density (g/cm3) of the thermoplastic particles has to be taken into account. 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, page 574-581. Alternatively, the density of the hydrophobic particles may 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 preferably at least 50, more preferably at least 60, most preferably at least 70% 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 may be selected from polyethylene, poly(vinyl)chloride, polymethyl(meth)acrylate, polyethyl(meth)acrylate, polyvinylidene chloride, poly(meth)acrylonitrile, polyvinylcarbazole, 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 styrene and (meth)acrylonitrile or derivatives thereof. The latter copolymers may comprise at least 30% by weight of polystyrene, more preferably at least 50% by weight of polystyrene. In order to obtain sufficient resistivity towards organic chemicals such as hydrocarbons used in e.g. plate-cleaners, the thermoplastic polymer particles preferably comprise at least 5% by weight, more preferably at least 30% by weight, 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.
The thermoplastic polymer particles comprise preferably a polymer or co-polymer having a weight average molecular weight ranging 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 are preferably applied onto the lithographic base in the form of a dispersion in an aqueous coating liquid. These water based dispersions can be prepared by polymerization in a water-based system e.g. by free-radical emulsion polymerization as described in U.S. Pat. No. 3,476,937 or EP-A 1 217 010 or by means of dispersing techniques of the 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 of the emulsion polymerization 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 adsorbed 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 and anionic surfactants are used. Most preferably the hydrophobic thermoplastic particles are stabilized with an 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 sodium lauryl phosphate; suitable non-ionic dispersion aids are for example ethoxylated lauryl alcohol and ethoxylated octyl- or nonylphenol.
Binder
The image-recording layer may further comprise a hydrophilic binder. Examples of suitable hydrophilic binders are homopolymers and copolymers of vinyl alcohol, (meth)acrylamide, methylol (meth)acrylamide, (meth)acrylic acid, hydroxyethyl(meth)acrylate, and maleic anhydride/vinylmethylether copolymers, copolymers of (meth)acrylic acid or vinylalcohol with styrene sulphonic acid.
Preferably the hydrophilic binder comprises polyvinylalcohol or polyacrylic acid.
The amount of hydrophilic binder may be between 2.5 and 50, preferably between 5 and 25, more preferably between 7 and 15% by weight 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 2 and 15, more preferably between 4 and 10, most preferably between 5 and 7.5.
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, and metal complexing agents are well-known components of lithographic coatings.
Preferably the image-recording layer comprises an organic compound, characterized 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 Formula VIII:




or a salt thereof and wherein R8 independently represent hydrogen, an optionally substituted straight, branched, cyclic or heterocyclic alkyl group or an optionally substituted aryl or (hetero)aryl group.

Compounds according to Formula VIII may be present in the image-recording layer in an amount between 0.05 and 15, preferably between 0.5 and 10, more preferably between 1 and 5% by weight relative to the total weight of the ingredients of the image-recording layer.
Optional Layers of the Coating
To protect the surface of the coating, in particular from mechanical damage, a protective layer may optionally be applied on top of the image-recording layer. The protective layer generally comprises at least one water-soluble polymeric binder, such as polyvinyl alcohol, poly-vinylpyrrolidone, partially hydrolyzed polyvinyl acetates, gelatin, carbohydrates or hydroxyethylcellulose. The protective layer may contain small amounts, i.e. less than 5% by weight, of organic solvents. The thickness of the protective layer is not particularly limited but preferably is up to 5.0 μm, more preferably from 0.05 to 3.0 μm, particularly preferably from 0.10 to 1.0 μm.
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 plate precursors are exposed.
To optimize the lithographic properties, the aluminum support is subjected to several treatments well known in the art such as for example: degrease, surface roughening, etching, anodization, 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 1 614 538.
A preferred aluminum substrate, characterized by an arithmetical mean center-line roughness Ra less than 0.45μ is described in EP 1 356 926.
Optimizing the pore diameter and distribution thereof of the grained and anodized aluminum surface may enhance the press life of the printing plate and may improve the toning behaviour. An optimal ratio between pore diameter of the surface of the aluminum support and the average particle diameter 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 diameter of the thermoplastic particles present in the image-recording layer of the coating, preferably ranges from 0.1:1 to 1.0:1, more preferably from 0.30:1 to 0.80:1.
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 U.S. Pat. No. 5,288,344, U.S. Pat. No. 5,368,659, U.S. Pat. No. 5,618,359, U.S. Pat. No. 5,735,975, U.S. Pat. No. 5,250,124, U.S. Pat. No. 5,032,196, U.S. Pat. No. 6,325,868, and U.S. Pat. No. 6,818,078. The following references describe the science of amorphous metals in much more detail and are incorporated as references: Introduction to the Theory of Amorphous Metals, N. P. Kovalenko et al. (2001); Atomic Ordering in Liquid and Amorphous Metals, S. I. Popel, et al; Physics of Amorphous Metals, N. P. Kovalenko et al (2001).
According to another embodiment, the 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 laminate thereof. Preferred examples of plastic film are poly-ethylene terephthalate 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, U.S. Pat. No. 3,971,660, U.S. Pat. No. 4,284,705, EP 1 614 538, EP 1 564 020 and US 2006/0019196.
Exposure
The printing plate precursor is image-wise exposed with infrared light, preferably near infrared light. The infrared light is converted into heat by an infrared light absorbing dye as discussed above. The heat-sensitive lithographic printing plate precursor of the present invention is preferably not sensitive to visible light. Most preferably, the coating is not sensitive to ambient daylight 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 750 to about 1500 nm, e.g. a semiconductor laser diode, a Nd: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 the image-recording layer, the pixel dwell time of the laser beam, which is determined by the spot diameter (typical value of modern plate-setters at 1/e2 of maximum intensity: 10-25 μm) and the scan speed and the resolution of the exposure apparatus (i.e. the number of addressable pixels per unit of linear distance, often expressed in dots per inch or dpi; typical value: 1000-4000 dpi).
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 N.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 (trademarks of Agfa Gevaert N.V.) make use of the XTD-technology.
Preferred lithographic printing plate precursors according to the present invention produce a useful lithographic image upon image-wise exposure with infrared light having an energy density, measured at the surface of said precursor, of 200 mJ/cm2 or less, more preferably of 180 mJ/cm2 or less, most preferably of 160 mJ/cm2 or less. With a useful lithographic image on the printing plate, 2 e dots (at 200 lines per inch or lpi) are perfectly visible on at least 1 000 prints on paper.
Due to the heat generated during the exposure step, the hydrophobic thermoplastic polymer particles may fuse or coagulate so as to form a hydrophobic phase which corresponds to the printing areas of the printing plate. Coagulation may result from heat-induced coalescence, softening or melting of the thermoplastic polymer particles. 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 preferably higher than 50° C., more preferably above 100° C.
Development
In one embodiment of the invention the printing plate precursor, after exposure, is developed off press by means of a suitable processing liquid. In the development step, the non-exposed areas of the image-recording layer are at least partially removed without essentially removing the exposed areas, i.e. without affecting the exposed areas to an extent that renders the ink-acceptance of the exposed areas unacceptable. The processing liquid can be applied to the plate e.g. by rubbing with an impregnated pad, by dipping, immersing, (spin-)coating, spraying, pouring-on, either by hand or in an automatic processing apparatus. The treatment with a processing liquid may be combined with mechanical rubbing, e.g. by a rotating brush. During the development step, any water-soluble protective layer present is preferably also removed. Suitable processing liquids are plain water or aqueous solutions.
In a preferred embodiment of the off press development, the processing liquid is a gum solution. A suitable gum solution which can be used in the development step is described in for example EP-A 1 342 568, paragraphs [0008] to [0022] and WO 2005/111727, page 5 line 32 to page 11 line 30.
In another preferred embodiment of the off press development, the processing liquid is an alkaline aqueous solution having a pH of at least 9, preferably at least 10, more preferably at least 11, most preferably at least 12. Suitable alkaline developers which can be used are described in the EP-As 1 614 539 and 1 164 540 and the unpublished EP-A 06 114 475 (filed 2006-05-24).
The development off press is preferably carried out at temperatures of from 20 to 40° C. in automated processing units as customary in the art. The development step may be followed by a rinsing step and/or a gumming step.
In another embodiment of the invention the printing plate precursor may be, after exposure, mounted on a printing press and developed on-press by supplying ink and/or fountain or a single fluid ink to the precursor.
In still another preferred embodiment of the invention the development off-press, with e.g. a gum solution, wherein the non-exposed areas of the image-recording layer are partially removed, may be combined with a development on-press, wherein a complete removal of the non-exposed areas is realized.
The plate precursor may 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 heated to elevated temperatures (so called ‘baking’). 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 150° C. for 10 minutes or at a temperature of 120° C. for 30 minutes. Baking can be done in conventional hot air ovens or by irradiation with lamps emitting in the infrared or ultraviolet wavelength region. This baking step results in an increased resistance of the printing plate to plate cleaners, correction agents and UV-curable printing inks increases.
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 U.S. Pat. No. 4,045,232, U.S. Pat. No. 4,981,517 and U.S. Pat. No. 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 WO 00/32705.
EXAMPLES
Preparation of the Thermoplastic Particles LX-01 and LX-02
Preparation of LX-01
In a double-jacketed reactor of 2 liter 10.8 g of Sodium Dodecyl Sulphate (SDS Ultra Pure obtained via Alkemi BV, Lokeren, Belgium) and 1243.9 g of demineralized water was added. The reactor was flushed with nitrogen and heated up to 80° C. When the reactor content reached a temperature of 80° C., 12 g of a 5% aqueous solution of sodium persulphate (Na2S2O8) was added. The reactor was subsequently heated for 15 minutes at 80° C., followed by dosing the monomer mixture (238.5 g of styrene and 121.5 g of acrylonitrile) during 180 minutes. Simultaneously with the monomer addition, an additional aqueous persulphate solution was added (24 g of a 5% aqueous Na2S2O8 solution). Upon completion of the monomer addition, the reactor was heated for 30 minutes at 80° C. To reduce the amount of residual monomer a redox-initiation system was added: 1.55 gram of sodium formaldehyde sulphoxylate dihydrate (SFS) dissolved in 120 g water and 2.57 g of a 70 wt. % solution of t-butyl hydroperoxide (TBHP) diluted with 22.5 g of water. The aqueous solutions of SFS and TBHP were added separately during 80 minutes. The reaction was then heated for another 10 minutes and subsequently cooled to room temperature. 100 ppm of 5-bromo-5-nitro-1,3-dioxane was added as biocide and the latex was filtered using coarse filter paper.
This resulted in the latex dispersion LX-01 with a solid content of 20.84% by weight and a pH of 3.46.
Preparation of LX-02:
In a double-jacketed reactor of 8 liter 40.0 g of sodium dodecyl sulphate (SDS Ultra Pure obtained via Alkemi BV, Lokeren, Belgium) and 5495.3 g of demineralized water was added. The reactor was flushed with nitrogen and heated up to 75° C. When the reactor content reached a temperature of 75° C., a mixture of 15.9 grams of styrene and 8.1 grams of acrylonitrile (i.e. 1.5% of the total monomer amount) was added to prepare a latex seed. After mixing for 10 minutes, to homogeneously disperse the added monomers, a part of the initiator solution (50% of the total amount of initiator) is added, i.e. 105.6 grams of a 5% aqueous sodium persulfate solution. The reactor is subsequently heated to 80° C. during 30 minutes followed by dosing a monomer mixture of 1044.1 gram of styrene and 531.9 grams of acrylonitrile during 180 minutes. Simultaneously, 105.6 grams of a 5% sodium persulfate solution was dosed, also in 180 minutes. Upon completion of the monomer addition, the reactor was heated for 30 minutes at 80° C. To reduce the amount of residual monomer a redox-initiation system was added: 6.99 gram of sodium formaldehyde sulphoxylate dihydrate (SFS) dissolved in 534 g water and 11.43 g of a 70% by weight solution of t-butyl hydroperoxide (TBHP) diluted with 100 g of water. The aqueous solutions of SFS and TBHP were added separately during 80 minutes. The reaction was then heated for another 10 minutes and subsequently cooled to room temperature. 100 ppm of 5-bromo-5-nitro-1,3-dioxane was added as biocide and the latex was filtered using coarse filter paper. This resulted in the latex dispersion LX-02 with a solid content of 20.74% by weight and a pH of 2.99.
Particle Size and Surface of the Hydrophobic Thermoplastic Particles
Two techniques were used to measure the particle diameter of the hydrophobic thermoplastic particles, as described in the detailed description:

    ØPCS: 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, Holtsville, N.Y., USA.
    ØV: is the volume average particle diameter obtained with hydrodynamic fractionation obtained with a PL-PSDA apparatus (Polymer Laboratories Particle Size Diameter Analyzer) from Polymer Laboratories Ltd, Church Stretton, Shropshire, UK.


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 (ρ, (g/cm3)) of the particles of 1.10 g/cm3 for LX-01 and LX-02. The density of the particles LX-01 and LX-02 (skeletal density according to ASTM D3766 standard) has been measured using the gas displacement method on an Accupyc 1330 helium-pycnometer (from Micromeritics).
The calculations are based on the following formulae:
ρ=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)
Øv=Volume particle diameter (nm)

    
    
        1 g of particles has a Volume (V) of (1/ρ)·10−6 m3.
        The Volume of 1 spherical particle=4/3·π·(Øv/2)3 
        The number (N) of spherical particles in 1 g is therefore:
    
    






  N
  =
  
    
      
        (
        
          1
          /
          ρ
        
        )
      
      ·
      
        10
        
          -
          6
        
      
    
    
      
        4
        /
        3
      
      ·
      π
      ·
      
        
          (
          
            
              ∅
              v
            
            /
            2
          
          )
        
        3
      
    
  




    
    
        The surface of 1 spherical particle=4·π·(ØV/2)2 
        The total surface of 1 g spherical particles containing N particles is therefore:
    
    






  S
  =
  
    
      
        
          (
          
            1
            /
            ρ
          
          )
        
        ·
        
          10
          
            -
            6
          
        
      
      
        
          4
          /
          3
        
        ·
        π
        ·
        
          
            (
            
              
                ∅
                v
              
              /
              2
            
            )
          
          3
        
      
    
    ·
    4
    ·
    π
    ·
    
      
        (
        
          
            ∅
            v
          
          /
          2
        
        )
      
      2
    
  




    
    
        
        
            or:
        
        
    
    






  
    S
    ⁢
    
      
    
    ⁢
    
      (
      
        
          m
          2
        
        ⁢
        
          /
        
        ⁢
        g
      
      )
    
  
  =
  
    
      6
      
        
          ρ
          ·
          
            ∅
            v
          
        
        ⁢
        
          
        
        ⁢
        
          (
          nm
          )
        
      
    
    ·
    
      10
      3
    
  




As mentioned above, the total surfaces of the particles, as given in the examples, are calculated with the PL-PSDA apparatus, taking into account the volume distribution of the particles. As an approximation, especially for homogeneous particles, the calculations may also be performed taking into account only the volume average particle size (ØV).
In Table 1 ØPCS, ØV and the total Surface of LX-01 and LX-02 are given.







TABLE 1







ØPCS, ØV, and total surface of LX-01 and LX-02










LX-01
LX-02















ØPCS (nm)
35
41



ØV (nm)
32
35



Surface (m2/g)
175
165










Preparation of the Lithographic Substrate

A 0.3 mm thick aluminum foil was degreased by spraying with an aqueous solution containing 34 g/l of NaOH at 70° C. for 6 seconds and rinsed with demineralized water for 3.6 seconds. The foil was then electrochemically grained during 8 seconds using an alternating current in an aqueous solution containing 15 g/l of HCl, 15 g/l of SO42− ions and 5 g/l of Al3+ ions at a temperature of 37° C. and a current density of about 100 A/dm2 (charge density of about 800 C/dm2). Afterwards, the aluminum foil was desmutted by etching with an aqueous solution containing 145 g/l of sulphuric acid at 80° C. for 5 seconds and rinsed with demineralized water for 4 seconds. The foil was subsequently subjected to anodic oxidation during 10 seconds in an aqueous solution containing 145 g/l of sulphuric acid at a temperature of 57° C. and a current density of 33 A/dm2 (charge density of 330 C/dm2), then washed with demineralized water for 7 seconds and post-treated for 4 seconds (by spray) with a solution containing 2.2 g/l of polyvinylphosphonic acid (PVPA) at 70° C., rinsed with demineralized water for 3.5 seconds and dried at 120° C. for 7 seconds. The support thus obtained is characterized by a surface roughness Ra of 0.35-0.4 μm (measured with interferometer NT1100) and have an anodic weight of about 4.0 g/m2.
Ingredients Used in the Preparation of the Printing Plate Precursors
Table 2 lists the ingredients, used in the preparation of the printing plate precursors.







TABLE 2





ingredients used in the preparation of the precursors
















PAA
Polyacrylic acid from Ciba Specialty Chemicals. PAA



was added to the coating solutions as a 10 wt %



aqueous solution


IR-1
Infrared light absorbing dye, chemical structure and



solution used see table 3.


CP-1
Contrast Pigment, Heliogen Blau D7490 from BASF



(20% aqueous dispersion).


CP-2
Contrast Pigment, PV Fast Violet RL from Clariant



(20% aqueous disperision).


D-1 to D-6
Dyes according to the present invention, chemical



structure and solution used see table 3.


CD-1 to CD-20
Contrast Dye, chemical structure and solution used



see table 3. CD-01 to CD-are comparative contrast



dyes.


HEDP
1-hydroxyethylidene-1,1-diphosphonic acid from



Solutia. HEDP was added to the coating solutions as



a 10 wt % aqueous solution.


FSO 100
Zonyl FSO 100, a perfluorinated surfactant from



Dupont.
















TABLE 3







chemical structure and solution used of IR-1, D-01 to D-6 and CD-01 to CD-20.










Solution
Chemical Structure













IR-1
1 wt. % in H2O






 


D-1
1 wt. % in H2O/MeOH (50/50)






 


D-2
1 wt. % in H2O/MeOH (50/50)






 


D-3
1 wt. % in H2O/MeOH (50/50)






 


D-4
1 wt. % in H2O/MeOH (50/50)






 


D-5
1 wt. % in H2O/MeOH (50/50)






 


D-6
1 wt. % in H2O/MeOH (50/50)






 


CD-01
1 wt. % in H2O






 


CD-02
1 wt. % in H2O






 


CD-03
1 wt. % in H2O/MeOH (50/50)






 


CD-04
1.61 wt. % in H2O






 


CD-05
1 wt. % in H2O






 


CD-06
1 wt. % in H2O






 


CD-07
2.5 wt. % in H2O






 


CD-08
1 wt. % in MeOH






 


CD-09
8.6 wt. % in H2O






 


CD-10
7.1 wt. % in H2O






 


CD-11
1 wt. % in H2O






 


CD-12
1 wt. % in H2O






 


CD-13
2 wt. % in H2O






 


CD-14
1 wt. % in H2O






 


CD-15
1 wt. % in H2O






 


CD-16
1 wt. % in H2O






 


CD-17
1 wt. % in H2O






 


CD-18
1 wt. % in H2O






 


CD-19
1 wt. % in H2O






 


CD-20
1 wt. % in H2O













Absorption Spectra of the Dyes D-01 to D-06

In table 4 the absorption maxima (λmax) of the dyes D-01 to D-06, dissolved in methanol, are given. The absorption spectra were measured with an Agilent 8453 spectrophotometer, from Agilent Technologies. The concentration of the contrast dyes in methanol was adjusted to obtain an absorbance at λmax between 0.25 and 2.50.







TABLE 4







Absorption maxima of D-01 to D-06, dissolved in MeOH









λmax (nm)














D-01
681



D-02
588



D-03
644



D-04
550



D-05
650



D-06
557










Example 1
Printing Plate Precursors PPP-1 to PPP-5
Preparation of the Coating Solutions
The coating solutions for the printing plate precursors 1 to 5 were prepared using the solutions, solids or dispersions as described above. The latex dispersion LX-01 or LX-02 was added to demineralized water followed by stirring for 10 minutes. Subsequently the IR-dye (IR-1) was added. After another 10 minutes the contrast pigments (CP-01, CP-02), the dyes according to the invention (D-01-D-6), if any, and the comparative contrast dyes (CD-01 to CD-20), if any, were added. After 60 minutes of stirring the polyacrylic acid (PAA) solution was slowly added and subsequently the HEDP solution was added. 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%). The resulting coating solution was finally filtered using French silk.
Preparation of the Printing Plate Precursors PPP-01 to PPP-05
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 μm. The coatings were dried at 60° C. Table 5 lists the resulting dry coating weight of the different components of the printing plate precursors.







TABLE 5







dry coating weight (g/m2) of ingredients of PPP-01 to PPP-05









PPP













PPP-01
PPP-02
PPP-03
PPP-04
PPP-05



(COMP)
(COMP
(INV)
(INV)
(INV)
















LX-01
0.542
0.542
0.542
0.542
0.542


IR-01
0.065
0.065
0.065
0.065
0.065


CP-01
0.035
—
—
—
—


CP-02
0.022
—
—
—
—


D-01
—
—
—
0.022
—


D-02
—
—
—
0.022
—


D-03
—
—
0.022
—
—


D-04
—
—
0.022
—
—


D-05
—
—
—
—
0.022


D-06
—
—
—
—
0.022


PAA
0.061
0.061
0.061
0.061
0.061


HEDP
0.030
0.030
0.030
0.030
0.030


FSO 100
0.006
0.006
0.006
0.006
0.006


Sum
0.760
0.704
0.747
0.747
0.747


ingredients









Exposure and Printing of Printing Plate Precursors PPP-01 to PPP-05

The printing plate precursors were then exposed on a Creo TrendSetter 3244 (trademark of CREO) 40 W fast head IR-laser plate-setter at 210-180-150-120-90 mJ/cm2 at 150 rotations per minute (rpm) with a 200 line per inch (lpi) screen and an adressability of 2400 dpi. These exposed printing plate precursors were subsequently processed in a COU85 Clean-Out Unit, from Agfa Gevaert NV, operating at a speed of 1.1 m/min and a temperature of 22° C., and using a RC520 gumming solution, from Agfa Gevaert NV.
After processing the clean-out was visually assessed and subsequently the printing plates were mounted on a GTO52 printing press, equipped with a VARN Kompac III dampening system. A compressible blanket was used and printing was done with 4% Emerald Premium 3520 as a fountain solution (Trademark of Anchor) and K+E 800 black 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 start printing. 1000 prints were made on 80 g offset paper.
Evaluation of the Printing Plate Precursors PPP-01 to PPP-05
The printing plate precursors are evaluated by the following characteristics:

    Sensitivity: the lowest exposure energy density at which 2% dots (200 lpi) are visible (by means of a 5× magnifying glass) on the 1000 print on paper.
    Clean-out 1: qualitative visual assessment of the plate clean-out after processing. A value 5 means that no stain is observed, whereas a value of 0 means that a substantial amount of stain is observed. For optimal lithographic properties, a value of 5 is required.
    Clean-out 2: After 750 prints, the paper sheet size is shortened and printing is continued for another 250 prints. After 1 000 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 then be 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 means 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.


Optical Densities are measured with a GretagMacbeth densitometer Type D19C.
In table 6 the lithographic properties of PPP-01 to PPP-05 are given together with the following characteristics of the lithographic printing plate precursors:

    IR/Surf (mg/m2): The amount (mg) of infrared light absorbing dye (mg), without taken into account the counter ion, per m2 of the total surface of the particles.
    IR+D/Surf (mg/m2): Total amount (mg) of infrared light absorbing dye (IR) and Dye (D), according to this invention, without taking into account counter ions, per m2 of the total surface of the particles.









TABLE 6







evaluation PPP-01 to PPP-05









PPP













PPP-01
PPP-02
PPP-03
PPP-04
PPP-05



(COMP)
(COMP)
(INV)
(INV)
(INV)
















IR/Surf
0.66
0.66
0.66
0.66
0.66


IR + D/Surf
0.66
0.66
1.06
1.07
1.06


Sensitivity
150
150
120
150
150


Clean out 1
2
—*
5
5
5


Clean out 2
2.5
2.5
4
4
5





*unable to evaluate due to absence of contrast.






With PPP-01, PPP-03, PPP-04 and PPP-05 a good visual contrast was obtained. With PPP-02, no visual contrast is observed.
From the results shown in table 6 can be concluded:
When no dyes according to the present invention are present in the image-recording layer, a bad clean-out is observed (comparative examples PPP-01 and PPP-02).
When dyes according to the present invention are present in the image-recording layer, a good clean-out, a high sensitivity and a sufficient visual contrast is observed (invention examples PPP-03 to PPP-05).
Example 2
Printing Plate Precursors PPP-06 to PPP-27
Preparation of the Printing Plate Precursors PPP-06 to PPP-27
The preparation of the printing plate precursors were performed as described in example 1. Table 7 lists the resulting dry coating weight of the different components of the printing plate precursors.







TABLE 7





dry coating weight (g/m2) of ingredients of PPP-06 to PPP-27

















PPP














PPP-06
PPP-07
PPP-08
PPP-09
PPP-10
PPP-11



(COMP)
(INV)
(COMP)
(COMP)
(COMP)
(COMP)





LX-01
0.455
0.455
0.455
0.455
0.455
0.455


IR-01
0.065
0.065
0.065
0.065
0.065
0.065


CP-01
0.035
—
—
—
—
—


CP-02
0.022
—
—
—
—
—


D-01
—
0.021
—
—
—
—


D-02
—
0.021
—
—
—
—


CD-01
—
—
0.042
—
—
—


CD-02
—
—
—
0.042
—
—


CD-03
—
—
—
—
0.042
—


CD-04
—
—
—
—
—
0.042


PAA
0.051
0.051
0.051
0.051
0.051
0.051


HEDP
0.024
0.024
0.024
0.024
0.024
0.024


FSO 100
0.005
0.005
0.005
0.005
0.005
0.005


Sum ingredients
0.657
0.642
0.642
0.642
0.642
0.642












PPP














PPP-12
PPP-13
PPP-14
PPP-15
PPP-16
PPP-17



(COMP)
(COMP)
(COMP)
(COMP)
(COMP)
(COMP)





LX-01
0.455
0.455
0.455
0.455
0.455
0.455


IR-01
0.065
0.065
0.065
0.065
0.065
0.065


CD-05
0.042
—
—
—
—
—


CD-06
—
0.042
—
—
—
—


CD-07
—
—
0.042
—
—
—


CD-08
—
—
—
0.042
—
—


CD-09
—
—
—
—
0.042
—


CD-10
—
—
—
—
—
0.042


PAA
0.051
0.051
0.051
0.051
0.051
0.051


HEDP
0.024
0.024
0.024
0.024
0.024
0.024


FSO 100
0.005
0.005
0.005
0.005
0.005
0.005


Sum ingredients
0.642
0.642
0.642
0.642
0.642
0.642












PPP














PPP-18
PPP-19
PPP-20
PPP-21
PPP-22
PPP-23



(COMP)
(COMP)
(COMP)
(COMP)
(COMP)
(COMP)





LX-01
0.455
0.455
0.455
0.455
0.455
0.455


IR-01
0.065
0.065
0.065
0.065
0.065
0.065


CD-11
0.042
—
—
—
—
—


CD-12
—
0.042
—
—
—
—


CD-13
—
—
0.042
—
—
—


CD-14
—
—
—
0.042
—
—


CD-15
—
—
—
—
0.042
—


CD-16
—
—
—
—
—
0.042


PAA
0.051
0.051
0.051
0.051
0.051
0.051


HEDP
0.024
0.024
0.024
0.024
0.024
0.024


FSO 100
0.005
0.005
0.005
0.005
0.005
0.005


Sum ingredients
0.642
0.642
0.642
0.642
0.642
0.642













PPP















PPP-24
PPP-25
PPP-26
PPP-27




(COMP)
(COMP)
(COMP)
(COMP)







LX-01
0.455
0.455
0.455
0.455



IR-01
0.065
0.065
0.065
0.065



CD-17
0.042
—
—
—



CD-18
—
0.042
—
—



CD-19
—
—
0.042
—



CD-20
—
—
—
0.042



PAA
0.051
0.051
0.051
0.051



HEDP
0.024
0.024
0.024
0.024



FSO 100
0.006
0.006
0.006
0.006



Sum ingredients
0.642
0.642
0.642
0.642










Exposure, development, printing and evaluation of the printing plate precursors PPP-06 to PPP-27

Exposure, development, printing and evaluation of the printing plate precursors PPP-06 to PPP-27 were performed as described in example 1.
In table 8 the lithographic properties of the printing plate precursors PPP-06 to PPP-27 are shown, together with the relevant parameters of the printing plate precursors relating to the present invention (see example 1).







TABLE 8





lithographic evaluation of PPP-06 to PPP-27

















PPP














PPP-06
PPP-07
PPP-08
PPP-09
PPP-10
PPP-11



(COMP)
(INV)
(COMP)
(COMP)
(COMP)
(COMP)





IR/Surf
0.79
0.79
0.79
0.79
0.79
0.79


IR + D/Surf
0.79
1.30
0.79
0.79
0.79
0.79


Sensitivity
180
180
210
>210
210
180


Clean out 1
3
5
4
3
3
3












PPP














PPP-12
PPP-13
PPP-14
PPP-15
PPP-16
PPP-17



(COMP)
(COMP)
(COMP)
(COMP)
(COMP)
(COMP)





IR-dye/Surf
0.79
0.79
0.79
0.79
0.79
0.79


IR + D/Surf
0.79
0.79
0.79
0.79
0.79
0.79


Sensitivity
210
180
210
210
210
210


Clean out 1
4
4
4
0
4
3












PPP














PPP-18
PPP-19
PPP-20
PPP-21
PPP-22
PPP-23



(COMP)
(COMP)
(COMP)
(COMP)
(COMP)
(COMP)





IR-dye/Surf
0.79
0.79
0.79
0.79
0.79
0.79


IR + D/Surf
0.79
0.79
0.79
0.79
0.79
0.79


Sensitivity
>210
210
210
210
210
180


Clean out 1
4
3
3
3
2
2













PPP















PPP-24
PPP-25
PPP-26
PPP-27




(COMP)
(COMP)
(COMP)
(COMP)







IR-dye/Surf
0.79
0.79
0.79
0.79



IR + D/Surf
0.79
0.79
0.79
0.79



Sensitivity
210
>210
210
210



Clean out 1
4
4
3
3










With all printing plate precursors PPP-06 to PPP-27 a good visual contrast was obtained.

From the results shown in table 8 it may be concluded:
When no dyes according to the present invention are present in the image-recording layer, a bad clean-out is observed (comparative examples PPP-06 and PPP-08 to PPP-27).
When dyes according to the present invention are present in the image-recording layer, a good clean-out, a high sensitivity and a sufficient visual contrast is observed (invention examples PPP-07).
Example 3
Printing Plate Precursors PPP-28 to PPP-36
Preparation of the Printing Plate Precursors PPP-28 to PPP-36.
The preparation of the printing plate precursors were performed as described in example 1. Table 9 lists the resulting dry coating weight of the different components of the printing plate precursors.







TABLE 9





dry coating weight (g/m2) of ingredients of PPP-28 to PPP-36

















PPP














PPP-28
PPP-29
PPP-30
PPP-31
PPP-32
PPP-33



(COMP)
(COMP)
(INV)
(INV)
(INV)
(INV)





LX-02
0.55 
0.55 
0.55 
0.55 
0.55 
0.55 


IR-01
0.05 
0.05 
0.05 
0.05 
0.05 
0.05 


CP-02
—
0.02 
—
0.02 
—
—


D-02
—
—
0.018
0.02 
0.025 
0.03 


CD-09
—
—
—
—
—
—


CD-10
—
—
—
—
—
—


PAA
0.046
0.046
0.046
0.046
0.046
0.046


HEDP
0.015
0.015
0.015
0.015
0.015
0.015


FSO 100
0.005
0.005
0.005
0.005
0.005
0.005


Sum
0.666
0.686
0.674
0.682
0.686
0.696


ingre-


dients












PPP













PPP-34
PPP-35
PPP-36




(INV)
(COMP)
(COMP)







LX-02
0.55 
0.55 
0.55 



IR-01
0.05 
0.05 
0.05 



CP-02
0.02 
—
—



D-02
0.03 
—
—



CD-09
—
0.02 
—



CD-10
—
—
0.02



PAA
0.046
0.046
0.046



HEDP
0.015
0.015
0.015



FSO 100
0.005
0.005
0.005



Sum ingredients
0.706
0.686
0.686










Exposure, development, printing and evaluation of the printing plate precursors PPP-28 to PPP-36.

The printing plate precursors were exposed on a Creo Trend-Setter 3244 40 W fast head IR-laser plate-setter at 210-180-150-120-90 mJ/cm2 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-88 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

    
    
        77.3 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 1000 g gum solution.
    
    


After development and gumming the printing plates were mounted on a GTO46 printing press. A compressible blanket was used and printing was done with the fountain Agfa Prima FS101 (trademark of Agfa) and K+E 800 black 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-28 to PPP-36.
Evaluation of the printing plate precursors PPP-28 to PPP-36 were performed as described in example 1.
In table 10 the lithographic properties of the printing plate precursors PPP-28 to PPP-36 are shown.







TABLE 10





lithographic evaluation of PPP-28 to PPP-36

















PPP














PPP-28
PPP-29
PPP-30
PPP-31
PPP-32
PPP-33



(COMP)
(COMP)
(INV)
(INV)
(INV)
(INV)





IR/Surf
0.53
0.53
0.53
0.53
0.53
0.53


IR + D/
0.53
0.53
0.70
0.72
0.77
0.82


Surf


Sensitivity
150
150
150
180
120
150


1


Sensitivity
210
200
200
210
210
210


2


Clean out
4
3.5
4.5
5
5
5


2












PPP













PPP-34
PPP-35
PPP-36




(INV)
(COMP)
(COMP)







IR-dye/Surf
0.53
0.53
0.53



IR + D/Surf
0.82
0.53
0.53



Sensitivity 1
150
150
180



Sensitivity 2
200
210
180



Clean out 2
4.5
4
3










With PPP-28, no visual contrast is obtained, with PPP-29 to PPP-36 a good visual contrast is obtained.

When no dyes according to the present invention are present in the image-recording layer, a bad clean-out is observed (comparative examples PPP-28, PPP-29, PPP-35 and PPP-36.
When dyes according to the present invention are present in the image-recording layer, a good clean-out, a high sensitivity and a sufficient visual contrast is observed (invention examples PPP-30 to PPP-34).
The present invention thus provides, among other advantages, a negative working lithographic printing plate precursor having a high sensitivity, good lithographic properties, e.g. clean-out, and enabling a visual inspection of the exposed image after exposure and development.

## Claims

1. A heat-sensitive negative-working lithographic printing plate precursor comprising:
(a) a support having a hydrophilic surface or which is provided with a hydrophilic layer; and
(b) an image-recording layer comprising hydrophobic thermoplastic polymer particles, an infrared light absorbing dye and an additional dye according to Formula I:




wherein
Q represents an optionally substituted mono-, tri- or penta-methine chain;
Z and Z′ independently represent O, NR′, S or CH═CH wherein R′ is an optionally substituted alkyl or (hetero)aryl group;
X and X′ independently represent hydrogen, halogen, O—CH3, an optionally substituted alkyl or (hetero)aryl group, or a condensed benzene ring;
L and L′ represent a linking group; and
G and G′ represent an acid group or salt thereof; and
wherein the additional dye according to Formula I has a most bathochromic light absorption peak at a wavelength between 451 and 750 nm.

2. The heat-sensitive negative working lithographic printing plate precursor according to claim 1, wherein the acidic groups, G and G′ in Formula I are selected from the group consisting of:
(a) a substituted sulphonamido acid group;
(b) a carboxylic acid group;
(c) a sulphonic acid group;
(d) a dithiosulphonic acid group;
(e) a sulphuric acid group;
(f) a phosphoric acid group; and
(g) a phosphonic acid group.

3. The heat-sensitive negative working lithographic printing plate precursor according to claim 1, wherein the linking groups L and L′ in Formula I are —(CH2)q—, wherein q is an integer ranging from 1 to 5.

4. The heat-sensitive negative working lithographic printing plate precursor according to claim 2, wherein the linking groups L and L′ in Formula I are —(CH2)q—, wherein q is an integer ranging from 1 to 5.

5. The heat-sensitive negative working lithographic printing plate precursor according to claim 1, wherein the sum of the amounts of the infrared light absorbing dye and the additional dye, without taking into account optional counter ions, is more than 0.70 mg per m2 of the total surface of the particles, wherein the surface is measured by Hydrodynamic Fractionation.

6. The heat-sensitive negative working lithographic printing plate precursor according to claim 1, wherein the sum of the amounts of the infrared light absorbing dye and the additional dye, without taking into account optional counter ions, is more than 0.80 mg per m2, wherein the surface is measured by Hydrodynamic Fractionation.

7. The heat-sensitive negative working lithographic printing plate precursor according to claim 1, wherein the average particle diameter of the hydrophobic thermoplastic particles, measured by photon correlation spectroscopy, is from 25 nm to 55 nm.

8. A method for making a lithographic printing plate comprising the steps of:
(a) providing a printing plate precursor according to claim 1;
(b) exposing said printing plate precursor to infrared light; and
(c) developing said exposed printing plate precursor with a gum solution.

9. A method for making a lithographic printing plate comprising the steps of:
(a) providing a printing plate precursor according to claim 5;
(b) exposing said printing plate precursor to infrared light; and
(c) developing said exposed printing plate precursor with a gum solution.

10. A method for making a lithographic printing plate comprising the steps of:
(a) providing a printing plate precursor according to claim 1;
(b) exposing said printing plate precursor to infrared light; and
(c) developing said exposed printing plate precursor with an alkaline aqueous solution.

11. A method for making a lithographic printing plate comprising the steps of:
(a) providing a printing plate precursor according to claim 6;
(b) exposing said printing plate precursor to infrared light; and
(c) developing said exposed printing plate precursor with an alkaline aqueous solution.

12. A heat-sensitive negative-working lithographic printing plate precursor comprising:
(a) a support having a hydrophilic surface or which is provided with a hydrophilic layer; and
(b) an image-recording layer comprising hydrophobic thermoplastic polymer particles, an infrared light absorbing dye and an additional dye according to any of Formulae II to V:





wherein
Z and Z′ independently represent 0, NR′, S or CH═CH wherein R′ is an optionally substituted alkyl or (hetero)aryl group;
X and X′ independently represent hydrogen, halogen, O—CH3, an optionally substituted alkyl or (hetero)aryl group, or a condensed benzene ring;
L and L′ represent a linking group; and
G and G′ represent an acid group or salt thereof; and
wherein Rm, R1 and R2 independently represent H, alkyl or aryl.

13. The heat-sensitive negative working lithographic printing plate precursor according to claim 12, wherein the acidic groups, G and G′ in Formulae II to V are selected from the group consisting of:
(a) a substituted sulphonamido acid group;
(b) a carboxylic acid group;
(c) a sulphonic acid group;
(d) a dithiosulphonic acid group;
(e) a sulphuric acid group;
(f) a phosphoric acid group; and
(g) a phosphonic acid group.

14. The heat-sensitive negative working lithographic printing plate precursor according to claim 12, wherein the linking groups L and L′ in Formulae II to V are —(CH2)q—, wherein q is an integer ranging from 1 to 5.

15. The heat-sensitive negative working lithographic printing plate precursor according to claim 13, wherein said linking groups L and L′ in Formulae II to V are —(CH2)q—, wherein q is an integer ranging from 1 to 5.

16. A heat-sensitive negative-working lithographic printing plate precursor comprising:
(a) a support having a hydrophilic surface or which is provided with a hydrophilic layer; and
(b) an image-recording layer comprising hydrophobic thermoplastic polymer particles, an infrared light absorbing dye and an additional dye; according to Formulae VI or VII:





wherein
p and p′ are integers ranging from 0 to 3;
X and X′ independently represent hydrogen, halogen, O—CH3, an optionally substituted alkyl or (hetero)aryl group, or a condensed benzene ring; and
M+ is a monovalent positive counter ion.

17. The heat-sensitive negative working lithographic printing plate precursor according to claim 16, wherein the sum of the amounts of the infrared light absorbing dye and the additional dye, without taking into account optional counter ions, is more than 0.70 mg per m2 of the total surface of the particles, wherein the surface is measured by Hydrodynamic Fractionation.

18. The heat-sensitive negative working lithographic printing plate precursor according to claim 16, wherein the sum of the amounts of the infrared light absorbing dye and the additional dye, without taking into account optional counter ions, is more than 0.80 mg per m2, wherein the surface is measured by Hydrodynamic Fractionation.

19. A method for making a lithographic printing plate comprising the steps of:
(a) providing a printing plate precursor according to claim 17;
(b) exposing said printing plate precursor to infrared light; and
(c) developing said exposed printing plate precursor with a gum solution.

20. A method for making a lithographic printing plate comprising the steps of:
(a) providing a printing plate precursor according to claim 18;
(b) exposing said printing plate precursor to infrared light; and
(c) developing said exposed printing plate precursor with an alkaline aqueous solution.

21. A method for making a lithographic printing plate comprising the steps of:
(a) providing a printing plate precursor according to claim 16;
(b) exposing said printing plate precursor to infrared light; and
(c) developing said exposed printing plate precursor with an alkaline aqueous solution.