CA2442421C - Lithographic imaging with constructions having mixed organic/inorganic layers - Google Patents

Abstract

The effects of interfacial transition between organic and inorganic layers of a lithographic printing member are ameliorated by incorporating an inorganic component within the matrix of the organic layer. In a first aspect, a lithographic printing plate having adjacent organic and inorganic layers is fabricated by depositing a curable polymer, softening the polymer, and integrating an inorganic material therewith. The polymer is then cured to immobilize the integrated deposition material, and the desired inorganic layer is applied over the deposited inorganic material (and any exposed portions of the polymer). In a second aspect, a graded structure is built up on a substrate in successive deposition steps. Both polymer precursors and an inorganic filler material are deposited in stages, with each stage containing a desired ratio of polymer to filler.

Description

LITHOGRAPHIC IiHAGING ~nTITH CONSTRZ7CTIONS HAVING MIXED
ORGANICfINORGANIC LAYERS
BACI~CGROUND OE° THE INVENTION
This is a divisional of Canadian National Phase Patent Application Serial Number 2,290,595, filed March 17, 1999.
Field of the Invention The present invention relates to digital printing apparatus and methods, and more particularly to imaging of lithographic printing-plate constructions on- or off-press using digitally controlled laser output.
Description of the Related Art In offset lithography, a printable image is present on a printing member as a pattern of ink-accepting (oleophilic) and ink-rejecting (oleophobic) surface areas.
Once applied to these areas, ink can be efficiently transferred to a recording medium in the imagewise pattern with substantial fidelity. Dry printing systems utilize printing members whose ink-rejecting portions are sufficiently phobic to ink as to permit its direct application. Ink applied uniformly to tl~e printing member is transferred to the recording medium only in the imagewise pattern. Typically, the printing member first makes contact with a compliant intermediate surface ca:Lled a blanket cylinder which, in turn, applies the imac.~e to the paper or ether recording medium. In typical shee~~-fed press systems, the recording medium is pinned to an impression cylinder, which brings it into contact with the blanket cylinder.
In a wet lithographic system, the non-image areas are hydrophilic, and the necessary ink-repellency is

2 provided by an initial application of. a dampening (or "fountain") solution to the plate prior to irking. The ink-abhesive fountain solution prevents ink from adhering to the non-image areas, but does not affect the oleophilic character of the image areas.
To circumvent the cumbersome photographic development, plate-mounting and plate-registration operations that typify traditional printing technologies, practitioners have developed electronic alternatives that store the imagewise pattern in digital form and impress the pattern directly onto the plate. Plate-imaging devices amenable to computer control include various forms of lasers. For example, rJ.S. Patent Nos. 5,351,617 and 5,385,092 describe an ablative recording system that uses low-power laser discharges to remove, in an imagewise pattern, one or more layers of a lithographic printing blank, thereby creating a ready-to-ink printing member without the need for photographic development. In accordance with those systems, laser output is guided from the diode to the printing surface and focused. onto that surface (or, desirably, onto the layer most susceptible to laser ablation, which will generally lie beneath the surface layer).
U.S. Patents 5,783,364 and 5,807,658 describe a variety of lithographic plate configurations for use with such imaging apparatus. In general, the plate constructions include an inorganic layer (i.e., a metal, combination of meals, or a metal/non-metal compound) situated on an organic polymeric layer. The inorganic layer ablates in response to imaging (e.g., infrared, or "IR"") radiation. In one approach, the inorganic layer represents the topmost surface of the plate and accepts fountain solution, while the underlying polymeric layer accepts ink. In another

3 approach, the inorganic layer serves only a radiation-absorption (rather than a lithographic) function, with the underlying layer accepting ink and an overlying layer either rejecting ink or accepting fountain solution. Ablation of the inorganic layer by an imaging pulse generally weakens the topmost layer as well, and this, combined with disruption of its anchorage (due to disappearance of the ablated inorganic layer), renders the topmost layer easily removable in a post-imaging cleaning step. kith either of these two approaches, application of an imaging pulse to a point on the plate ultimately creates an image spot having an affinity for ink or an ink-abhesive fluid differing from that of unexposed areas, the pattern of such spots forming a lithographic plate image.
These types of plates can pose manufacturing challenges, as well as performance limitations, owing to the abrupt transition between an inorganic layer and an organic, polymeric layer. The divergent physical and chemical characteristics of such distinct layers can compromise their anchorage to one another - a critical performance requirement - as well as the durability of the inorganic layer. For example, because inorganic and organic materials typically have very different coefficients of thermal expansion and elastic moduli, even perfectly adhered inorganic layers may undergo failure (e.g., fracturing) due to temperature variations or the stress of plate manipulation and use. The different responses of two adjacent layers to an external condition can easily cause damage that would not occur in either layer by itself.
To improve interiayer anchorage, polymeric layers may be selected (or applied as intermediate coatings) based on chemical compatibility with inorganic materiai_. A
polymeric layer may also be pretreated (e. g., through plasma

-4-exposure) to modify the surface for greater interfacial compatibility with a subsequently applied inorganic layer.
These approaches, however, have limited utility in addressing the effects of transition between fundamentally different materials.
DESCRIPTION OF THE INVENTION
Brief Summary of the Invention In one aspect of the present invention, there is provided a method of printing comprising: a. providing a printing member fabricated according to steps comprising: i.
depositing, onto a substrate, a mixture of a polymer precursor and a filler material comprising an inorganic compound, the polymer precursor and the filler being present in a ratio; ii.
repeating step (i) with respect to the same substrate a plurality of times with an increasing amount of filler relative to the polymer precursor, thereby producing a graded structure with the amount of filler increasing away from the substrate; iii. curing the polymer precursor; and iv. applying a layer over a surface of the structure, the layer and the surface having different affinities for at least one printing liquid selected from the group consisting of ink and an abhesive fluid for ink, the layer, but not the structure, being subject to ablative removal by exposure to laser radiation; b. selectively exposing, in a pattern representing an image, the printing member to laser output so as to ablate selected portions of the layer, thereby directly producing an array of image features; c. applying ink to the member; and d. transferring the ink to a recording medium.
In a second aspect, there is provided a method of fabricating a lithographic printing plate, the method comprising: a. depositing, onto a substrate, a mixture of a polymer precursor and a filler material comprising an

-5-inorganic compound, the polymer precursor and the filler being present in a ratio; b. repeating step (a) with respect to the same substrate a plurality of times with a different ratio; c.
curing the polymer precursor; and d. applying a layer over a surface of the structure, the layer and the surface having different affinities for at least one printing liquid selected from the group consisting of ink and an abhesive fluid for ink, the layer, but not the structure, being subject to ablative removal by exposure to laser radiation.
The present invention reduces the abruptness of interfacial transition by altering the effective properties of the organic layer (to which the inorganic layer is applied) by incorporating an inorganic component within the matrix of the organic layer. One embodiment of the invention comprises a method of fabricating a lithographic printing plate having adjacent organic and inorganic layers. A first layer comprising a curable polymer is softened, and an inorganic material -- compatible with or, in some cases, compositionally identical to -- the soon-to-be-applied inorganic layer is deposited onto a surface of the softened polymer. The inorganic material overspreads the surface and integrates within the soft polymeric layer; at this point, it may be desirable to assist the migration of the inorganic material into the polymer (e.g., by charging the inorganic material and applying an opposite charge to a conductor underlying the polymer). The polymer is then cured to immobilize the integrated deposition material, thereby forming a composite, and the desired inorganic layer is applied over the deposited inorganic material (and any exposed portions of the polymer).
This second inorganic layer, and possibly the previously deposited inorganic material as well, is subject to ablative removal by exposure to laser radiation. The second inorganic layer and the 5a organic/inorganic composite have different affinities for ink and/or an ink-abhesive fluid. The inorganic layer may, for example, be a metallic inorganic material as disclosed in previously referenced U.S. patents 5,783,364 and 5,807,658. Despite the introduction of such an inorganic material within the matrix of the polymer, the natural affinity characteristics (e.g., oleophilicity) of the polymer may be retained. For example, while the inorganic phase may have a pronounced effect on the stiffness and heat-transport properties of the composite, thereby enhancing physical compatibility with a pure inorganic layer, it may not significantly affect surface energy (so that the composite retains the affinity for ink and/or an ink-abhesive fluid that characterized the original polymer).
The deposition material may fully cover the surface of the polymeric material, forming a continuous layer thereover, or may instead form an intermittent pattern over the surface. In the former case, imaging radiation may remove both the second inorganic layer and the deposition material from the polymer to expose the surface of the composite.
The polymer is generally chosen both for its lithographic affinity characteristics and also for its ability to be cured into a rigid, three-dimensional structure that permanently immobilizes the inorganic deposition material. Not suitable for the present invention are polymeric materials that exhibit a low glass-transition temperature (which permits repeated, temperature-dependent transitions between soft and rigid states) unless provided with crosslinking groups that facilitate permanent cure(and thereby defeat further phase transitions). In a preferred embodiment, the polymer comprises an acrylic polymer combined with a multifunctional acrylate monomer, which are 5b crosslinked following deposition of the inorganic material.
Acrylates, like many inorganic deposition materials, can be deposited under vacuum, permitting the er:tire fabrication process to be carried out in a single operation.
In general, the deposition material will be ink-receptive and the second layer hydrophilic. This need not be the case, however, nor do these affinity characteristics mandate a wet plate. For example, as described in U.S.
Patent No. 5,783,364, the second layer can underlie a topcoat having a different affinity characteristic.
Ablation of the secand layer disrupts the anchorage of the topcoat, rendering it easily removed in a post-imaging cleaning step to reveal the deposition material (and possibly the polymeric layer as well). The topcoat may be silicone or a fluoropolymer in the case of a dry plate, or a hydrophilic polymer if_ a polymer-topcoated wet plate is desired. Of course, application of a polymeric layer over the inorganic second layer raises the same compatibility issues resolved through use of the inorganic deposition material.
In a second embodiment, a graded structure is built up on a substrate in successive deposition steps.
Both polymer precursors and an inorganic filler material are deposited in stages, with each stage containing a desired ratio of polymer to filler. In a preferred embodiment, the proportion of filler increases in each sv~age, resulting in a concentration gradient with the amount of filler increasing away from the substrate. The polymer precursors may be cured after each stage of

-6-deposition, permanently immob~.li~ing the d~.stributaon of organic and inorganic material. A top layer is applied over a surface of the structure, the top layer and the surface having different affinities for ink and/or an ink-abhesive fluid. The top layer, but-not the underlying graded structure, may be subject to ablative removal by exposure to laser radiation.
The polymer precursor and the fuller material may be.
deposited as a vapor or as a liquid. In one embodiment, the precursor is an acrylic polymer combined with a multifunctional ao acrylate monomer, the curing step crosslinking the monomers with the polymer. ~nce again, the structure is typically oleophilic and the deposited inorganic layer hydrophilic, but the result need not be a wet plate.
In use, a printing plate in accordance with the invention is is selectively exposed, in a pattern representing an .image, to imaging radiation (emanating, for exa~tple, from one or more lasers whose output is scanned over the surface of the plate) so as to ablate selected portions of the inorganic layer and, possibly, exposed portions of the deposition material, thereby 2o directly producing an array of i.anage features. Ink is applied to the plate and transferred to a recording medium in the conventional fashion., As used herein, the term °'plate" or °'member" refers to any type of printing member or surface capable of recording an image defined by regions exhibiting 25 differential affinities for ink and/or fountain solution;
suitable.configurations include the traditional planar lithographic plates that are mounted on the plate cylinder of a printing press, but can also include cylinders (e. g., the roll surface of a plate cylinder), an endless belt, or other so arrangement.
Brief Description of the Drawings The foregoing discussion will be understood. more readily from the following detailed description of the invention, when 35 taken in conjunction with the, accompanying drawings, in which:
FIG. 1 is an enlarged sectional view of a lithographic plate having a mixed organ.ic/inorganic substrate, an

7 inorganic layer thereover, and. an optional topmost polymeric layer; and FIG. 2 is an enlarged sectional view of a lithographic plate having a graded organic/inorganic substrate and an inorganic layer thereover.
Detailed Description of the Preferred Embodiments Imaging apparatus suitable for use in conjunction with the present printing members includes at least one laser device that emits in the region of maximum plate responsiveness, i.e., whose lambda~aX closely approximates the wavelength region where the plate absorbs most strongly.
Specifications for lasers that emit in the near-IR region are fully described in the '617 and '092 patents; lasers emitting in other regions of the electromagnetic spectrum are well-known to those skilled in the art.
Suitable imaging configurations ar_e also set forth in detail in the '617 and '092 patents. Briefly, laser output can be provided directly to the plate surface via lenses or other beam-guiding components, or transmitted to the surface of a blank printing plate from a remotely sited laser using a fiber-optic cable. A controller and associated positioning hardware maintains the beam output at a precise orientation with respect to the plate surface, scans the output over the surface, and activates the laser at positions adjacent selected points or areas of the plate.
The controller responds to incoming image signals corresponding to the original document or picture being copied onto the plate to produce a precise negative or positive image of that original. The image signals are 7a stored as a bitmap data file on a computer. Such files rnay be generated by a raster image processor (RIP) or other suitable means. For example, a RIP can accept input dat<~ in page-description language, which defines all of the features required to be transferred onto the printing plate, or as a combination of page-description language and one or more image data files.

-The bitmaps are constructed to define the hue of the color as well as screen frequencies and angles~
The imaging apparatus can operate on its own, functioning solely as a platemaker, or can be incorporated directly iwto a s lithographic printing press. In the latter case, printing rnay commence immediately after application of the image to a blank plate, thereby reducin=~ press set-up time considerably. The imaging apparatus can ?be configured as a flatbed recorder or as a drum recorder, with the lithographic plate blank mounted to the interior or exterior cylindrical surface of the drum.
Obviously; the exterior drum design is more appropriate t~ use in situ, on a lithographic press, in which case the print cylinder itself constitutes the drum component of the recorder or plotter.
is In the drum configuration, the requisite relative motion between the laser beam and the plate is achieved by rotating the drum (and the plate mounted thereon) about its axis and moving the beam parallel to the rotation axis, thereby scanning the plate circumferentially so the image eagre~ws°° in the axial so direction. Alternatively, the beam can move parallel to the drum axis and, after each pass across the plate, increment angularly so that the image on the plate "grows'°
circumferentially. In both cases, after a complete scan by the beam, an image corresponding (positively or negatively) tce the zs original document or picture will have been applied to they surface of the plate.
In the flatbed configuration, the beam is drawn acre>ss either axis of the plate, and is indexed along the other atxis after each pass. ~f course, the requisite relative motion 3o between the beam and the plate may be produced by movement: of the plate rather than (or in addition toj~ m~vement of the beam.
Regardless of the manner in which t:he beam is scannE:d, it is generally preferabrLe (for on-press applications) to employ a plurality of lasers and guide the~.r outputs to a single w~°iting ss array. The writing array is then indexed, after completion of each pass across or a:Long the plate, a d:LStance determined by the number of beams eananating from the array, and by the _9_ desired resolution (i.e., the number of image points per unit length). Off-press applications, which can be designed to accommodate very rapid plate movement (e.g., through use of high-speed motors) and thereby utilize high laser pulse rates, s can fre9uently utilize a single laser as an imaging source.
Representative printing members in accordance with the present invention are illustrated in FIGS. 1 and 2. In FIG. 1, a printing plate 100 comprises a polymeric layer.102 and an inorganic layer 104. A deposition material 106 is integrated io within the matrix of polymer 102 and, covering all or much of the entire top surface thereof, provides a transition layer w 106s between layers 102 and 104. While material 106 may in fact be no more chemically compatible with the polymer of layer 102 than would be the inorganic material of layer 104, its physical integration within the matrix of layer 102 affords strong mechanical adhesion. As shown, the surface layer 106s extends into the matrix of polymer 102 ~as a series of projections or "nails." The firmly anchored layer 106s is chemically compatible with inorganic layer 104 and therefore zo exhibits substantial adhesion to this layer.
Plate 100 may be manufactured as follows. A substrate 110, which may be metal, plastic (e.g., polyester), paper, a pigment, or .some other durable graphic-arts material, accepts a coating of a polymeric material to form layer 102. This polymeric zs material may, for example, be an acrylic polymer soluble in methyl ethyl ketone (MEK) and/or other solvents. The acrylic polymer is combined with selected multifunctional acrylate monomers and coated (cast) from solvent onto substrate 110.
The multifunctional acrylate acts as a typical ester 3o plasticizes, promoting adhesion and lowering the softening (melting) point of the polymer mixture. The ACRYLOID acrylic polymers*H-44;~*H-72, and *H-82supplied by Rohm & Haas, represent suitable solvent-soluble acrylics;
dipentaerythritolpentaacrylate (e. g., the *SR-399 product as supplied by Sartomer) represents a suitable multifunctional acrylate.
* Trade-mark The substrate-borne acrylic mixture is heated to the softening point, whereupon deposition material 106 is applied to the exposed surface thereof. Material 106 may comprise one or more metals and/or metal alloys, intermetallics (i..e., two s or more metals combined iii ~ definite ratio), and/or compositions including one or more metals in combination with one or more nonmetals. Preferred nonmetals for such compositions include boron, carbon, nitroc;en, oxygen, fluorine, and silicon. Material 106 may also be a hard inorganic compound such as silicon dioxide. Tt should be stressed that the deposition material. can comprise a plLCrality of different substances fulfilling the foregoing criteria.
Material 106 may be applied by conventional. roll (web) coating, or by intermitaent-motion machin~a such as those as employed for glass coating. Alternatively, material 106 may be applied by a vacuum coating process such as vacuum evaporation, electron-beam (EB) evaporation, or sputtez:ing. The implementational details of such processes are well-characterized in the art. The deposition process may involve so . controlled cooling to withdraw the latent, heat resulting from condensation of the inorganic material from the vapor phase.
With the polymer 102 still in the softened state, it may be desirable to assist the migration of inorganic material 106 into polymer 102 in order to form the projections discussed zs above. One approach i~~.to statically charge the inorganic material 106 and apply an epposite charge to substrate 110.
Layer 102 is then cured, 'causing it to intensively crosslink and thereby ~"freeze°° the inorganic material 106 'to impart permanence. An acrylate layer 102 can be cured by :EB
o ' exposure. The cured~polymer exhibits substantially greater temperature resistance than the original, uncured. polymer (that is, fohowing cure, layer 102 can no longer be readily softened) and its solubility in the solvents) fr-om which it Was originally coated is substantially deirreased, i~ not 3s eliminated.
Layer 104 is then applied to the surface 106s (which typically includes exposed portions of layer 102, since it is generally not necessary to ensure complete: coverage of layE:r 102 by inorganic mater~..al 106), typically by vacuum deposition.
Lsayer 104 may, for example, be a very thin (50-500 1~, with 300 A preferred for titanium) layer of a metal. that: may or may not s de~relop a native oxide surface upon exposure to air. This layer ablates in response t~ IR radiation, and an a.mage is imposed onto the plate through patterned exposure. The metal or the oxide surface thereof exhibits hydmophilic properties that provide the basis for use of this construction as a .o lithographic printing plate. Imagewise r~:moval_, by ablation, of layer 104 exposes surface 106s; if ful.l.y covered by inorganic material 106,. this layer, too, stay be ablated to expose the surface of composite layer 102. The ultimately exposed layer is choserE for oleophilicity; accordingly, wh~_le ~s layer 104 accepts fountain solution, layer 102 and/or inorc;anic material 106 reject foicntain solution but accept ink.
The metal of lay~:r 104 in this embodiment is at least: one d-block (transition} metal, aluminum, ~.nd9~um or tin. In the case of a mixture, the metals are present as an alloy or an zo intermetallic. Again, the development, on more active metals, of an oxide layer can treats surface morphologies that improve hydrophilicity.
Alternatively, layer 104 array be a hard, durable, hydrophilic, metallic eLnorganic layer comprising a compound of as at least one metal with at least one non-metal, or a mixture of such compounds. ~nce again, layer 104 ablatively absorbs imaging radiation, and consequently is applied at a thickness of only 100-2000 A. The metal component of layer 104 in this form may be a d-block (transition) metal, an f-block so (lanthanide) metal, aluminum, indium or t:Ln, or a mixture of any of the foregoing (an ally or,.in cases in which a more definite composition exists, an intermetallic}. Preferred metals include titanium, zirconium, vanadium, niobium, tantalum, molybdenum and tungsten. The note-metal component may 35 be one or more of the 'p-block elements boron, carbon, nitrogen, oxygen and silicon. ~. metal/non-metal compound. in accordance herewith may or may not have a definite s-toichiometry, and may in some cases (e. g., Al-Si compounds) be an alloy.
Preferred metal/non-metal combinations include TiN, TiON, TiOX (where 0. 9 <- x <- 2. 0) , TiC, and TiClv.
If desired, an additional layer 112 can be applied over layer 104 to ach~_eve different affinity or physical characteristics. For example, layer 112 may be a silicone or fluoropolymer material that rejects ink, thereby transforming construc~:ion 100 into a dry plate. During imaging, ablation of ~_ayer 104 disrupts the anchorage of layer 112, rendering s_t easily removed in a post-imaging cleaning step to reveal the surface 106s or layer 102.
Useful materials for layer 112 and techniques of coating are disclosed in U.S. Patent Nos. 5,339,737 and Re. 35,512.
Basically, suitable silicone materials are applied using a wire-wound rod, then dried and heat-cured to produce a uniform coating depos~.ted at, for example, 2 g/m2.
A second plate embodiment is shown in FIG. 2. In this case, the construction 150 includes a graded layer :155 having a concentration of inorganic material 106 that increases with distance from substrate 110. Layer 155 is built up in successive stages as follows. A first coating 160 of polymeric material 102 is applied onto substrate _L10, preferably either by vapor condensation or by coating.
Particularly if layer i06 is deposited under vacuum, polymeric materials amenable to similar ~~eposition conditions may be preferred for layer 102, allowing consecutive layers to be built up in multiple depositions within. the same chamber or a linked series of chambers 7ander common vacuum. One suitable approach is detailed in U.S.
Patent Nos. 5,440,4460 4,954,3710 4,696,'719; 4,490,774;
4,647,818; 4,842,893 and 5,C32,46i. In accordance ~3 therewith, an acrylate monomer is applied as a vapor under vacuum. For example, the monomer may be flash evaporated and injected into a vacuum chamber, where it condenses onto the surface, The monomer is subsequently crosslinked by exposure to actinic (c;enerally ultraviolet, or UV) radiation or an EB source.
A related approach is described in U.S. Patent No.
5,260,095. In accordance with this patent, a.n acrylate monomer may be spread or coated onto a surface under vacuum, rather than condensed from a vapor. Again, the deposited monomer is crosslinked by UV or EB exposure.
Either of tYvese approaches may be used to apply layer 102 onto substrate 110. Moreover, their applicability is not limited to monomers; oligomers or larger polymer fragments or precursors can be applied in accordance with either technique, and subseauently crosslinked. Useful acrylate materials include conventional monomers and oligomers (monoacrylates, diacrylates, methacrylates, etc.), as described at cots. 8-10 of the '446 patent, as well as acrylates chemically tailored for particvalar application;.
Representative monoacrylates include isodecyl acrylate, lauryl acrylate, tridecyl acrylate, caprolactone acrylate, ethoxylated nonyl phenyl acrylate, isobornyl acrylate, tripropylene glycol methyl ether monoacrylate, and neopentyl glycol propoxylate methylether monoacrylate; useful diacrylates include 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, polyethylene glycol (200) diacrylate, tetraethylene glycol diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (600) diacrylate, propoxylated neopentyl glycol diacrylate,. the *IRR-214 product supplied by UCB Radcure (aliphatic diacrylate 13a monomer), propoxylated 1,6-hexanediol diacrylate, and ethoxylated 1,6-hexanediol diacrylate; and useful triacrylates include ~;rime-thylolpropane triacrylate (TMP'rA) and ethoxylated TMPTA.
Finally, acrylate-functional or other suitable resin coatings can be applied onto substrate 110 in routine fashion (under atmosprieric conditions), according to techniques well-known in the art. In one such approach, one or more acrylates are coated directly onto substrate 110 and later cured. In another approach, one or more acrylates is combined with a solvent (or solvents) and cast onto substrate 110, following which the solvent is evaporated and the deposited acrylate eventually cured. Volatile solvents, which. promote highly uniform application at low coating weights, are preferred.
Acrylate coatings can a3lso include non--ac:rylate functional s compounds soluble or dispersible into an acrylate.
Alternatives to <~crylate polymers a:re of course possible.
For example, it may be desirable to utilize an energetic organic material (such as an acetylene derivative, an azid.o or a2l.de derlVatlve, Or a nitro-funCtl.onal Compound) that Can.
to generate gas - typically explosively -- when the overlying inorganic layer 104 is heated.
After layer I60 of polymer 102 is applied but prior to curing, the inorganic filler 1t~6 is applied onto polymer 102 in a desired ratio relative to polymer 102.w In an uncured state, is polymer 102 accepts inorganic material 106 in a manner analogous to a_thermally softened layer. as described above.
Generally, it is not necessary to draw material 106 into layer 160, since layer 160 is generally quite thin. Particularly when applied by deposition techniques such as reactive zo sputtering, material 106 can form a pattern of patches or islands over the surface layer 160, which. is then cured aoe set forth above.
Application of layer 160 by vapor condensation affords greater control over the pattern of depov;ition. Polymer :L02 as can be applied under conditions that do not permit coalescrence and consequent film formation, thereby allowing creation of a discontinuous polymer layer. Inorganic maternal 106 is then deposited over the discontinuous pattern,. so that the organic layer is effectively bound within the inorganic material :rather than vice versa. As~discussed above,. application of mate:rial~
I06 from vapor .generally requires provi.s~i.on for removal of the latent heat of condensation.
Following deposition and curing of layer 160, the process is repeated for subsequent layers 162, 164, 166, which are 35 applied with d~.fferen'~ ratios. of inorganic material 106. to polymer material 102. Preferably, the proportion of inorganic material increases in each stage, resulting in a graded -~ 15-structure with the amount of inorganic material increasing away from substrate 110 as illustrated. The composite Layer 155 provides a gradual transition from an organic polymer to a mixed organic/inarganic material. The dispersed islands oj:
s inorganic material can be made to occur in °°units°' (grainsi, particles, crystals, etc.) that are one or more orders of magnitude smaller than solids traditionally dispersed in organic binders as pigments.
~iternatively, it is possible to apply layers 16~~I66 to without individually curing each layer before applying the next one, i.e., delaying curing until the entire sequence of layers has been applied. This approach may provide efficiency and processing benefits~
Following compl.e~tion of layer 155, layer 104 is appl;i.ed is as discussed above ande once again, an opi:.ional layer I12 can be added thereover.
It will therefore be seen that the foregoing techniques provide a basis for improved lithographic printing and superior plate constructions. The terms and expressions employed herein zo are used as terms of descriptian and not of limitation, and there is no intention~ in the use of such terms and expressions, of excluding any equivalents of the features shown and described or po~t~..ons ther~af, but it is recognized that various modifications are possible within the scope of the 25 ~lnventl0n Claimed.

Claims (31)

CLAIMS:

1. A method of printing comprising:
a. providing a printing member fabricated according to steps comprising:
i. depositing, onto a substrate, a mixture of a polymer precursor and a filler material comprising an inorganic compound, the polymer precursor and the filler being present in a ratio;
ii. repeating step (i) with respect to the same substrate a plurality of times with an increasing amount of filler relative to the polymer precursor, thereby producing a graded structure with the amount of filler increasing away from the substrate;
iii. curing the polymer precursor; and iv. applying a layer over a surface of the structure, the layer and the surface having different affinities for at least one printing liquid selected from the group consisting of ink and an abhesive fluid for ink, the layer, but not the structure, being subject to ablative removal by exposure to laser radiation;
b. selectively exposing, in a pattern representing an image, the printing member to laser output so as to ablate selected portions of the layer, thereby directly producing an array of image features;
c. applying ink to the member; and d. transferring the ink to a recording medium.

2. The method of claim 1 wherein the polymer precursor and the filler maternal are deposited as a vapor.

3. The method of claim 1 wherein the polymer precursor and the filler material are deposited as a liquid.

4. The method of claim 1 wherein the polymer precursor is cured by crosslinking to form a matrix.

The method of claim 4 wherein the polymer precursor comprises an acrylic polymer combined with a multifunctional acrylate monomer, the curing step crosslinking the monomers with the polymer.

6. The method of claim 1 wherein the surface is ink-receptive and the layer is hydrophilic.

7. The method of claim 6 wherein the layer comprises a compound of at least one metal with at least one non-metal.

8. The method of claim 7 wherein the at least one non-metal is selected from the group consisting of boron, carbon, nitrogen, silicon and oxygen.

9. The method of claim 7 wherein the layer comprises at least one of (i) a d-block transition metal, (ii) an f-block lanthanide, (iii) aluminum, (iv) indium and (v) tin.

10. The method of claim 9 wherein the layer comprises titanium.

11. The method of claim 10 wherein the layer comprises at least one oxide of titanium.

12. The method of claim 10 wherein the layer comprises titanium oxynitride.

13. The method of claim 1 wherein the filler comprises a compound of at least one metal with at least one non-metal.

14. The method of claim 13 wherein the at least one non-metal is selected from the group consisting of boron, carbon, fluorine, nitrogen, oxygen and silicon.

15. The method of claim 1 wherein the substrate comprises a pigment.

16. A method of fabricating a lithographic printing plate, the method comprising:
a. depositing, onto a substrate, a mixture of a polymer precursor and a filler material comprising an inorganic compound, the polymer precursor and the filler being present in a ratio;
b. repeating step (a) with respect to the same substrate a plurality of times with a different ratio;
c. curing the polymer precursor; and d. applying a layer over a surface of the structure, the layer and the surface having different affinities for at least one printing liquid selected from the group consisting of ink and an abhesive fluid for ink, the layer, but not the structure, being subject to ablative removal by exposure to laser radiation.

17. The method of claim 16 wherein step (a) is repeated a plurality of times with an increasing amount of filler relative to the polymer precursor, thereby producing a graded structure with the amount of filler increasing with distance from the substrate.

18. The method of claim 16 wherein the polymer precursor and the filler material are deposited as a vapor.

19. The method of claim 16 wherein the polymer precursor and the filler material are deposited as a liquid.

20. The method of claim 16 wherein the polymer precursor is cured by crosslinking to form a matrix.

21. The method of claim 20 wherein the polymer precursor comprises an acrylic polymer combined with a multifunctional acrylate monomer, the curing step crosslinking the monomers with the polymer.

22. The method of claim 16 wherein the surface is ink-receptive and the layer is hydrophilic.

23. The method of claim 22 wherein the layer comprises a compound of at least one metal with at least one non-metal.

24. The method of claim 23 wherein the at least one non-metal is selected from the group consisting of boron, carbon, nitrogen, silicon and oxygen.

25. The method of claim 23 wherein the layer comprises at least one of (i) a d-block transition metal, (ii) an f-block lanthanide, (iii) aluminum, (iv) indium and (v) tin.

26. The method of claim 25 wherein the layer comprises titanium.

27. The method of claim 16 wherein the layer comprises at least one oxide of titanium.

28. The method of claim 16 wherein the layer comprises titanium oxynitride.

29. The method of claim 16 wherein the filler comprises a compound of at least one metal with at least one non-metal.

30. The method of claim 29 wherein the at least one non-metal is selected from the group consisting of boron, carbon, fluorine, nitrogen, oxygen and silicon.

31. The method of claim 16 wherein the substrate comprises a pigment.