# Patent

## Title
Method for developing multilayer imageable elements

## Abstract

A method for forming an image by imaging and developing a multi-layer imageable element is disclosed. When thermally imageable, multi-layer imageable elements that have been imaged using stochastic screening are developed, a much smaller variation in dot percentage throughout the developer loading cycle is observed when a smaller initial charge of developer and a higher replenishment rate than are used in a conventional developing process are used. The developer is a solvent based developer with a pH below about 10.5. The developed imageable elements are useful as lithographic printing plates.

## Background
FIELD OF THE INVENTION
The invention relates to lithographic printing. In particular, this invention relates to a method for forming an image using multi-layer, positive-working, thermally imageable elements that are useful as lithographic printing plate precursors.
BACKGROUND OF THE INVENTION
In conventional or “wet” lithographic printing, ink receptive regions, known as image areas, are generated on a hydrophilic surface. When the surface is moistened with water and ink is applied, the hydrophilic regions retain the water and repel the ink, and the ink receptive regions accept the ink and repel the water. The ink is transferred to the surface of a material upon which the image is to be reproduced. Typically, the ink is first transferred to an intermediate blanket, which in turn transfers the ink to the surface of the material upon which the image is to be reproduced.
Imageable elements useful as lithographic printing plate precursors typically comprise an imageable layer applied over the hydrophilic surface of a substrate. The imageable layer includes one or more radiation-sensitive components, which may be dispersed in a suitable binder. Alternatively, the radiation-sensitive component can also be the binder material. Following imaging, either the imaged regions or the unimaged regions of the imageable layer are removed by a suitable developer, revealing the underlying hydrophilic surface of the substrate. If the imaged regions are removed, the precursor is positive-working. Conversely, if the unimaged regions are removed, the precursor is negative-working. In each instance, the regions of the imageable layer (i.e., the image areas) that remain are ink-receptive, and the regions of the hydrophilic surface revealed by the developing process accept water and aqueous solutions, typically a fountain solution, and repel ink.
Two types of screening are used in lithographic printing. In conventional halftone screening, sometimes called Amplitude Modulation (AM) screening, the halftone dots that together simulate the original image are arranged on a fixed geometric grid. By varying the size of the halftone dots the image can be simulated. In stochastic screening, sometimes called Frequency Modulated (FM) screening, the dots are same size but the number of dots and their location is varied to simulate the original image. The concept of stochastic screening is that halftone dots placed randomly, instead of in a fixed pattern, will not cause moiré patterns.
Imaging of the imageable element with ultraviolet and/or visible radiation is typically carried out through a mask, which has clear and opaque regions. Imaging takes place in the regions under the clear regions of the mask but does not occur in the regions under the opaque regions. If corrections are needed in the final image, a new mask must be made. This is a time-consuming process. In addition, dimensions of the mask may change slightly due to changes in temperature and humidity. Thus, the same mask, when used at different times or in different environments, may give different results and could cause registration problems.
Direct digital imaging, which obviates the need for imaging through a mask, is becoming increasingly important in the printing industry. Imageable elements for the preparation of lithographic printing plates have been developed for use with infrared lasers. Thermally imageable, mufti-layer elements are disclosed, for example, in Shimazu, U.S. Pat. No. 6,294,311, U.S. Pat. No. 6,352,812, and U.S. Pat. No. 6,593,055; Patel, U.S. Pat. No. 6,352,811; and Savariar-Hauck, U.S. Pat. No. 6,358,669, and U.S. Pat. No. 6,528,228; the disclosures of which are all incorporated herein by reference.
Although conventional developers and methods of processing work well with imaged thermally imageable multi-layer elements that have been imaged using conventional halftone screening, unacceptable variations in dot percentages are observed throughout the developer loading cycle when the imageable elements have been imaged using stochastic screening. The resultant tone, images are inconsistent and liable to fatten with plates processed later in the developer loading cycle. Thus, a need exists for a method for processing imageable elements that have been imaged using stochastic screening that does not produce unacceptable variations in dot percentages throughout the developer loading cycle.
SUMMARY OF THE INVENTION
It has been discovered that, when thermally imageable, multi-layer imageable elements that have been imaged using stochastic screening are developed, a much smaller variation in dot percentage throughout the developer loading cycle is obtained when a smaller initial charge of developer and a much higher replenishment rate than are used in a conventional developing process are used. Thus, the invention is a method for forming an image comprising the steps of:

    
    
        a) thermally imaging a multi-layer imageable element and forming an imaged imageable element comprising imaged and complementary unimaged regions;
        wherein:
        imaging is carried out using stochastic screening;
        the imageable element comprises a substrate, an underlayer over the substrate, and a top layer over the underlayer;
        the element comprises a photothermal conversion material;
        the top layer is substantially free of the photothermal conversion material;
        the top layer is ink receptive;
        before thermal imaging, the top layer is not removable by an alkaline developer;
        after thermal imaging, the imaged regions are removable by the developer; and
        the underlayer is removable by the developer; and
        b) developing the imaged imageable element with the developer and removing the imaged regions without substantially affecting the unimaged regions;

wherein:

        the developer is a solvent based developer;
        the developer has a pH below about 10.5, preferably below about 10.2; and
        a replenisher is added to the developer; and
        the volume of replenisher added to the developer is about 80 ml/m2 to about 400 ml/m2, preferably about 100 ml/m2 to about 300 ml/m2, of imaged element developed in the developer.
    
    


Preferably, the developer is sprayed onto the imaged imageable element during the developing step.
In another aspect of the invention, a volume of replenisher equal to about 0.1% to about 1.5%, especially about 0.25% to about 1.5%, of the volume of developer being used for developing is added to the developer per square meter of imaged element developed in the developer.


DETAILED DESCRIPTION OF THE INVENTION
Unless the context indicates otherwise, in the specification and claims, the terms binder, dissolution inhibitor, novolac resin, photothermal conversion material, organic solvent, and similar terms also include mixtures of such materials. Unless otherwise specified, all percentages are percentages by weight. Thermal imaging refers to imaging with a hot body, such as a thermal head, or with infrared radiation.
The mixture produced by the addition of a replenisher to the developer originally placed in the processor reservoir (the “original developer”) will be referred to as the developer. The material added to the original developer will be referred to as the replenisher, even though it may have the same composition as the original developer.
Developing the Imaged Imageable Elements
Thermally imageable, multi-layer imageable elements may be prepared and imaged as described below. Imaging produces an imaged element, which comprises a latent image of imaged regions and complementary unimaged regions. Developing, also referred to as processing, of the imaged element to form a printing plate converts the latent image to an image by removing the imaged regions, revealing the hydrophilic surface of the underlying substrate.
The developer penetrates and removes the imaged regions of the imageable layer and the underlying layer or layers without substantially affecting the complimentary unimaged regions. While not being bound by any theory or explanation, it is believed that image discrimination is based on a kinetic effect. The imaged regions of the top layer are removed more rapidly in the developer than the unimaged regions. Development is carried out for a long enough time to remove the imaged regions of the top layer and the underlying regions of the other layer or layers of the element, but not long enough to remove the unimaged regions of the top layer. Hence, the top layer is described as being “not removable” by, or “insoluble” in, the developer prior to imaging and the imaged regions are described as being “soluble” in, or “removable” by, the developer because they are removed, i.e. dissolved and/or dispersed, more rapidly in the developer than the unimaged regions. Typically, the underlayer is dissolved in the developer and the top layer is dissolved and/or dispersed in the developer.
High pH developers have been used for multi-layer positive-working imageable elements. However, it has been discovered that the imaged multi-layer positive working imageable elements can be developed in a solvent based developer. Solvent based developers, also known as negative developers, have been used to develop negative-working, rather than positive-working, imageable elements.
Solvent based alkaline developers typically have a pH below about 10.5, especially below 10.2 (measured at 25° C.). Solvent-based developers comprise water and an organic solvent or a mixture of organic solvents. They are typically free of silicates, alkali metal hydroxides, and mixtures of silicates and alkali metal hydroxides. The developer is a single phase. Consequently, the organic solvent or mixture of organic solvents must be either miscible with water or sufficiently soluble in the developer that phase separation does not occur. Optional components include anionic, nonionic and amphoteric surfactants (up to 3% on the total composition weight), and biocides (antimicrobial and/or antifungal agents).
The following solvents and mixtures thereof are suitable for use in solvent-based developers: the reaction products of phenol with ethylene oxide (phenol ethoxylates) and with propylene oxide (phenol propoxylates), such as ethylene glycol phenyl ether (phenoxyethanol); benzyl alcohol; esters of ethylene glycol and of propylene glycol with acids having six or fewer carbon atoms, and ethers of ethylene glycol, diethylene glycol, and propylene glycol with alkyl groups having six or fewer carbon atoms, such as 2-ethoxyethanol, 2-(2-epthoxy)ethoxyethanol, and 2-butoxyethanol. A developer that comprises phenoxyethanol is preferred. The developer typically comprises about 0.5 wt % to about 15 wt %, preferably about 3 wt %- to about 5 wt %, of the organic solvent or solvents, based on the weight of the developer. Typical commercially available solvent based developers include: AQUA-IMAGE® Developer, PRONEG® D501 Developer, MX 1725 Developer, MX 1587 Developer, 956′ Developer, 955 Developer, and SP200, all available from Kodak Polychrome Graphics, Norwalk, Conn., USA.
The imaged element can be developed in an immersion processor or, preferably, in a spray-on processor. In an immersion processor, the imaged imageable element is immersed in developer, and the developer circulated around the element. In contrast, in a spray-on processor, the developer is sprayed onto the imaged imageable element, but the element is not immersed in the developer. Especially preferred spray-on processors are the 85NS Processor and the Sword II Processor, manufactured by Gluntz and Jensen, Elkwood, Va., USA. Typical processing conditions are: processing speed, about 0.76 m/min to about 1.2 m/min (about 2.5 ft/min to about 4 ft/min), especially about 1.07 m/min (about 3.5 ft/min); and developer temperature, about 20° C. to about 25° C., especially about 22° C. to about 24° C.
In use, batches of developer are typically used for periods of several days to several weeks before they are replaced with fresh developer. During this time, the developer becomes loaded with components of the imageable layer that have been removed during development. The pH of the developer may decrease because the developer becomes loaded with components of the imageable layer that have been removed during the development process. In addition, some of the developer is removed from the developing, bath with the developed printing plates (drag-out).
In a conventional development process, the processor reservoir is filled with the original developer at the beginning of the cycle. Processor reservoirs may hold, for example, about 56.8 L (about 15 gallons) of developer. To maintain the activity and level of the developer, a replenisher, which may have the same composition as the original developer, is periodically added so that a balance between drag-out and feed-in is reached, and the amount of developer in the processor reservoir remains relatively constant.
Conventional replenishment rates are typically about 1 ml to about 3 ml of replenisher per square foot (about 10 to about 30 ml/m2) of imaged element developed, more typically about 2 ml of replenisher per square foot (about 20 ml/m2) of imaged element developed. Thus, in a conventional development process, a volume of replenisher equal to about 0.03% to 0.06% of the total volume of developer in the processor is added per square meter of imaged element developed in the developer.
However, it has been discovered that when thermally imageable, multi-layer imageable elements that have been imaged using stochastic screening are developed, a much smaller variation in dot percentage throughout the developer loading cycle is obtained when a smaller initial charge of developer and a much higher replenishment rate are used. A decrease in dot size variation throughout the developer loading cycle is also observed when elements that have been imaged by conventional halftone screening (AM screening) are developed under these conditions, but the method of the invention is most useful with elements that have been imaged using stochastic screening.
In the method of the invention, a smaller amount of original developer is used. The processor reservoir is only about 15% to about 80%, typically about 33% to about 80%, more typically about 60% to 75%, full. For example, only about 2 gallons (about 7 L) to about 12 gallons (about 45.2 L), typically about 5 gallons (about 18.9 L) to 12 gallons (about 45.2 L); more typically about 10 gallons (about 37.8 L), of developer is placed in an about 15 gallon (about 56.81 L) reservoir.
The replenisher preferably has the same composition as the original developer, but, if desired, the replenisher may-have a different composition than the original developer. A much higher rate of replenisher addition is used than in a conventional development process. A volume of replenisher equal to about 0.1% or more, generally about 0.1% to about 1.5%, of the volume of developer being used for processing (i.e., the amount of developer in the processor) is added to the developer per square meter of imaged element developed in the developer. About 8 ml to 40 ml of replenisher per square foot (about 80 ml/m2 to about 400 ml/m2), typically 10 ml to 30 ml of replenisher per square foot (about 100 ml/m2 to about 300 ml/m2), more typically about 20 ml per square foot (about 200 ml/m2) of imaged imageable developed in the developer is typically added to the developer in the processor. Thus, in the method of the invention, a volume of replenisher equal to about 0.25% to 1.5% of the total volume of developer in the processor is typically added to the developer per square meter of imaged element developed in the developer.
Following processing, the resulting printing plate is rinsed with water and dried. Drying may be conveniently carried out by infrared radiators or with hot air. After drying, the printing plate may be treated with a gumming solution comprising one or more water-soluble polymers, for example polyvinylalcohol, polymethacrylic acid, polymethacrylamide, polyhydroxyethylmethacrylate, polyvinylmethylether, gelatin, and polysaccharide such as dextrine, pullulan, cellulose, gum arabic, and alginic acid. A preferred material is gum arabic.
The developed and gummed plate can be baked to increase the press runlength of the plate. Baking can be carried out, for example, at about 220° C. to about 260° C. for about 5 minutes to about 15 minutes, or at a temperature of about 110° C. to about 130° C. for about 25 to about 35 min.
Thermally Imageable, Multi-Layer Imageable Elements
Thermally imageable, multi-layer imageable elements comprises a substrate, an underlayer, and a top layer. Others layers may be present. The elements also comprise a photothermal conversion material. They are disclosed, for example, in Shimazu, U.S. Pat. No. 6,294,311, U.S. Pat. No. 6,352,812; and U.S. Pat. No. 6,593,055; Patel, U.S. Pat. No. 6,352,811; and Savariar-Hauck, U.S. Pat. No. 6,358,669, and U.S. Pat. No. 6,528,228; as well as U.S. Pat. application 09/638,556, filed Aug. 14, 2000, the disclosures of which are all incorporated herein by reference. Commercially available thermally imageable, multi-layer imageable elements include the Sword Excel (Kodak Polychrome Graphics, Norwalk, Conn., USA).
Substrate
The substrate comprises a support, which may be any material conventionally used to prepare imageable elements useful as lithographic printing plates. The support is preferably strong, stable and flexible. It should resist dimensional change under conditions of use so that color records will register in a full-color image. Typically, it can be any self-supporting material, including, for example, polymeric-films such as polyethylene terephthalate film, ceramics, metals, or stiff papers, or a lamination of any of these materials. Metal supports include aluminum, zinc, titanium, and alloys thereof.
Typically, polymeric films contain a sub-coating on one or both surfaces to modify the surface characteristics to enhance the hydrophilicity of the surface, to improve adhesion to subsequent layers, to improve planarity of paper substrates, and the like. The nature of this layer or layers depends upon the substrate and the composition of subsequent coated layers. Examples of subbing layer materials are adhesion-promoting materials, such as alkoxysilanes, aminopropyltriethoxysilane, glycidoxypropyltriethoxysilane and epoxy functional polymers, as well as conventional subbing materials used on polyester bases in photographic films.
The surface of an aluminum support may be treated by techniques known in the art, including physical graining, electrochemical graining, chemical graining, and anodizing. The substrate should be of sufficient thickness to sustain the wear from printing and be thin enough to wrap around a cylinder in a printing press, typically about 100 μm to about 600 μm. Typically, the substrate comprises an interlayer between the aluminum support and the underlayer. The interlayer may be formed by treatment of the aluminum support with, for example, silicate, dextrine, hexafluorosilicic acid, phosphate/fluoride, polyvinyl phosphonic acid (PVPA) or vinyl phosphonic acid copolymers.
The back side of the support (i.e., the side opposite the underlayer and top layer) may be coated with an antistatic agent and/or a slipping layer or matte layer to improve handling and “feel” of the imageable element.
Underlayer
The underlayer comprises a polymeric material that is preferably soluble in the developer to prevent sludging of the developer. In addition, the polymeric material is preferably insoluble in the solvent used to coat the top layer so that the top layer can be coated over the underlayer without dissolving the underlayer. Other ingredients, such as resole resins, added copolymers, photothermal conversion materials, and surfactants, may also be present in the underlayer.
The underlayer comprises a polymeric material that is preferably soluble in the developer. In addition, the polymeric material is preferably insoluble in the solvent used to coat the imageable layer so that the imageable layer can be coated over the underlayer without dissolving the underlayer. Useful polymeric materials include carboxy functional acrylics., vinyl acetate/crotonate/vinyl neodecanoate copolymers, styrene maleic anhydride copolymers, phenolic resins, maleated wood rosin, and combinations thereof. Underlayers that provide resistance both to fountain solution and aggressive washes are disclosed: in Shimazu, U.S. Pat. No. 6,294,311, incorporated herein by reference.
Particularly useful polymeric materials are polyvinylacetals and copolymers that comprise N-substituted maleimides, especially N-phenylmaleimide; methacrylamides, especially methacrylamide; and acrylic and/or methacrylic acid, especially methacrylic acid. The preferred polymeric materials of this type are copolymers of N-phenylmaleimide, methacrylamide, and methacrylic acid, more preferably those that contain about 25 to about 75 mol %, preferably about 35 to about 60 mol % of N-phenylmaleimide; and about 50 mol %, preferably about 15 to about 40 mol % of methacrylamide; and about 5 to about 30 mol %, preferably about 10 to about 30 mmol %, of methacrylic acid. Other hydrophilic mono me rs, such as hydroxyethyl methacrylate, may be used in place of some or all of the methacrylamide. Other alkaline soluble monomers, such as acrylic acid, may be used in place of some or all of the methacrylic acid. These polymeric materials are soluble in a methyl lactate/methanol/dioxolane (15:42.5:42.5 wt %) mixture, which can be used as the coating solvent for the underlayer. However, they are poorly soluble in solvents such as acetone and toluene, which can be used as solvents to coat the imageable layer on top of the underlayer without dissolving the underlayer.
These polymeric materials can be prepared by methods, such as free radical polymerization, well known to those skilled in the art. One or more other polymeric materials may also be present in the combination. Preferred other polymeric materials, when present, are novolac resins.
Top Layer
The top layer is over the underlayer. The top layer becomes soluble or dispersible in the developer following thermal exposure. It typically comprises an ink-receptive polymeric material, known as the binder, and a dissolution inhibitor. Alternatively, or additionally, the polymeric material comprises polar groups and acts as both the binder and dissolution inhibitor.
Any top layer used in multi-layer thermally imageable elements may be used with in the imageable elements of the invention. These are described for example in Savariar-Hauck, U.S. Pat. No. 6,3358,669, the disclosure of which is incorporated herein by reference, and U.S. Pat. application 09/638,556, filed Aug. 14, 2000, the disclosure of which is incorporated herein by reference.
Preferably, the binder in the top layer is a light-stable, water-insoluble, developer-soluble, film-forming phenolic resin. Phenolic resins have a multiplicity of phenolic hydroxyl groups, either on the polymer backbone or on pendent groups. Novolac resins, resol resins, acrylic resins that contain pendent phenol groups, and polyvinyl phenol resins are preferred phenolic resins. Novolac resins are more preferred. Novolac resins are commercially available and are well known to those skilled in the art. They are typically prepared by the condensation reaction of a phenol, such as phenol, m-cresol, o-cresol, p-cresol, etc, with an aldehyde, such as formaldehyde, paraformaldehyde, acetaldehyde, etc. or a ketone, such as acetone, in the presence of an acid catalyst. Typical novolac resins include, for example, phenol-formaldehyde resins, cresol-formaldehyde resins phenol-cresol-formaldehyde resins, p-t-butylphenol-formaldehyde resins, and pyrogallol-acetone resins. Particularly useful novolac resins are prepared by reacting m-resol, mixtures of m-cresol and p-cresol, or phenol with formaldehyde using conventional conditions.
A solvent soluble novolac resin is one that is sufficiently soluble in a coating solvent to produce a coating solution that can be coated to produce a top layer. In some cases, it may be desirable to use a novolac resin with the highest weight average molecular weight that maintains its solubility in common coating solvents, such as acetone, tetrahydrofuran, and 1-methoxypropan-2-ol. Top layers comprising novolac resins, including for example m-cresol only novolac resins (i.e. those that contain at least about 97 mol % m-cresol) and m-cresol/p-cresol novolac resins that have up to 10 mol % of p-cresol, having a weight average molecular weight of about 10,000 to at least about 25,000, may be used. Top layers comprising m-cresol/p-cresol novolac resins with at least 10 mol % p-cresol, having a weight average molecular weight of about 8,000 to about 25,000, may also be used. In some instances, novolac resins prepared by solvent condensation may be desirable.
The top layer typically comprises a dissolution inhibitor, which functions as a solubility-suppressing component for the binder. Dissolution inhibitors have polar functional groups that are believed to act as acceptor sites for hydrogen bonding with the hydroxyl groups present in the binder. The acceptor sites comprise atoms with high electron density, preferably selected from electronegative first row elements, especially carbon, nitrogen, and oxygen. Dissolution inhibitors that are soluble in the developer are preferred.
Useful polar groups for dissolution inhibitors include, for example, diazo groups; diazonium groups; keto groups; sulfonic acid ester groups; phosphate ester groups; triarylmethane groups; onium groups, such as sulfonium, iodonium, and phosphonium; groups in which a nitrogen atom is incorporated into a heterocyclic ring; and groups that contain a, positively charged atom, especially a positively charged nitrogen atom, typically a quaternized nitrogen atom, i.e., ammonium groups. Compounds that contain a positively charged (i.e., quaternized) nitrogen atom useful as dissolution inhibitors include, for example, tetraalkyl ammonium compounds, and quaternized heterocyclic compounds such as quinolinium compounds, benzothiazolium compounds, pyridinium compounds, and imidazolium compounds. Compounds containing other polar groups, such as ether, amine, azo, nitro, ferrocenium, sulfoxide, sulfone, and disulfone may also be useful as dissolution inhibitors. The dissolution inhibitor may be a monomeric and/or polymeric compound that comprises an diazobenzooquinone moiety and/or a diazonaphthoquinone moiety.
A preferred group of dissolution inhibitors are triarylmethane dyes, such as ethyl violet, crystal violet, malachite green, brilliant green, Victoria blue B, Victoria blue R, Victoria blue BO, BASONYL® Violet 610, and D11 (PCAS, Longjumeau, France). These compounds can also act as contrast dyes, which distinguish the unimaged regions from the imaged regions in the developed imageable element.
When a dissolution inhibitor is present in the top layer, it typically comprises at least about 0.1 wt %, typically about 0.5 wt % to about 30 wt %, preferably about 1 wt % to 15 wt %, based on the dry weight of the layer.
Alternatively, or additionally, the polymeric material in the top layer can comprise polar groups that act as acceptor sites for hydrogen bonding with the hydroxy groups present in the polymeric material and, thus, act as both the polymeric material and dissolution inhibitor. The level of derivatization should be high enough that the polymeric material acts as a dissolution inhibitor, but not so high that, following the thermal imaging, the polymeric material is not soluble in the developer. Although the degree of derivatization required will depend on the nature of the polymeric material and the nature of the moiety containing the polar groups introduced into the polymeric material, typically about 0.5 mol % to about 5 mol %, preferably about 1 mol % to about 3 mol %, of the hydroxyl groups will be derivatized. Derivatization of phenolic resins with compounds that contain the diazonaphthoquinone moiety is well known and is described, for example, in West, U.S. Pat. Nos. 5,705,308, and 5,705,322.
One group of polymeric materials that comprise polar groups and function as dissolution inhibitors are derivatized phenolic polymeric materials in which a portion of the phenolic hydroxyl groups have been converted to sulfonic acid esters, preferably phenyl sulfonates or p-toluene sulfonates. Derivatization can be carried out by reaction of the polymeric material with, for example, a sulfonyl chloride such as p-toluene sulfonyl chloride in the presence of a base such as a tertiary amine. A useful material is a novolac resin in which about 1 mol % to 3 mol %, preferably about 1 mol % to about 2.5 mol %, of the hydroxyl groups have been converted to phenyl sulfonate or p-toluene sulfonate (tosyl) groups.
Photothermal Conversion Material
Imageable elements that are to be imaged with infrared radiation typically comprise an infrared absorber, known as a photothermal conversion material. Photothermal conversion materials absorb radiation and convert it to heat. Although a photothermal conversion material is not necessary for imaging with a hot body, imageable elements that contain a photothermal conversion material may also be imaged with a hot body, such as a thermal head or an array of thermal heads.
The photothermal conversion material may be any material that can absorb radiation and convert it to heat. Suitable materials include, for example, dyes and pigments. Suitable pigments include, for example, carbon black, Heliogen Green, Nigrosine Base, iron (III) oxide, manganese oxide, Prussian Blue, and Paris blue. Because of its low cost and wide absorption bands that allow it to be used with imaging devices having a wide range of peak emission wavelengths, one particularly useful pigment is carbon black. The size of the pigment particles should not be more than the thickness of the layer that contains the pigment. Preferably, the size of the particles will be half the thickness of the layer or less.
To prevent sludging of the developer by insoluble material, photothermal conversion materials that are soluble in the developer are preferred. The photothermal conversion material may be a dye with the appropriate absorption spectrum and solubility. Dyes, especially dyes with a high extinction coefficient in the range of 750 nm to 1200 nm, are preferred. Examples of suitable dyes include dyes of the following classes: methine, polymethine, arylmethine, cyanine, hemicyanine, streptocyanine, squarylium, pyrylium, oxonol, naphtho-quinone, anthraquinone, porphyrin, azo, croconium, triarylamine, thiazolium, indolium, oxazolium, indocyanine, indotricarbocyanine, oxatricarbocyanine, phthalocyanine, thiocyanine, thiatricarbocyanine, merocyanine, cryptocyanine, naphthalocyanine, polyaniline, polypyrrole, polythiophene, chalcogeno-pyryloarylidene and bis(chalcogenopyrylo)polymethine, oxyindolizine, pyrazoline azo, and oxazine classes. Absorbing dyes are disclosed in numerous publications, for example, Nagasaka, EP 0,823,327; DeBoer, U.S. Pat. No. 4,973,572; Jandrue, U.S. Pat. No. 5,244,771; Patel, U.S. Pat. No. 5,208,135; and Chapman, U.S. Pat. No. 5,401,618. Other examples of useful absorbing dyes include: ADS-830A and ADS-1064 (American Dye Source, Montreal, Canada), EC2117 (FEW, Wolfen, Germany), Cyasorb IR 99 and Cyasorb IR 165 (Glendale Protective Technology), Epolite IV-62B and Epolite III-178 (Epoline), SpectralR 830A and SpectralR 840A (Spectra Colors), as well as IR Dye A, and IR Dye B, whose structures are shown below. 




To prevent ablation during imaging with infrared radiation, the top layer is substantially free of photothermal conversion material. That is, the photothermal conversion material in the top layer, if any, absorbs less than about 10% of the imaging radiation, preferably less than about 3% of the imaging radiation, and the amount of imaging radiation absorbed by the top layer, if any, is not enough to cause ablation of the top layer.
The amount of infrared absorber is generally sufficient to provide an optical density of at least 0.05, and preferably, an optical density of from about 0.5 to at least about 2 to 3 at the imaging wavelength. As is well known to those skilled in the art, the amount of compound required to produce a particular optical density can be determined from the thickness of the underlayer and the extinction coefficient of the infrared absorber at the wavelength used for imaging using Beer's law. When the infrared absorber is present in the underlayer, infrared absorber typically comprises about 0.1 to 20% by weight, more preferably about 0.5 to 10% by weight, of the underlayer, based on the total weight of the underlayer.
Other Layers
When an absorber layer is present, it is between the top layer and the underlayer. The absorber layer preferably consists essentially of the infrared absorber and, optionally, a surfactant. It may be possible to use less of the infrared absorber if it is present in a separate absorber layer. The absorber layer preferably has a thickness sufficient to absorb at least 90%, preferably at least 99%, of the imaging radiation. Typically, the absorber layer has a coating weight of about 0.02 g/m2 to about 2 g/m2, preferably about 0.05 g/m2 to about 1.5 g/m2. Elements that comprise an absorber layer are disclosed in Shimazu, U.S. Pat. No. 6,593,055, the disclosure of which is incorporated herein by reference.
To further minimize migration of the infrared absorber from the underlayer to the top layer during manufacture and storage of the imageable element, the element may comprise a barrier layer between the underlayer and the top layer. The barrier layer comprises a polymeric material that is soluble in the developer. If this polymeric material is different from the polymeric material in the underlayer, it is preferably soluble in at least one organic solvent in which the polymeric material in the underlayer is insoluble. A preferred polymeric material for the barrier layer is polyvinyl alcohol. When the polymeric material in the barrier layer is different from the polymeric material in the underlayer, the barrier layer should be less than about one-fifth as thick as the underlayer, preferably less than a tenth of the thickness of the underlayer.
Preparation of the Imageable Element
The imageable element may be prepared by sequentially applying the underlayer over the hydrophilic surface of the substrate; applying the absorber layer or the barrier layer if present, over the underlayer; and then applying the top layer using conventional techniques.
The terms “solvent” and “coating solvent” include mixtures of solvents. These terms are used although some or all of the materials may be suspended or dispersed in the solvent rather than in solution. Selection of coating solvents depends on the nature of the components present in the various layers.
The underlayer may be applied by any conventional method, such as coating or lamination. Typically the ingredients are dispersed or dissolved in a suitable coating solvent, and the resulting mixture coated by conventional methods, such as spin coating, bar coating, gravure coating, die coating, or roller coating. The underlayer may be applied, for example, from mixtures of methyl ethyl ketone, 1-methoxypropan-2-ol, butyrolactone, and water; from mixtures of diethyl ketone, water, methyl lactate, and butyrolactone; and from mixtures of diethyl ketone, water, and methyl lactate.
When neither a barrier layer nor an absorber layer is present, the top layer is coated on the underlayer. To prevent the underlayer from dissolving and mixing with the top layer, the top layer should be coated from a solvent in which the underlayer layer is essentially insoluble. Thus, the coating solvent for the top layer should be a solvent in which the components of the top layer are sufficiently soluble that the top layer can be formed and in which any underlying layers are essentially insoluble. Typically, the solvents used to coat the underlying layers are more polar than the solvent used to coat the top layer. The top layer may be applied, for example, from diethyl ketone, or from mixtures of diethyl ketone and 1-methoxy-2-propyl acetate. An intermediate drying step, i.e., drying the underlayer, if present, to remove coating solvent before coating the top layer over it, may also be used to prevent mixing of the layers.
Alternatively, the underlayer, the top layer or both layers may be applied by conventional extrusion coating methods from a melt mixture of layer components. Typically, such a melt mixture contains no volatile organic solvents.
Imaging of the Imageable Elements
The element may be thermally imaged with a laser or an array of lasers emitting modulated near infrared or infrared radiation in a wavelength region that is absorbed by the imageable element. Infrared radiation, especially infrared radiation in the range of about 800 nm to about 1200 nm, is typically used for imaging. Imaging is conveniently carried out with a laser emitting at about 830 nm, about 1056 nm, or about 1064 nm. Suitable commercially available imaging devices include image setters such as the CREO® Trendsetter (CREO, Burnaby, British Columbia, Canada), the Screen PlateRite Model 4300, Model 8600, and Model 8800 (Screen, Rolling Meadows, Chicago, Ill., USA), and the Gerber Crescent 42T (Gerber Systems, South Windsor, Conn., USA).
Alternatively, the imageable element may be thermally imaged using a hot body, such as a conventional apparatus containing a thermal printing head. A suitable apparatus includes at least one thermal head but would usually include a thermal head array, such as a TDK Model No. LV5416 used in thermal fax machines and sublimation printers the GS618-400 thermal plotter (Oyo Instruments, Houston, Tex., USA), or the Model VP-3500 thermal printer (Seikosha America, Mahwah, N.J., USA).
Industrial Applicability
The method of the invention produces an image that is useful as a lithographic printing plate. After the imageable element has been imaged and developed to form a lithographic printing plate, printing can then be carried out by applying a fountain solution and then lithographic ink to the image on its surface. The fountain solution is taken up by the surface of the hydrophilic substrate revealed by the imaging and development process, and the ink is taken up by the regions not removed by the development process. The ink is then transferred to a suitable receiving material (such as cloth, paper, metal, glass or plastic) either directly or indirectly using an offset printing blanket to provide a desired impression of the image thereon.
EXAMPLES
Glossary


    956 Developer Solvent based (phenoxyethanol) developer (Kodak Polychrome Graphics, Norwalk, Conn., USA)
    CREO® Trendsetter 3230 Commercially available platesetter, using Procom Plus software and operating at a wavelength of 830 nm (Creo Products, Burnaby, BC, Canada)
    Sword Excel Thermally sensitive, positive working, multi-layer, printing plate precursor (Kodak Polychrome Graphics, Norwalk, Conn., USA).
    Sword II Processor Spray-on type processor, 850 mm width (Glunz and Jensen, Elkwood, Va., USA)


Comparative Example 1
A Sword Excel printing plate precursor was imaged with 830 nm radiation, using an internal test pattern on a CREO® 3230 Trendsetter at an exposure energy of 120 mJ/cm2 (250 rpm and 13.25 W laser power). The internal test pattern contained 1, 2, 3, 5, 10, 15, 20, 30, 40, 45, 50, 55, 60, 70, 80, 85, 90, 95, 98, 99, 99.5 and 100% dot images. Imaging was carded out using CREO® Staccato (FM) 10 micron and 20 micron screen rulings.
The resulting imaged precursor was developed using an 850 Sword 11 Plate Processor in the following configuration 956 Developer; 20 inch, 15 micron wound developer filter (Stonehand, Denver, Colo., USA); two plush rollers in the developer tank; processing speed, 1.07 m/min (3.5 ft/min); initial charge of developer, 56.8 L (15 gallons); developer replenishment rate, 21.5 ml/m2 (2 ml/ft2) of imaged precursor developed in the developer. The 956 Developer was used as the replenisher. The processor had been recently cleaned and new developer and filters installed. The resolution of the resulting printing plate was measured using an X-Rite 528 densitometer (CannonDirect, Bethel, Ohio, USA).
After the imaged precursor had been developed, 9.3 M2 (100 ft2) increments of imaged (as above, but with a solid, 100% exposure pattern, in AM mode) Sword Excel precursor were developed through the processor so that the developer was subjected to dissolving and dispersing the top layer and underlayer composition in a manner seen in a pre-press environment. After each about 9.3 m2 (100 ft2) increment, the pH of the developer was measured.
After about 140 m2 (1500 ft2) of imaged precursor had been developed, another Sword Excel precursor was imaged as above using CREO® Staccato 10 micron and 20 micron screen rulings, developed, and its resolution measured.
Further about 9.3 m2 (100 ft2) increments of AM imaged precursor were developed. After about 205 m2 (2200 ft2) of imaged precursor had been developed, another Sword Excel precursor was imaged as above using the CREO® Staccato 10 micron and 20 micron screen rulings, developed, and its resolution measured. The pH readings of the developer during the developer cycle are shown in Table 1. Resolution for the resulting printing plates is shown in Table 2.









TABLE 1





Area processed (ft2)
pH
Temperature (° C.)a

















0
9.75
21.6


100
9.72
21.6


200
9.70
21.5


300
9.69
21.6


400
9.67
22.3


500
9.62
21.9


600
9.60
22.2


700
9.59
22.3


800
9.59
22.4


900
9.58
22.5


1000
9.57
22.5


1100
9.58
22.7


1200
9.57
22.9


1300
9.56
23.2


1400
9.56
23.6


1500
9.56
23.1


1600
9.52
22.6


1700
9.49
22.1


1800
9.48
22.0


1900
9.46
22.1


2000
9.42
22.7


2100
9.37
23.1


2200
9.34
23.2





aTemperature at which the pH was measured. 






The developer shows an unacceptable downward drift in pH (0.41 unit) over the lifetime of the developer.










TABLE 2









10 Micron
20 Micron



Staccato Screen
Staccato Screen









Theoretical dot
Area Processed (ft2)














(%)
0
1500
2200
0
1500
2200





50
47
48
52
46
48
50


60
56
57
62
56
57
59









With a 10 micron FM screen ruling, the observed dot percentages vary throughout the cycle by 5 and 6%. With a 20 micron FM screen ruling, the observed dot percentages vary throughout the cycle by 3 and 4%. This would be unacceptable in a typical pre-press environment.
Example 1
The procedure of example 1 was repeated except that:

    
    
        a) the initial charge of 956 Developer was 37.8 L (10 gallons).
        b) the volume of replenisher added to the developer was 215 ml/ml2 (20 ml/ft2) of imaged precursor developed in the developer. The 956 Developer was used as the replenisher.
        c) the internal test pattern contained 1, 5, 10, 20, 50, 70, 99% dot images us ing CREO® Staccato (FM) 10 micron and 20 micron screen rulings, and a test pattern containing 1, 20, 50, 70, and 98% dot images using a 240 line pairs per inch (lpi) round dot AM screen ruling.
        d) after processing was completed, the processor was recharged with new 956 Developer and another precursor was imaged, developed, and measured.
    
    


The pH readings of the developer during the developer loading cycle are shown in Table 3. The resolution readings using the Staccato 10 micron and 20 micron screen rulings are shown in Table 4. The resolution readings using the 240 line pairs per inch (lpi) round dot AM screen ruling is shown in Table 5.









TABLE 3





Area processed (ft2)
pH
Temperaturea (° C.)

















0
9.70
23.8


100
9.65
23.8


200
9.63
23.8


300
9.60
23.8


400
9.57
23.8


500
9.60
24.3


600
9.59
24.1


700
9.58
23.0


800
9.59
23.3


900
9.59
24.3


1000
9.58
23.9


1100
9.57
24.1


1200
9.57
24.1


1300
9.57
23.8


1400
9.57
24.2


1500
9.58
24.0


1600
9.57
23.8


1700
9.59
22.9


1800
9.60
22.9


1900
9.58
23.2


2000
9.56
23.4


2100
9.56
23.3


2200
9.56
23.2


2300
9.55
23.0


2400
9.55
22.9


2500
9.55
23.4


2600
9.57
23.2


2700
9.58
23.1


2800
9.57
23.8


2900
9.56
23.4


3000
9.55
23.1





aTemperature at which the pH was measured. 






The downward drift in pH (0.15 unit) over the lifetime of the developer is acceptable.









TABLE 4









Area Processed (ft2)

















Theoretical dot (%)
0
300
400
500
1000
1500
2000
2200
3000
0a












10 Micron Staccato Screen

















 1
0
0
1
1
1
1
2
2
1
0


 5
4
5
5
5
5
4
5
4
4
4


10
10
10
9
11
9
10
11
11
11
10


20
19
19
21
20
20
20
21
21
20
19


50
49
49
51
49
51
50
52
50
51
49


70
69
69
69
70
71
70
72
72
71
69


99
99
99
99
98
99
99
99
99
99
99









20 Micron Staccato Screen

















 1
1
1
1
1
1
1
2
2
2
1


 5
4
4
4
4
5
6
5
5
5
5


10
9
9
10
9
10
10
10
10
10
10


20
19
19
20
19
20
20
20
20
21
19


50
49
49
50
49
50
51
51
50
51
49


70
69
69
71
69
68
70
71
71
71
69


99
99
99
99
99
98
99
99
98
99
99





aNew Developer 















TABLE 5









240 lpi, round dot AM screen ruling



Area Processed (ft2)

















Theoretical dot (%)
0
300
400
500
1000
1500
2000
2200
3000
0a




















1
2
2
2
2
2
2
2
2
2
2


20
20
21
21
21
20
20
21
21
20
21


50
50
50
50
51
51
51
51
51
50
50


70
71
71
70
70
70
71
71
71
71
70


98
99
98
99
99
98
99
98
98
99
98





aNew Developer 






Using a 10 micron FM screen ruling, the actual dot percentages vary throughout the developer loading cycle up to 3%. Using a 20 micron FM screen ruling, the actual dot percentages vary throughout the developer loading cycle up to 3%. This variation is acceptable in a typical pre-press environment. The images produced from AM screening under the method of the invention are excellent; having only 1% variability throughout the lifetime of the developer.
Example 2
The procedure of Comparative Example 1 was repeated except that:

    
    
        a) pH was not measured.
        b) the initial charge of 956 Developer was 37.8 L (10 gallons).
        c) the volume of replenisher added to the developer was 215 ml/m2 (20 ml/ft2) of imaged precursor developed in the developer. The 956 Developer was used as the replenisher.
        d) the internal test pattern contained 1, 2, 3, 5, 10, 15, 20, 30, 40, 45, 50, 55, 60, 70, 80; 85, 90, 95, 98, 99, 99.5 and 100% dot images using CREO® Staccato (FM) 10 micron and 20 micron screen rulings and the 240 line pairs per inch (lpi) round dot AM screen ruling.
    
    


Test plate resolution readings are given in Table 6.











TABLE 6









10 Micron
20 Micron
240 lpi,



Staccato
Staccato
round dot



Screen
Screen
AM screen








Theoretical
Area Processed (ft2)













dot (%)
0
1500
0
1500
0
1500
















 1
1
1
1
1
1
1


 2
1
1
2
1
1
2


 3
2
2
2
2
3
3


 5
4
4
4
4
4
4


10
8
8
8
8
9
10


15
13
13
14
14
14
15


20
17
17
18
18
19
20


30
27
28
27
28
29
29


40
38
40
39
39
39
39


45
45
45
44
44
44
44


50
50
49
50
49
49
49


55
55
56
55
55
54
54


60
60
61
60
60
60
60


70
71
71
71
70
70
70


80
80
81
80
81
80
80


85
85
86
86
85
85
85


90
90
91
90
90
90
91


95
95
96
95
95
95
96


98
98
99
98
98
98
99


99
99
100
99
99
99
100


  99.5
99
100
99
99
100
100


100  
100
100
100
100
100
100









With a 10 micron, FM screen ruling, the observed dot percentages vary up to 3% throughout the cycle. Using a 20 micron FM screen ruling, the observed dot percentages vary up to 3% throughout the cycle. This would be acceptable in a typical pre-press environment. The images produced from AM screening using the method of the invention are excellent, having only 1% variability throughout the lifetime of the developer.
Having described the invention, we now claim the following and their equivalents.

## Claims

1. A method for forming an image, the method comprising the steps of:
a) thermally imaging a multi-layer imageable element and forming an imaged imageable element comprising imaged and complementary unimaged regions; 
wherein: 
imaging is carried out using stochastic screening; 
the imageable element comprises a substrate, an underlayer over the substrate, and a top layer over the underlayer; 
the element comprises a photothermal conversion material; 
the top layer is substantially free of the photothermal conversion material; 
the top layer is ink receptive; 
before thermal imaging, the top layer is not removable by an alkaline developer; 
after thermal imaging, the imaged regions are removable by the developer; and 
the underlayer is removable by the developer, and 
b) developing the imaged imageable element with the developer and removing the imaged regions without substantially affecting the unimaged regions; 
wherein: 
the developer is a solvent based developer; 
the developer has a pH below about 10.5; and 
a replenisher is added to the developer; and 
the volume of replenisher added to the developer is about 80 ml/m2 to about 400 ml/m2 of imaged element developed in the developer.

2. The method of claim 1 in which the replenisher has the same composition as the developer.

3. The method of claim 1 in which the developer is sprayed onto the imaged imageable element during step b).

4. The method of claim 1 the volume of replenisher added to the developer is about 100 ml/m2 to about 300 ml/m2 of imaged element developed in the developer.

5. The method of claim 4 in which the replenisher has the same composition as the developer.

6. The method of claim 5 in which the developer has a pH below about 10.2.

7. The method of claim 4 in which the developer has a pH below about 10.2.

8. The method of claim 7 in which the developer comprises phenoxyethanol.

9. The method of claim 8 in which the top layer comprises a novolac resin and a dissolution inhibitor.

10. The method of claim 9 in which the underlayer comprises a copolymer of N-phenylmaleimide, methacrylamide, and methacrylic acid.

11. The method of claim 10 in which the developer is sprayed onto the imaged imageable element during step b); the processing speed is about 0.76 m/min to about 1.2 m/min; and the temperature of the developer is about 20° C. to about 25° C.

12. The method of claim 11 in which the replenisher has the same composition as the developer.

13. The method of claim 1 in which the top layer comprises a novolac resin and a dissolution inhibitor.

14. The method of claim 13 in which the underlayer comprises a copolymer of N-phenylmaleimide, methacrylamide, and methacrylic acid.

15. The method of claim 14 in which:
the developer is sprayed onto the imaged imageable element during step b); 
the volume of replenisher added to the developer is about 100 ml to about 300 ml/m2 of imaged element developed in the developer; 
the developer has a pH below about 10.2, and 
the developer comprises phenoxyethanol.

16. The method of claim 15 in which the replenisher has the same composition as the developer.

17. A method for forming an image, the method comprising the steps of:
a) thermally imaging a multi-layer imageable element and forming an imaged imageable element comprising imaged and complementary unimaged regions; 
wherein: 
imaging is carried out using stochastic screening; 
the imageable element comprises a substrate, an underlayer over the substrate, and a top layer over the underlayer; 
the element comprises a photothermal conversion material; 
the top layer is substantially free of the photothermal conversion material; 
the top layer is ink receptive; 
before thermal imaging, the top layer is not removable by an alkaline developer; 
after thermal imaging, the imaged regions are removable by the developer; and 
the underlayer is removable by the developer, and 
b) developing the imaged imageable element with the developer and removing the imaged regions without substantially affecting the unimaged regions; 
wherein: 
the developer is a solvent based developer; 
the developer has a pH below about 10.5; and 
a replenisher is added to the developer; and 
the volume of replenisher added to the developer per square meter of imaged element developed is equal to about 0.1% to about 1.5% of the volume of the developer.

18. The method of claim 17 in which the developer is sprayed onto the imaged imageable element during step b).

19. The method of claim 18 in which the developer has a pH below about 10.2, and the developer comprises phenoxyethanol.

20. The method of claim 19 in which the volume of replenisher added to the developer per square meter of imaged element developed is equal to about 0.25% to about 1.5% of the volume of the developer.

21. The method of claim 20 in which the top layer comprises a novolac resin and a dissolution inhibitor; and the underlayer comprises a copolymer of N-phenylmaleimide, methacrylamide, and methacrylic acid.

22. The method of claim 21 in which the processing speed is about 0.76 m/min to about 1.2 m/min; and the temperature of the developer is about 20° C. to about 25° C.

23. The method of claim 22 in which the replenisher has the same composition as the developer.

24. The method of claim 17 in which the volume of replenisher added to the developer per square meter of imaged element developed is equal to about 0.25% to about 1.5% of the volume of the developer.