LOW VOLUME ABLATABLE PROCESSLESS IMAGING MEMBER AND METHOD OF USE

Abstract: A thermal imaging member can be imaged using infrared radiation such as from an IR-emitting laser and used for lithgraphic printing. The imaging member includes a support having an ink-repellant thermally sensitive imaging layer and an ink-repellant surface layer that is swellable in waterless ink solvents. Imaging ablates the imaging and surface layers, but minimal debris is generated so wiping or washing is not required. The imaging layer including a thermally sensitive copolymer of silicone "soft" segments and thermally sensitive "hard" segments, as well as a photothermal conversion material that is IR radiation sensitive.

Description: LOW VOLUME ABLATABLE PROCESSLESS IMAGING MEMBER AND METHOD OF USE FIELD OF THE INVENTION This invention relates in general to lithographic imaging members suitable for on- or off-press imaging, and particularly to waterless imaging members that require no wet processing or wiping after imaging. This invention also relates to a method of imaging such imaging member using for example digital means, and to a method of printing with the imaged members. BACKGROUND OF THE INVENTION Very common lithographic printing plates include a metal or polymeric support having thereon an imaging layer that is sensitive to visible or UN light. Both positive- and negative-working printing plates can be prepared in this fashion. After exposure to a light source, and possibly to a heat source, either imaged or non-imaged areas are removed using wet processing chemistries. Thermally sensitive printing plates are becoming more common and are available at least from Kodak Polychrome Graphics. Such imaging members include an imaging layer comprising a mixture of dissolvable polymers and an infrared radiation-absorbing compound. While these imaging members can be imaged using digital means (such as lasers) and can be utilized in what is known as "computer-to-press" imaging systems, they still require post-imaging wet processing using alkaline developer solutions. Dry planography or waterless printing is well known in the art of lithographic offset printing and has several advantages over conventional offset printing. Dry planography is particularly advantageous for short run and on-press applications. It simplifies press design by eliminating the fountain solution and aqueous delivery train. Careful ink water balance is unnecessary, thus reducing rollup time and material waste. An unexposed waterless printing plate typically comprises a layer of ink repellent material over a layer of ink accepting material or an ink-accepting surface. Because of their low surface energies and their ability to swell in the long- chain alkane solvents used in printing inks, silicone rubbers, such as poly(dimethylsiloxane) (identified herein as "PDMS") and other derivatives of poly(siloxanes), have long been recognized as preferred waterless-ink repelling materials. Preparation of the printing plates involves the imagewise removal of the ink repellent silicone rubber to expose the underlying ink accepting material or surface. Various methods of removing the silicone rubber layer have been developed. Imaging of dry planographic printing plates with infrared lasers has been described in Canadian Patent 1,050,805 (Eames) and by Nechiporenko and Markova, "Advances in Printing Science and Technology," Proceedings of the 15 th International Conference of Printing Research Institutes. June 1979, Pentech Press, London, pp. 139-148. The silicone rubber layer is coated over a heat-absorbing layer containing an infrared absorbing material in nitrocellulose. Imagewise exposure with an infrared laser partially disrupts the heat-absorbing layer, allowing it and the overlying silicone layer to be removed from the exposed regions with a solvent. Infrared imaging of printing plates with "ablatable" layers has also been described in US-A-4,718,340 (Love III), WO 92/07716 (Landsman), WO 94/18005 (Verburgh et al), US-A-5,379,698 (Nowak et al), US-A-5,310,869 (Lewis), US-A-5,339,737 (Lewis et al), US-A-5,385,092 (Lewis et al), US-A-5,351,617 (Williams), US-A-5,353,705 (Lewis et al) and US-A-5,487,338 (Lewis). These documents describe the use of direct digital imaging on-press or a platesetter. In each of these methods, mechanical wiping or washing with liquids is required to remove the silicone rubber debris clinging to the plate after exposure. This problem arises because of the conflicting needs to have wear-resistant silicone layers for long press runs while maintaining the ease of layer removal during thermal imaging. Wiping has several drawbacks. It is difficult to reproducibly remove all stray material with automated cleaning stations. Moreover, wiping can scratch or abrade the printing plate. A truly processless printing plate, that is one that does not require a separate processing step to remove the silicone rubber debris after imaging, would have several advantages. The post-imaging development or wiping step would be eliminated, simplifying the process for preparing the printing plate. In addition, any scratching or abrading of the plate surface caused by development would be eliminated. If desired, the plate could be exposed on the printing press, eliminating any potential damage to the plate caused by handling and mounting on the press after imaging. There are three key requirements for an ink repellent polymer to be useful for a thermally imageable, processless printing plate that is imaged using ablation. The ink repellent polymer must form a solid film at room temperature to resist damage from the press. It also must release ink, and must be easily removed by the imaging step alone or by the normal action of the press after imaging. Copending U.S. Serial No. 08/749,050 (noted above) discloses a class of silicone copolymers that exhibit these desirable attributes. The plates prepared using those copolymers can be imaged and used to print many thousands of impressions. Unfortunately such printing plates still suffer from the conflicting need to be durable on press but readily thermally imaged without the need for wiping or washing. Optimum exposure for ablation plates is therefore relatively high, leading to undesirable system costs in power and time. A need exists in the industry for a thermally imageable processless and waterless imaging member in which the ink repellent layer is a polymer that is wear resistant and easily ablatable during thermal imaging with a low volume of residual debris. SUMMARY OF THE INVENTION The problems noted above have been overcome with a thermal imaging member comprising an ink-accepting support having thereon: (a) an ink-repellant, thermally sensitive imaging layer that comprises a photothermal conversion material and a thermally sensitive copolymer comprising one or more silicone segments and one or more thermally sensitive "hard" segments, the silicone segments comprising from about 50 to about 99 weight % of the copolymer, the imaging layer being capable of becoming ink-accepting upon exposure to thermal energy, and (b) an ink-repellant surface layer that is swellable in waterless ink solvents. This invention also provide a method of imaging comprising: A) providing the imaging member described above, and B) imagewise ablating the surface layer of the imaging member using infrared radiation to provide a surface image. Further, this invention provides a method of printing comprising after the step A and B noted above: C) inking the surface image and imagewise transferring the ink to a receiving material. The imaging members of this invention provide several advantages. They require relatively low thermal exposure during imaging. Furthermore, a much lower volume of polymer material needs to be removed and collected, upon imaging. As a result, the imaging method does not require a wiping step or washing with liquids. Thus, the imaging members can be directly imaged using digital information supplied for example using a laser. They have high writing sensitivity, high image quality, short roll up time and long run length. The particular imaging layer includes a thermally sensitive copolymer having silicone segments and thermally sensitive "hard" segments. These "hard" segments provide physical integrity and thermal sensitivity while the silicone segments provide ink releaseability. The balancing of relative amounts of these segments provides all of the desired properties for the imaging layer. The surface layer is highly durable, but thin so that there is limited debris from the imaging process. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a highly schematic, cross-sectional view of one embodiment of the imaging members of this invention having a support and two supported layers. FIG. 2 is a highly schematic, cross-sectional view of another embodiment of the imaging members of this invention having a support and three supported layers. DETAILED DESCRIPTION OF THE INVENTION A representative imaging member of this invention is illustrated in FIG. 1 as having support 106 having thereon ink-repellant, thermally sensitive imaging layer 102 and ink-repellant surface layer 100. Another embodiment is shown in FIG. 2 as having support 106 having thereon adhesion-promoting layer 104, ink-repellant, thermally sensitive imaging layer 102 and ink-repellant surface layer 100. Further details of these and other components of the imaging members of this invention are provided below. Upon exposure infrared radiation penetrates the transparent, ink- repellent surface layer to be absorbed in the imaging layer. The imaging layer is heated with explosive force, disrupting and ablating the thin overlying surface layer. Concurrently, the affinity for waterless ink of the imaging layer is enhanced thought a process of physical and or chemical switching not fully understood. The net result of exposure is to produce ink-accepting areas surrounded by an ink-repellent background. It is well known that the ink-repelling nature of PDMS layers depends not only on their intrinsic properties (that is polymer composition) but also on extrinsic properties (that is how thick the layer is). Thin layers of crosslinked PDMS (for example < 0.3 μm) on an ink-accepting support such as a polyester support do not repel ink well. A salient feature of this invention is the ability of both layers to swell in waterless ink solvent before exposure. The relatively thick imaging layer can transmit some of its ink repelling nature, presumably through solvent diffusion, to the overlying ink-repelling surface layer. The various preferred features of the imaging members and methods of use are now described. Support: The thermal imaging members of this invention include an ink- accepting support that can be any self-supporting material including polymeric films, glass, ceramics, metals or stiff papers, or a lamination of any of these materials. The thickness of the support can vary depending upon the desired use and imaging and printing equipment used. In most applications, the thickness should be sufficient to sustain the wear from printing and thin enough to wrap around a printing form (or cylinder). A preferred support is composed of a polyester such as poly(ethylene terephthalate) (for example MYLAR polyester film sold by E.I. dupont de Nemours Co. and MELINEX polyester film sold by ICI Films) or poly(ethylene naphthalate) and has a thickness of from about 100 to about 310 μm. In another embodiment, the support is composed of a metal foil such as an aluminum foil having a thickness of from about 100 to about 600 μm. Thus, supports useful in the practice of the invention are strong, stable and flexible. Paper substrates are typically "saturated" or coated with polymers to impart water resistance, dimensional stability and strength. The support can be coated or treated in suitable fashion to improve adhesion of upper layers. For example, a subbing or adhesion-promoting layer can be composed of materials such as alkoxysilanes, aminopropyltriethoxysilane, glycidoxypropyltriethoxysilane and epoxy functional polymers, as well as conventional subbing layer materials used on polyester supports for photographic silver halide films and papers. One or more IR radiation reflecting layers, such as layers of evaporated metals, can also be incorporated between the support and the thermally sensitive imaging layer. The backside of the support may be coated with antistatic agents, slipping layers or matte layers to improve handling or "feel" of the imaging member. There may be a protective overcoat on either side of the support, as long as the protective overcoat on the "imaging" side is readily ablated along with the surface layer on that side. The imaging member comprises at least two coextensive layers. By "coextensive" is meant that they cover essentially the same area of the support. The coextensive thermally sensitive imaging layer is nearest the support, and the ink- repellant surface layer is located above that imaging layer and usually contiguous or adjacent thereto. The imaging members of this invention can be of any useful form including, but not limited to, printing plates, printing cylinders, printing sleeves and printing tapes (including flexible printing webs). Preferably, the imaging members are printing plates. Printing plates can be of any useful size and shape (for example, square or rectangular) having the requisite heat-sensitive imaging layer disposed on a suitable support. Printing cylinders and sleeves are known as rotary printing members having the support and heat-sensitive layer in a cylindrical form. Hollow or solid metal cores can be used as substrates for printing sleeves. Thermally Sensitive Imaging Layer: The thermally sensitive imaging layer includes one or more thermally sensitive copolymers containing both "hard" and "soft" (silicone) segments. Thus, this layer comprises a copolymer of soft silicone segments (S) linked to hard segments (H) as represented by the following Structure I: H — S I The S segment is swellable in a lithographic ink solvent, contributes to the overall copolymer the property of ink release and is preferably a polysiloxane of the following general Structure II: Ri m R 2 II wherein "m" designates the size of the siloxane polymer and can be 5 to 10,000 and Ri and R 2 define the form of the siloxane polymer, and can be independently suitable organic radicals including, but not limited to, substituted or unsubstituted alkyl group of 1 to 20 carbons (such as methyl, ethyl, isopropyl, trifluoromethyl and cyanoalkyl), substituted or unsubstituted aryl groups of 6 to 10 carbon atoms in the aromatic ring (such as phenyl, napthyl and 7-methylphenyl), and long ether sequences such as repeating oxyalkylene groups. While mostly linear, there can be branching points or additional functional groups associated with these Ri and R 2 groups. Preferably, Ri and R 2 are independently substituted or unsubstituted alkyl of 1 to 4 carbon atoms and more preferably, each is a methyl group. Examples of particularly useful S segments are polydimethylsiloxane and polymethy phenyl siloxane. S segments generally comprise from about 50% to about 99% (preferably from about 80 to about 90%) of the copolymer based on the total copolymer weight. The structures of the S segments can be siloxane polymers as described above. In addition to the siloxane groups, the S segment may contain terminal or pendant X linking groups that facilitate the coupling of S segments to H segments. The nature, location and number of these linking groups depends upon the specific chemistry used to build H segments and the specific architecture desired in the copolymers. Useful X linking groups include, but are not limited to, aminoalkyl and hydroxyalkyl groups wherein the alkyl portion (linear or branched) has for example 1 to 6 carbon atoms. A preferred linking group is an aminopropyl group. With regards to location and number, the X linking groups can be attached as terminal groups shown as follows in Structure III: III or as pendant groups shown as follows in Structure IN below wherein m and c(a+b) designate the size of the silicone and c designates the number of pendant groups. Ri and R 2 are as defined above, and R 3 is the same as Ri or R 2 . IN Diblock copolymers of S and H segments would have one terminal X linking group, triblocks with an H segment at the center would have one terminal X linking group on the silicone, triblocks with a S segment at the center or multiblock sequences would have two terminal X linking groups on the silicone. Graft copolymers with S segments side chains would have one terminal X linking group. Graft copolymers having H segments as the side chain would have one or more pendant X linking groups depending on the number of H segment side chains. Combinations of the above may be used to achieve more complex structures in which case multiple locations for X and a variety of different functional groups may be used. The identity of the functional groups will depend upon the chemistry of the H segments as described below. Silicone polymers are widely used in waterless printing applications because they release ink. However, silicone polymer films in the uncrosslinked form are either fluids or gums and lack the physical properties needed for handling and printing. Therefore, silicones are generally crosslinked by a number of methods including reactions between silicone hydride and Si-vinyl, reactions between Si-OH or Si-OR groups, and other well known crosslinking chemistries. Although crosslinking imparts robust physical properties to the film, the resulting network is not readily broken down by heat. Therefore, the imaging layer containing the silicone segments exposed to laser imaging retains its integrity and is not altered enough to be easily removed. The H segments of the copolymer useful in this invention generally comprise less than 50% on a weight basis of the copolymer and impart good physical properties and thermal sensitivity. The physical properties are a result of associations between the H segments that have the effect of crosslinking the copolymer. The associations may include high glass transition temperature (Tg) glassy domains, hydrogen bonding, ionic associations, crystallinity or combinations of these interactions. It may also include but does not necessarily require chemical bonds. The second contribution of the H segments is thermal sensitivity. The noted H segment associations can break down at elevated temperatures more readily than the silicone chain or the silicone crosslinked bonds noted above. Therefore laser imaging can reduce the integrity of the layer and the resulting layer can be easily removed either during or after exposure by the normal application of the process. The thermal breakdown of associations in the H segments may be due to glass to liquid transition (Tg), breakdown in hydrogen bonding, melting, and breaking of chemical bonds or combinations of these effects. The -H-S- structure in the copolymer is intended to indicate the two components of the polymer and the properties they impart but does not limit the many ways they may be combined. Thus, the structure would include a diblock copolymer of -H-S-, triblock copolymers of -H-S-H- or -S-H-S-, or multiple sequences as in (-H- S-) n wherein "n" represents the number of sequences and can be from 0 to 20 (preferably from 0 to 3). In addition, the S segments can be side chains attached to an H main segment, or there may be H side segments attached to an S main segment. The side or main chains may also be diblock, triblock or higher multiple sequences of H and S segments. Multi-armed star architectures where the arms are combinations of H and S segments are also contemplated. The H segment can be derived from a variety of polymers including, but not limited to, polyurethanes, polyesters, polycarbonates, polyureas, polyimides, polyamic acid, polyamic acid salts, polyamides, epoxides from bisamines and bisepoxides, phenol formaldehyde, urea formaldehyde, melamine formaldehyde, epichlorohydrin-bisphenol A epoxides, carbodiimide polymers derived from bisisocyanates, and a wide variety of condensation polymers derived from pairs of difunctional monomers. Preferred copolymers useful in the imaging layer can be represented below in Structure N in which AA and BB represent two difunctional monomers: N wherein "r" is at least 2 and i, R 2 , "n" and "m" are as defined above. In the case of polyurethanes, the resulting A-B linkages are urethanes, AA and BB are difunctional monomers derived from the isocyanate and alcohol parts of the urethane group. In the case of polyesters, the resultant A-B linkages are esters, AA and BB are difunctional monomers derived from the carboxylate and alcohol parts of the ester group. In other words, AA and BB type monomers generally have the same reactive groups in the same molecule. Polyureas, polycarbonates, polyimides, polyamic acid analogue of the polyimide either as the free acid or in the salt of the acid form, polyamides, formaldehyde copolymers can be described in similar fashion. For carbodiimide polymers, AA and BB would both be diisocyanates. A mixture of AA groups and a mixture of BB groups may be used in any of these examples. In these embodiments, the nature of the X linking group is dependent upon the composition of the H segment. X can be derived from an alkyl or aryl group attached to the silicon atom and contains additional functional groups capable of reacting with the corresponding AA group. Where AA is an isocyanate or carboxylate, X would be derived from an alkyl or aryl substituted with hydroxyl, amine or thiol groups. Where AA is an amine, the corresponding groups would contain an isocyanate, carboxylate or epoxy. Where AA is a hydroxyl or thiol, X would contain an isocyanate or carboxylate. Where AA is a methyoyl-substituted phenol, X would contain a phenolic or urea group. A variety of such materials are described in the Gelest catalogue (Gelest Inc. Tullytown, PA) for functional silicones and include aminopropyl, epoxypropoxypropyl, hydroxyalkyl, mercaptopropyl and carboxypropyl groups. Condensation polymers can also be formed from monomers of the AB variety (different reactive groups in the same molecule) that contain both of the functional groups needed to form the final polymers as shown below in Structures NI and NIL These include polyesters, polyamides, phenoxy resins, etc. Examples of such polymers are polyesters formed from / hydroxybenzoic acid wherein A is the hydroxyl component and B is the carboxylate component. In this case, the coupling of an H segment to a S segment would require a mixture of Y and X on the siloxane wherein Y is a carboxylate reactive group such as hydroxyl, amine, thiol, epoxy and X is a hydroxyl reactive group such as carboxylate, isocyanate, etc. Alternatively, the H segments can be capped with a difunctional AA monomer to give an A-capped H segment capable of reacting with an X-functionalized S segment. -N -Y J- -Si 1 - -O-Vsi — X- 2 R2 NI or Nil In the above structures "n" can be any integer (including 0 if at least one AA or BB is present in the H segment) up to 20 (preferably 0 to 3) and "m" can range from 5 to 10,000 while "n" and "m" bear a relationship such that for large values of "n" and for large molecular weights of AA, BB, or AB, the substituents Ri and R 2 on the silicone and "m" must be large enough to give the overall structure a silicone content of greater than 50% (of total copolymer weight). Structures NI and Nil represent X and Y as terminal groups and H and S segments as a multiblock copolymer. Other architectures (graft, stars, branched or other block sequences) could also be present by using the appropriate number and location of X coupling groups on the silicone. In the case of highly substituted silicones, the final copolymer will have a branched structure or crosslinked structure and may, as a practical matter, have to be formed on the substrate during the film forming operation. In the case of linear polymers, "r" represents the multiplicity of the H-S repeating sequence or the overall molecular weight and can range from 1 to 100. A wide variety of H segments can be prepared that are derived from vinyl monomers including acrylates, methacrylates, acrylic acid, methacrylic acid, cyanoacrylates, styrene, α-methylstyrene, vinyl esters, vinyl halides, vinylidene halides, maleic anhydride, maleimides, vinyl pyridine, olefins as well as copolymer mixtures of these monomers. Also, polymers derived from ring opening polymerization monomers such as cyclic ethers, lactams, lactones, and oxazolines, and from carbonyl monomers such as acetaldehyde and phthalaldehyde. These polymers and copolymers can be described by the general Structure NIII: Nπi wherein (N) n represents a sequence derived from the above monomers and X represents the coupling of that sequence to the silicone segments. The nature of X depends on the type of monomer and polymerization. In the case of anionic polymerization of the N monomers in Structure VIII, the growing N anion can initiate cyclic siloxane polymerization directly at the silicon atom in which case no X would be required. In the case of graft architecture, the anionic polymerization of siloxane could be terminated with a vinyl, aldehyde, ether or oxazoline functional group that would subsequently be copolymerized with a N monomer. Also, aminoalkyl terminated siloxanes could initiate the anionic polymerization of Ν-carboxyanhydrides or of cyanoacrylates. Carboxy- or hydroxy- terminated siloxanes could initiate polymerization of lactones. Alkyl halide terminated silicones could initiate oxazoline polymerizations. A wide variety of vinyl monomer could be polymerized where X represents a radical initiator (such as an azo or peroxide group) attached to the siloxane. The more preferred embodiments of this invention will now be described in detail. The ink-repellant, thermally sensitive imaging layer can comprise a copolymer of a S segment linked to an H segment as represented in Structure IX: IX wherein AA is a diisocyanate and BB is a diol, n is 0 to 3 and Ri and R 2 are methyl. The X linking group on the end of the silicone is -CH 2 CH 2 CH 2 ΝH 2 . The amine group reacts with AA to couple the H and S segments. The illustrated structure is repeated "r" times to produce a higher molecular weight copolymer. Additional examples of AA and BB are listed below. The relative amounts of silicone to non-silicone can be adjusted by lengthening or shortening either the number of siloxane repeating units ("m") or the number of urethane repeating units ("n"). The silicone segment can be of molecular weight greater than 400 and can be a combination of different molecular weights. The upper end of the silicone molecular weight range is limited only by the reliability of attaching at least one (preferably two or more) reactive X linking groups to the chain, either as terminal or pendant functional groups. The silicone is predominately dimethylsiloxane but may contain substituents other than methyl, including but not limited to, phenyl, fluoroalkyl, cyanoalkyl, or long ether sequences groups, to adjust physical properties such as Tg. The urethane portion of the copolymer need not be entirely bisphenol and diisocyanate and may be filled with a wide variety of diols or diamines that may be monomeric, oligomeric or polymeric. The copolymer structure may be branched or crosslinked if multifunctional reactants are used. In this case, solution gelation would be avoided by completing the reaction during the drying step. Excess multifunctional isocyanates can be added to react with the urethane or urea linkages to give allophonate or biuret crosslinks. Crosslinking of the silicone segments can be achieved by any one many functional chemistries as described above. Examples of AA groups include but are note limited to 1,6- hexamethylenediisocyanate (HMDI), 4,4'-diphenylmethane diisocyanate (MDI), 4,4' dicyclohexylmethane diisocyanate (RMDI), l-isocyanato-3-isocyanatomethyl-3,5,5- trimethyl-cyclohexane (IPDI), 2,4 and 2,6-toluene diisocyanate (TDI) and other well known aliphatic and aromatic di- and multifunctional isocyanates. Examples of BB include but are not limited to 4,4'- isopropylidenediphenol (GH), 4,4'-isopropylidenebis(2,6-dichlorophenol) (TCBA), 4,4'-isopropylidenebis(2,6-dibromophenol), 4,4'-isopropylidenebis(2- hydroxyethoxybenzene) (AE), 4,4'-(octahydro-4,7-methano-5H-inden-5-ylidene) bis(2-hydroxyethoxybenzene) (GY), and GK A particularly preferred copolymer useful in the present invention is represented by Structure X: X wherein the disocyanate is based on MDI, m is 225, n has an average value of 0.8 and p is 12. In this particular embodiment, the H segment does not contain any diol (r is 0) and the S segment is a combination of two silicones of different chain lengths and compositions. The X linking group on the end of the silicone is -CH 2 CH 2 CH 2 NH 2 . A detailed description of the preparation of the preferred copolymer is as follows, but it should be understood that other copolymers useful herein can be similarly prepared. The noted copolymer of Structure X was prepared by slowly adding a solution of MDI (16.53g) in a toluene/tetrahydrofuran mixture (500ml:50ml) to a mixture of bisaminopropylsilicone (543g, Mn is 16,400, 0.036 mole% vinyl repeating units) and a shorter bisaminopropylsilicone (DMS-A11, Gelest, 30g, Mn is 900, no vinyl groups) in 3 liters of toluene. The solution was then heated to 60°C to offset the viscosity increase that occurred during MDI addition. The addition time was approximately 2 hours. The final concentration of the copolymer was 16.2% w/w and its molecular weight was 190,000. The thermally sensitive imaging layer also includes one or more photothermal conversion materials that are capable of converting light to heat and are also capable of aiding in the ablation of exposed area. The photothermal conversion materials absorb appropriate radiation from an appropriate energy source (such as an IR laser), converting the energy into heat. Preferably, the radiation absorbed is in the infrared and near-infrared regions of the electromagnetic spectrum. Such materials can be dyes, pigments, evaporated pigments, semiconductor materials, alloys, metals, metal oxides, metal sulfides or combinations thereof, or a dichroic stack of materials that absorb radiation by virtue of their refractive index and thickness. Borides, carbides, nitrides, carbonitrides, bronze-structured oxides and oxides structurally related to the bronze family but lacking the WO 2 9 component, are also useful. A wide range of such materials is well known and suitable for use in the imaging members of this invention. For example, materials that are useful with laser-induced thermal reactions are known in the art and described for example in US- A-4,912,083 (Chapman et al), US-A-4,942,141 (DeBoer et al), US-A-4,948,776 (Evans et al), US-A-4,948,777 (Evans et al), US-A-4,948,778 (DeBoer), US-A- 4,950,639 (Evans), US-A-4,952,552 (Chapman et al), US-A-4,973,572 (DeBoer) and US-A-5,036,040 (Chapman et al). Any of these photothermal conversion materials can be used in the present invention. Pigments are preferred over amorphous dyes. In a preferred embodiment, carbon black particles were found to work particularly well. Carbon blacks that are surface-functionalized with solubilizing groups are well known in the art and these types of materials are preferred photothermal conversion materials for this invention. Carbon blacks which are grafted to hydrophilic, nonionic polymers, such as FX-GE-003 (manufactured by Nippon Shokubai), or which are surface-functionalized with anionic groups, such as CAB-O- JET ® 200 or CAB-O- JET ® 300 (manufactured by the Cabot Corporation) are especially preferred. Carbon blacks available as Black Pearls 280 (Cabot) are especially preferred. Mixtures of pigments and dyes, or both, can also be used. Useful infrared radiation absorbing dyes include those illustrated as follows: I Dye 1 p-Toluenesulfate- IR Dye 2 Same as Dye 1 but with chloride as the anion. IRDye 3 IRDye 4 IRDye 5 I-RDyeό IRDye 7 IRDye8 I Dye 9 Useful oxonol compounds that are infrared radiation sensitive include Dye 5 noted above and others described in copending and commonly assigned U.S.S.N.09/444,695, filed November 22, 1999 by DoMinh et al. The photothermal conversion material(s) are generally present in an amount sufficient to provide an optical density of at least 0.3 (preferably of at least 0.5 and more preferably of at least 1.0) at the operating wavelength of the imaging laser. The particular amount needed for this purpose would be readily apparent to one skilled in the art, depending upon the specific material used. Incorporation of the photothermal conversion material in the imaging layer in an appropriate concentration renders it sensitive to laser radiation and capable of generating an image by laser- induced thermal switching. The thermally sensitive imaging layer has a thickness in the range of from about 0.1 to about 10 μm and more preferably in the range of from about 1 to about 5 μm. The thermally sensitive imaging layer formulation can be applied to the support (or adhesion-promoting layer) using any suitable equipment and procedure, such as spin coating, knife coating, gravure coating, dip coating or extrusion hopper coating, out of a suitable solvent such as 2-butanone, toluene or tetrahydrofuran. The formulation can also be applied by spraying onto a suitable support (such as an on-press printing cylinder) as described in US-A-5,713,287 (Gelbart). Surface Layer: The ink-repellant surface layer is composed of crosslinked silicone polymers including but not limited to crosslinked poly(dimethylsiloxane) and other derivatives of poly(alkylsiloxanes) well known in the art of waterless printing (such as those described in CA-1,050,805, and US-A-5,310,869, 5,339,737, US-A-5,385,092 and 5,487,338, all noted above and incorporated herein). These polymers may be straight or branched and can be crosslinked by any number of well-known chemistries such as hydro silylati on of vinyl-substituted siloxanes or alkoxy silane condensation. This layer can also include one or more conventional surfactants for coatability or other properties, or dyes or colorants to allow visualization of the written image, or any other addenda commonly used in the lithographic art, as long as the concentrations are low enough so that there is no significant interference with the ability of the desired properties of the surface layer. The dry thickness of the surface layer is generally at least 0.1 μm, and preferably at least 0.2 μm. Generally, the dry thickness is no more than 1 μm and preferably no more than 0.7 μm. The surface layer can be applied to the imaging layer using the conventional coating techniques and solvents described above for applying the imaging layer to the support. Adhesion-promoting Layer: Referring to FIG 2, an optional layer 104 can be composed of any material that functions to improve adhesion of the imaging layer to the support. Examples of such materials include but are not limited to poly(vinyl chloride), poly(vinylidene chloride), poly(vinyl chloride-co-vinylidene chloride), chlorinated poly(propylene), poly( vinyl chloride-co-vinyl acetate), poly(vinyl chloride-co-vinyl acetate-co-maleic anhydride), ethyl cellulose, nitrocellulose, poly(acrylic acid) esters, linseed oil-modified alkyd resins, rosin-modified alkyd resins, phenol-modified alkyd resins, phenolic resins, poly(esters), poly(isocyanate) resins, poly(urethanes), poly(ureas), poly(vinyl acetate), poly(amides), chroman resins, gum damar, ketone resins, maleic acid resins, vinyl polymers such as poly(styrene) and poly(vinyltoluene) or copolymers of vinyl polymers with methacrylates or acrylates, low-molecular weight polyethylene, phenol-modified pentaerythritol esters, poly(styrene-co-indene-co-acrylonitrile), poly(styrene-co-indene), poly(styrene-co- acrylonitrile), copolymers with siloxanes, poly(alkenes) and poly(styrene-co- butadiene) all of which may be used either alone or in combination. Polymers that are crosslinked or branched can also be used. For example, poly(styrene-co-indene-co-divinylbenzene), poly(styrene-co-acrylonitrile- co-divinylbenzene) or poly(styrene-co-butadiene-co-divinylbenzene) can be used for this purpose. Coating of this layer can also be carried out using the coating methods and solvents described above for other layers in the imaging members. Imaging Method: The imaging method of this invention includes imagewise heating the imaging member preferably by means of a focused laser beam, and applying ink in a suitable manner. Ink is repelled from the portions of the imaging member that are not heated. The imaging members are then suitable for use with typical lithographic presses configured to print with waterless inks. More particularly, the imaging member of this invention is exposed to a suitable source of energy that generates or provides heat, such as a focused laser beam or a thermoresistive head, in the foreground areas where ink is desired in the printed image, typically from digital information supplied to the imaging device. No additional heating, wet processing, or mechanical or solvent cleaning is needed before the printing operation. A laser used to expose the imaging member of this invention is preferably a diode laser, because of the reliability and low maintenance of diode laser systems, but other lasers such as gas or solid state lasers may also be used. The combination of power, intensity and exposure time for laser imaging would be readily apparent to one skilled in the art. Specifications for lasers that emit in the near-IR region, and suitable imaging configurations and devices are described in US-A- 5,339,737 (noted above), incorporated herein by reference. The imaging member is typically sensitized so as to maximize responsiveness at the emitting wavelength of the laser. For dye sensitization, the dye is typically chosen such that its O max closely approximates the wavelength of laser operation. The imaging apparatus can operate on its own, functioning solely as a platesetter, or it can be incorporated directly into a lithographic printing press. In the latter case, printing may commence immediately after imaging, thereby reducing press set-up time considerably. The imaging apparatus can be configured as a flatbed recorder or as a drum recorder, with the imaging member mounted to the interior or exterior cylindrical surface of the drum. In the drum configuration, the requisite relative motion between the imaging device (such as a laser beam) and the imaging member can be achieved by rotating the drum (and the imaging member mounted thereon) about its axis, and moving the imaging device parallel to the rotation axis, thereby scanning the imaging member circumferentially so the image "grows" in the axial direction. Alternatively, the thermal energy source can be moved parallel to the drum axis and, after each pass across the imaging member, increment angularly so that the image "grows" circumferentially. In both cases, after a complete scan by the laser beam, an image corresponding to the original document or picture can be applied to the surface of the imaging member. In the flatbed configuration, the laser beam is drawn across either axis of the imaging member, and is indexed along the other axis after each pass. Obviously, the requisite relative motion can be produced by moving the imaging member rather than the laser beam. While laser imaging is preferred in the practice of this invention, imaging can be provided by any other means that provides thermal energy in an imagewise fashion. For example, imaging can be accomplished using a thermoresistive head (thermal printing head) in what is known as "thermal printing", described for example in US-A-5,488,025 (Martin et al). Thermal print heads are commercially available (for example, as Fujitsu Thermal Head FTP-040 MCSOOl and TDK Thermal Head F415 HH7-1089). Without the need for any wet processing after imaging, printing can then be carried out by applying a lithographic ink and fountain solution to the imaging member printing surface, and then transferring the ink to a suitable receiving material (such as cloth, paper, metal, glass or plastic) to provide a desired impression of the image thereon. If desired, an intermediate "blanket" roller can be used to transfer the ink from the imaging member to the receiving material. The imaging members can be cleaned between impressions, if desired, using conventional cleaning means. The following examples illustrate the practice of the invention and are not meant to limit it in any way. Methods and Materials for the Examples: Exposure and Printing Conditions: All of the lithographic plates were exposed using an external lathe-type drum printer with a 450 mW per channel laser beam (830 nm), 9 channels per revolution, a spot size of approximately 25 μm x 25 μm, recording at 2400 lines per inch (945 lines per cm) with a half step interline configuration and drum speeds between 300 and 900 rpm (revolutions per minute) corresponding to exposures of from 1500 to 350 mJ/cm 2 , and having a drum circumference of 53 cm. These imaging conditions do not necessarily correspond to the optimum exposure for these samples. Imaged printing plates were printed, without wiping or further processing, using a commercially available Heidelberg GTO offset press without the fountain roller or fountain solution. The waterless inks used were either K50-95932- Black (available from INX International, Rochester NY), Kohl and Madden Sharp and Dry Waterless CTP Dense Black NA 19944 or Kohl and Madden Sharp and Dry Waterless CTP Process Cyan as indicated below. Imaging Layer Formulation: The copolymers used are based upon Structure X (noted above). In particular, Polymer HS98 had the following characteristics: m was 225, n was 0.8 (Average Value), Mn of silicone #1 was 16,700, p was 12, Mn of silicone #2 was 900, and an overall copolymer molecular weight of 190,000. Polymer HS104 had the following characteristics: m was 435, n was 1.6 (Average Value), Mn of silicone #1 was 32,400, p was 12, Mn of silicone #2 was 900, and an overall copolymer molecular weight of 344,000. A carbon black dispersion was prepared by adding 82.9 g of a 16.2% solution of Polymer HS98 in toluene, 6.7 g of carbon black (see examples below) and about 200 g of 2 mm zirconium oxide XR beads (Zircoa Inc.) to 60.4 g of 2-butanone. The dispersion was placed on a roller-mill for about 36 hours then course filtered to remove the grinding media. This resulted in a dispersion having a polymer-to-carbon ratio of 2: 1 by weight. Polymer-to-carbon ratios in the examples varied from 2: 1 to 1 :2 as noted below. Thermally Sensitive Imaging Layer: An imaging layer was prepared by mixing the following components; 8.9 g of the copolymer plus carbon-black dispersion described above, 0.53 g of a 0.2% solution of the catalyst [platinum-divinyltetramethyldisiloxane complex (SIP6831.0, Gelest Inc.)] in 2-butanone, 0.11 g of a 10% solution of inhibitor [3- methyl- l-pentyn-3-ol (Aldrich)] in 2-butanone and 0.64 g of a 10% solution of a polymer crosslinker [PS 120 (United Chemical Technologies)] in 2-butanone to 4.85 g of 2-butanone. This formulation was coated at 37.9 ml/m onto the support using a syringe pump and translating slot hopper. Some samples were "pre-cured" in an oven for 10 minutes at 100°C before the ink-repelling surface layer was applied as indicated below. Ink-Repelling Surface Layer: A typical ink-repelling layer was prepared by adding the following components in the noted proportions: 6.5 g of a 10% solution of poly(dimethylsiloxane) vinyldimethyl terminated (PS225, United Chemical Technologies) in n-hexane, 0.65 g of a 0.2% solution of catalyst [platinum- divinyltetramethyldisiloxane complex (SIP6831.0, Gelest Inc.)] in toluene, 0.65 g of a 10%) solution of inhibitor [3-methyl-l-pentyn-3-ol (Aldrich)] in 2-butanone and 0.5 g of a 10% solution of a polymer crosslinker [PS 120 (United Chemical Technologies)] in toluene, to 6.7 g of n-hexane. This formulation was coated onto the imaging layer described above using a syringe pump and translating slot hopper at 10.9 ml/m 2 . All samples were cured in an oven for 10 minutes at 100°C after the surface layer was dried. Examples 1-10: A series of imaging members were prepared as described above (see also TABLE I), imagwise exposed, inked and used for printing. Examples 1 and 8 were Control imaging members lacking an ink-repelling surface layer and outside the present invention. Examples 2-7, 9 and 10 represent imaging members of the present invention. The ink-repellant surface layer of Example 2 formed a strong bond to the imaging layer. It was more resistant to solvents than the Control imaging member having HS copolymer at the surface and was considerably more resistant to physical deformation as measured with a subjective finger-rub test. Similar results were obtained whether or not the imaging layer was heated (pre-cured) before the ink- repelling layer was applied. Imaging members were used for printing directly after imaging without wiping or further processing. TABLE I Plate Imaging Layer* Ink-Repelling Layer* Pre-cure** Comment Example Bottom Surface 1 150HS9875C8%PS120 None yes Control 2 150HS9875C8%PS120 30 PS2558%PS120 no Prototype 3 150HS9875C8%PS120 30 PS2558%PS120 yes With pre-cure 4 150HS9875C8%PS120 45 PS2558%PS120 yes Thicker Top 5 150 HS9875C 8% PS120 35 HS1048%PS120 no HS Control 6 150HS9875C8%PS120 35 HS1048%PS120 yes HS Control 7 150HS9875C8%PS120 75 HS1048%PS120 no HS Control 8 150HS9875C8%PS120 None yes Control Replicate 9 150HS9875C8%PS120 30 PS2558%PS120 yes Replicate 10 150HS9875C8%PS120 30 PS2558%PS120 yes Replicate Polymer and carbon dry coverage in g/cm , crosslinker as % wt with-respect-to polymer weight * Pre-cure implies a 10 minute heating step before the top layer was applied, a "no" implies that the sample was cured only after the last layer was applie With the imaging members of this invention, solid patches rolled up within one or two sheets. D max density was excellent and the background ran cleanly within a few impressions. Sensitivity was also much greater than observed for typical ablation plates. For example, exposures with as little as 600 mJ/cm 2 produced acceptable image density while plates containing only HS copolymer typically required more than twice that exposure. Referring again to TABLE I, several variations were examined. Control imaging members 1 and 8 revealed important clues to the underlying mechanism by which they function. These controls printed with a dark image against a gray (toned) background. The unexposed HS copolymer was capable of repelling ink but the high concentration of carbon particles at the surface interfered. The thin PDMS layer of the imaging members of Examples 2-4 provides a clean, higher surface-energy interface. However, it has been previously demonstrated that thin PDMS layers, on ink accepting supports, do tone. Thus, while either layer alone does not adequately repel ink, the combination does. Microscopic examination shows that imaged areas were not totally ablated during exposure and were not significantly dislodged on press. This suggests that the carbon-plus-HS copolymer truly functions as a physical and or chemical switch and is not just the result of the uncovered support carrying ink. In Examples 5-7, an HS copolymer was used in place of PDMS in the ink-repelling layer. These plates functioned but exhibited higher background toning than PDMS even when the surface HS copolymer layer was made thicker. The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

Claims: CLAIMS 1. A thermal imaging member comprising an ink-accepting support having thereon: (a) an ink-repellant, thermally sensitive imaging layer that comprises a photothermal conversion material and a thermally sensitive copolymer comprising one or more silicone segments and one or more thermally sensitive "hard" segments, said silicone segments comprising from about 50 to about 99 weight % of said copolymer, said imaging layer being capable of becoming ink-accepting upon exposure to thermal energy, and (b) an ink-repellant surface layer that is swellable in waterless ink solvents. 2. The imaging member of claim 1 wherein said photothermal conversion material is an infrared radiation absorbing material. 3. The imaging member of claim 2 wherein said photothermal conversion material comprises carbon black or is an infrared radiation absorbing dye. 4. The imaging member of claim 3 wherein said carbon black is a polymer-grafted or anionic surface-functionalized carbon black. 5. The imaging member of claim 1 wherein said support is a polyester or aluminum support. 6. The imaging member of claim 1 wherein said support is an on- press printing cylinder. 7. The imaging member of claim 1 wherein said thermally sensitive copolymer is represented by Structure I: H — S I wherein S represents a soft silicone segment, and H represents a hard segment, said S segments representing from about 50 to about 99 weight % of the total copolymer weight. 8. The imaging member of claim 1 wherein said thermally sensitive copolymer is represented by Structure II, III or IN: II III IN wherein m is from 5 to 10,000 and Ri and R 2 are independently substituted or unsubstituted alkyl group of 1 to 20 carbons, substituted or unsubstituted aryl groups of 6 to 10 carbon atoms in the aromatic ring, or ether sequences having repeating oxyalkylene groups, X is a linking group, R 3 is the same as Ri or R 2 , c(a+b) designates the size of the silicone and c designates the number of pendant groups. 9. The imaging member of claim 7 wherein said H segments are derived from an acrylate, methacrylate, acrylic acid, methacrylic acid, cyanoacrylate, styrene, α-methylstyrene, vinyl ester, vinyl halide, vinylidene halide, maleic anhydride, maleimide, vinyl pyridine, olefin or a mixture of any of these. 10. The imaging member of claim 1 wherein said thermally sensitive copolymer is represented by Structure N: N wherein AA and BB represent two difunctional monomers, r is at least 2, m is from 5 to 10,000 and Ri and R are independently substituted or unsubstituted alkyl group of 1 to 20 carbons, substituted or unsubstituted aryl groups of 6 to 10 carbon atoms in the aromatic ring, or ether sequences having repeating oxyalkylene groups. 11. The imaging member of claim 1 wherein said thermally sensitive copolymer is represented by Structure NI or Nil: Nil wherein X and Y represent terminal groups, AA, BB and AB are derived from two difunctional monomers, r is at least 2, m is from 5 to 10,000 and Ri and R 2 are independently substituted or unsubstituted alkyl group of 1 to 20 carbons, substituted or unsubstituted aryl groups of 6 to 10 carbon atoms in the aromatic ring, or ether sequences having repeating oxyalkylene groups. 12. The imaging member of claim 1 wherein said thermally sensitive copolymer is represented by Structure Nffl: Rl Ri -(—V- — X — Si- θ — Si-A- X- R 2 R2 VIII wherein N is derived from a cyclic ether, lactam, lactone, oxazoline, acetaldehyde or phthalaldehyde monomer, X is a linking group, r is at least 2, m is from 5 to 10,000, n is from 0 to 20, and Ri and R are independently substituted or unsubstituted alkyl group of 1 to 20 carbons, substituted or unsubstituted aryl groups of 6 to 10 carbon atoms in the aromatic ring, or ether sequences having repeating oxyalkylene groups. 13. The imaging member of claim 1 wherein said thermally sensitive copolymer is represented by Structure IX: IX wherein AA is a diisocyanate, BB is a diol, m is from 5 to 10,000, n is 0 to 3, r is at least 2, R \ and R 2 are methyl groups, and X is -CH 2 CH 2 CH 2 ΝH 2 . 14. The imaging member of claim 1 wherein said thermally sensitive copolymer is represented by Structure X: 15. The imaging member of claim 1 wherein said photothermal conversion material is present in an amount sufficient to provide an optical density of at least 0.3. 16. The imaging member of claim 1 wherein said thermally sensitive imaging layer has a dry thickness of from about 0.01 to about 10 μm, and said surface layer has a dry thickness of from about 0.1 to about 1 μm. 17. The imaging member of claim 16 wherein said thermally sensitive imaging layer has a dry thickness of from about 1 to about 5 μm, and said surface layer has a dry thickness of from about 0.2 to about 0.7 μm. 18. The imaging member of claim 1 further comprising an adhesion-promoting layer between said support and said imaging layer. 19. The imaging member of claim 1 wherein said surface layer comprises a crosslinked silicone polymer. 20. A method of imaging comprising: A) providing the imaging member of claim 1 , and B) imagewise ablating said surface layer of said imaging member using infrared radiation to provide a surface image. 21. The method of claim 20 wherein said imagewise exposing is carried out using an IR radiation emitting laser, or a thermoresistive head. 22. The method of claim 20 wherein said imaging member is provided in A by spraying a formulation for said imaging layer onto a cylindrical support. 23. A method of printing comprising: A) providing the imaging member of claim 1, B) imagewise ablating said surface layer of said imaging member using infrared radiation to provide a surface image, and C) inking said surface image and transferring said ink to a receiving material.

Inventors: BAILEY DAVID B, BURBERRY MITCHELL S, BAILEY, DAVID, B., BURBERRY, MITCHELL, S.
Applicants: KODAK POLYCHROME GRAPHICS CO, KODAK POLYCHROME GRAPHICS CO., LTD.
Application year: 2001
Main classification: B41M5
IPC codes: B41C1, B41M5, B41N1, C08G18, C08G81, G03F7