EP1654119B1 - Mehrlagige abbildbare elemente - Google Patents

Mehrlagige abbildbare elemente Download PDF

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Publication number
EP1654119B1
EP1654119B1 EP04780824A EP04780824A EP1654119B1 EP 1654119 B1 EP1654119 B1 EP 1654119B1 EP 04780824 A EP04780824 A EP 04780824A EP 04780824 A EP04780824 A EP 04780824A EP 1654119 B1 EP1654119 B1 EP 1654119B1
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EP
European Patent Office
Prior art keywords
mol
underlayer
top layer
imaged
phenylmaleimide
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EP04780824A
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English (en)
French (fr)
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EP1654119A1 (de
Inventor
Paul Kitson
Kevin B. Ray
S. Peter Pappas
Celin Savariar-Hauck
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Eastman Kodak Co
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Eastman Kodak Co
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Priority claimed from US10/641,888 external-priority patent/US7049045B2/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • B41C1/1016—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials characterised by structural details, e.g. protective layers, backcoat layers or several imaging layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/02—Positive working, i.e. the exposed (imaged) areas are removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/06—Developable by an alkaline solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/14—Multiple imaging layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
    • B41C2210/262—Phenolic condensation polymers, e.g. novolacs, resols

Definitions

  • the invention relates to lithographic printing.
  • this invention relates to multi-layer, positive-working, thermally imageable elements that are useful in forming lithographic printing plates.
  • ink receptive regions are generated on a hydrophilic surface.
  • 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.
  • 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.
  • 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.
  • the regions of the imageable layer i.e ., the image areas
  • the regions of the hydrophilic surface revealed by the developing process accept water and aqueous solutions, typically a fountain solution, and repel ink.
  • 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.
  • EP-A-1 312 483 discloses an imaging element comprising:
  • thermally imageable elements that are both bakable and resistant to press chemistries, such as inks, fountain solution, and the solvents used in washes, such as UV washes. Bakability is highly desirable because baking increases the press runlength.
  • the invention is a positive-working, thermally imageable element that is resistant to press chemistry and can be baked to increase press runlength.
  • the imageable element comprises a substrate; an underlayer over the substrate; and a top layer over the underlayer; in which:
  • the underlayer may additionally comprise a resin having activated methylol or activated alkylated methylol groups, preferably a resole resin.
  • the underlayer may further additionally comprise (1) a first added copolymer or (2) the first added copolymer, and a second added copolymer.
  • the first added copolymer is a copolymer of N-phenylmaleimide; methacrylamide; acrylonitrile; and compound (b), represented by the formula represented by the formula: CH 2 C(R 4 )CO 2 CH 2 CH 2 -NH-CO-NH- p -C 6 H 4 -R 3 , in which R 3 is OH, COOH, or SO 2 NH2; and R 4 is H or methyl; and, optionally, 1 to 30 wt%, preferably, when present, 3 to 20 wt% of compound (c), represented by the formula represented by the formula: CH 2 C(R 6 )CONH- p -C 6 H 4 -R 5 in which R 5 is OH, COOH, or SO 2 NH 2 ; and R 6 is H or methyl.
  • compound (c) represented by the formula represented by the formula: CH 2 C(R 6 )CONH- p -C 6 H 4 -R 5 in which R 5 is OH, COOH, or SO
  • the second added copolymer is a copolymer of N-phenylmaleimide, methacrylamide, and methacrylic acid.
  • the invention is a method for forming an image by imaging and developing the imageable element.
  • the invention is an image useful as a lithographic printing plate formed by imaging and developing the imageable element.
  • the imageable elements are positive working thermally imageable multi-elements that are resistant to the press chemistries used in lithographic printing, especially in printing processes using ultraviolet-curing inks, where rinsing agents with a high content of esters, ethers or ketones are used. In addition, they can be baked to increase press run length.
  • binder resole resin, surfactant, dissolution inhibitor, novolac resin, resin having activated methylol or activated alkylated methylol groups, photothermal conversion material, polymeric material, first added copolymer, second added copolymer, coating solvent, compound (a), compound (b), compound (c), 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 invention is an imageable element as defined in claim 1 useful as precursor for a lithographic printing plate.
  • the imageable element comprises a substrate with a hydrophilic surface, an underlayer, and a top layer.
  • a photothermal conversion material is present, either in the underlayer and/or in a separate absorber layer.
  • 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.
  • 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.
  • polymeric films typically 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, and the like.
  • the nature of this layer or layers depends upon the substrate and the composition of subsequent layers.
  • 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 ⁇ m to about 600 ⁇ m.
  • 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), a vinyl phosphonic acid copolymer, or a water-soluble diazo resin.
  • 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.
  • the underlayer comprises a polymeric material that, after baking, surprisingly provides resistance to solvents and common printing room chemicals, such as fountain solution, inks, plate cleaning agents, rejuvenators, and rubber blanket washing agents, as well as to alcohol substitutes, which are used in fountain solutions.
  • the underlayer also is resistant to rinsing agents with a high content of esters, ethers, and ketones, which are used with ultraviolet curable inks.
  • the underlayer is between the hydrophilic surface of the substrate and the top layer. After imaging, it is removed by the developer in the imaged regions to reveal the underlying hydrophilic surface of the substrate.
  • the underlayer comprises a polymeric material that is preferably soluble in the developer to prevent sludging of the developer.
  • 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 resins that have activated methylol and/or activated alkylated methylol groups, added copolymers, photothermal conversion materials, and surfactants, may also be present in the underlayer.
  • R 1 is C 1 to C 12 alkyl, preferably C 1 to C 4 alkyl, phenyl, C 1 to C 12 substituted phenyl, C 1 to C 12 aralkyl, or Si(CH 3 ) 3 .
  • Typical C 1 to C 12 alkyl groups are 2-methylbutyl, 3-methylbutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 2-methylhexyl, 2-ethylpentyl, 5-methylhexyl, 2,2,4-trimethylpentyl, cyclopentyl, cyclohexyl, and alkyl groups of one to four carbon atoms, such as methyl, ethyl, i -propyl, n -propyl, cyclopropyl, cyclobut
  • Typical C 1 to C 12 substituted phenyl groups are p -methylphenyl, m-methylphenyl, o-methylphenyl, p -methoxyphenyl, m -methoxyphenyl, o- methoxyphenyl, p -ethoxyphenyl, p -ethylphenyl, p - i -propylphenyl, p- chlorophenyl, p -bromophenyl, p -cyanophenyl, m -cyanophenyl, p -fluorophenyl, p -nitrophenyl, p -thiomethoxyphenyl, p -(N,N-dimethylamino)phenyl, pentafluorophenyl, pentachlorophenyl, p -trifluoromethylphenyl, 3,5-dichlorophenyl, 3,5-dimethylphenyl, 3,5
  • Typical C 1 to C 12 aralkyl groups are benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylpropyl, and 3-phenyl propyl.
  • R 1 is an alkyl group of one to four carbon atoms, phenyl, benzyl, 2-phenylethyl, or trimethylsilyl.
  • Preferred alkyl groups of one to four carbon atoms are i -butyl, s- butyl, t -butyl, and n -butyl.
  • R 2 is hydrogen or methyl, preferably methyl.
  • the polymeric material comprises about 20 mol% to about 75 mol%, preferably about 35 mol% to about 60 mol%, of N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, or a mixture thereof.
  • N-Phenylmaleimide is preferred.
  • the underlayer may additionally comprise a resin or resins having activated methylol and/or activated alkylated methylol groups.
  • resins include, for example: resole resins and their alkylated analogs; methylol melamine resins and their alkylated analogs, for example melamine-formaldehyde resins; methylol glycoluril resins and alkylated analogs, for example, glycoluril-formaldehyde resins; thiourea-formaldehyde resins; guanamine-formaldehyde resins; and benzoguanamine-formaldehyde resins.
  • melamine-formaldehyde resins and glycoluril-formaldehyde resins include, for example, CYMEL® resins (Dyno Cyanamid Co., Ltd.) and NIKALAC® resins (Sanwa Chemical Co., Ltd.).
  • the resin or resins having activated methylol and/or activated alkylated methylol groups is preferably a resole resin or a mixture of resole resins.
  • Resole resins are well known to those skilled in the art. They are prepared by reaction of a phenol with an aldehyde under basic conditions using an excess of phenol.
  • Commercially available resole resins include, for example, GP649D99 resole (Georgia Pacific) and BKS-5928 resole resin (Union Carbide).
  • the underlayer may comprise a first added copolymer.
  • the underlayer may also comprise a second added copolymer.
  • the second added copolymer comprises, in polymerized form, N-phenylmaleimide, methacrylamide, and methacrylic acid. These copolymers comprise about 25 to about 75 mol%, preferably about 35 to about 60 mol% of N-phenylmaleimide; about 10 to 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 mol%, of methacrylic acid. These copolymers are disclosed in Shimazu, U.S. Pat. No. 6,294,311 , and Savariar-Hauck, U.S. Pat. No. 6,528,228 .
  • the polymeric materials and the added copolymers can be prepared by methods, such as free radical polymerization, which are well known to those skilled in the art and which are described, for example, in Chapters 20 and 21, of Macromolecules, Vol. 2, 2nd Ed., H.G. Elias, Plenum, New York, 1984 .
  • Useful free radical initiators are peroxides such as benzoyl peroxide (BPO), hydroperoxides such as cumyl hydroperoxide and azo compounds such as 2,2'-azobis(isobutyronitrile) (AIBN).
  • Suitable solvents include liquids that are inert to the reactants and which will not otherwise adversely affect the reaction.
  • Typical solvents include, for example, esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl propyl ketone, and acetone; alcohols such as methanol, ethanol, isopropyl alcohol, and butanol; ethers such as dioxane and tetrahydrofuran, and mixtures thereof.
  • esters such as ethyl acetate and butyl acetate
  • ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl propyl ketone, and acetone
  • alcohols such as methanol, ethanol, isopropyl alcohol, and butanol
  • ethers such as dioxane and tetrahydrofuran, and mixtures thereof.
  • a photothermal conversion material When a photothermal conversion material is present, it typically comprises about comprises 0.1 wt% to about 25 wt%, preferably about 5 wt% to about 20 wt%, more preferably about 10 wt% to 15 wt%, of the underlayer, based on the total weight of the underlayer.
  • a surfactant When a surfactant is present in the underlayer, it typically comprises 0.05 wt% to about 1 wt%, preferably about 0.1 wt% to about 0.6 wt%, more preferably about 0.2 wt% to 0.5 wt%, based on the total weight of the underlayer.
  • the resole resin typically comprises about 7 wt% to about 15 wt%, preferably about 8 wt% to about 12 wt%, more preferably about 10 wt% of the underlayer, based on the total weight of the underlayer.
  • the underlayer When the underlayer does not comprise either the resin having activated methylol or activated alkylated methylol groups, the first added copolymer, or the second added copolymer, the underlayer typically comprises about 5 wt% to about 20 wt% of the photothermal conversion material and about 80 wt% to about 95 wt% the polymeric material. When the photothermal conversion material is not present, the underlayer typically comprises about 95 wt% to about 100 wt% of the polymeric material.
  • the underlayer typically comprises the resole resin, the photothermal conversion material, optionally the surfactant, and about 60 wt% to about 90 wt%, preferably about 65 wt% to about 80 wt%, of the polymeric material.
  • the underlayer typically comprises the resole resin, optionally the surfactant, and about 85 wt% to abut 93 wt%, preferably about 88 wt% to about 92 wt% of the polymeric material.
  • the underlayer typically comprises the resole resin, the photothermal conversion material, optionally the surfactant, about 40 wt% to about 80 wt%, preferably about 50 wt% to about 70 wt%, of the polymeric material, and about 5 wt% to about 25 wt%, preferably about 10 wt% to about 20 wt%, of the first added copolymer.
  • the underlayer typically comprises the resole resin, optionally the surfactant, and about 60 wt% to 85 wt%, preferably about 65 wt% to about 80 wt% of the polymeric material, and about 5 wt% to about 30 wt%, preferably about 10 wt% to about 25 wt%, of the first added copolymer.
  • the underlayer typically comprises the resole resin, the photothermal conversion material, optionally the surfactant, about 15 wt% to about 45 wt%, preferably about 20 wt% to about 40 wt%, of the polymeric material, about 5 wt% to about 25 wt%, preferably about 10 wt% to about 20 wt%, of the first added copolymer, and about 15 wt% to about 45 wt%, preferably about 20 wt% to about 40 wt%, of the second added copolymer.
  • the underlayer typically comprises the resole resin, optionally the surfactant, and about 15 wt% to about 50 wt%, preferably about 20 wt% to about 45 wt% of the polymeric material, about 5 wt% to about 30 wt%, preferably about 10 wt% to about 20 wt%, of the first added copolymer, and about 15 wt% to about 50 wt%, preferably about 20 wt% to about 45 wt%, of the second added copolymer.
  • 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.
  • 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. 6,358,669 , and Hauck, U.S. Pat. No. 6,555,291 .
  • 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.
  • 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.
  • 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 .
  • 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. Top layers comprising these resins are disclosed in Pat. Pub. No. US 2004/0067432 A1 .
  • 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 a diazobenzoquinone moiety and/or a diazonaphthoquinone moiety.
  • Other useful 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 dyes can also act as contrast dyes, which distinguish the unimaged regions from the imaged regions in the developed imageable element.
  • a dissolution inhibitor 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.
  • 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 thermal imaging, the polymeric material is not soluble in the developer.
  • 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.
  • 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 1.5 mol% to about 2.5 mol%, of the hydroxyl groups have been converted to phenyl sulfonate or p -toluene sulfonate (tosyl) groups.
  • 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.
  • 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.
  • 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.
  • Suitable dyes include dyes of the following classes: methine, polymethine, arylmethine, cyanine, hemicyanine, streptocyanine, squarylium, pyrylium, oxonol, naphthoquinone, anthraquinone, porphyrin, azo, croconium, triarylamine, thiazolium, indolium, oxazolium, indocyanine, indotricarbocyanine, oxatricarbocyanine, phthalocyanine, thiocyanine, thiatricarbocyanine, merocyanine, cryptocyanine, naphthalocyanine, polyaniline, polypyrrole, polythiophene, chalcogenopyryloarylidene 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 .
  • 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), SpectraIR 830A and SpectraIR 840A (Spectra Colors), as well as IR Dye A, and IR Dye B, whose structures are shown below.
  • 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.
  • 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.
  • the absorber layer When an absorber layer is present, it is between the top layer and the underlayer.
  • the absorber layer preferably consists essentially of the photothermal conversion material and, optionally, a surfactant. It may be possible to use less of the photothermal conversion material 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/m 2 to about 2 g/m 2 , preferably about 0.05 g/m 2 to about 1.5 g/m 2 . Elements that comprise an absorber layer are disclosed in Shimazu, U.S. Pat. No. 6,593,055 .
  • 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.
  • 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.
  • 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.
  • the top layer is coated on the underlayer.
  • the top layer should be coated from a solvent in which the underlayer layer is essentially insoluble.
  • 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.
  • 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.
  • the underlayer, the top layer or both layers may be applied by conventional extrusion coating methods from a melt mixture of layer components.
  • a melt mixture typically contains no volatile organic solvents.
  • 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, Illinois, USA), and the Gerber Crescent 42T (Gerber).
  • 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, Illinois, USA), and the Gerber Crescent 42T (Gerber).
  • 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, TX, USA), or the Model VP-3500 thermal printer (Seikosha America, Mahwah, NJ, USA).
  • Imaging produces an imaged element, which comprises a latent image of imaged regions and complementary unimaged regions.
  • Development of the imaged element to form a printing plate, or printing form converts the latent image to an image by removing the imaged regions, revealing the hydrophilic surface of the underlying substrate.
  • Suitable developers depend on the solubility characteristics of the ingredients present in the imageable element.
  • the developer may be any liquid or solution that can penetrate and remove the imaged regions of the imageable element without substantially affecting the complementary 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.
  • 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.
  • the underlayer is dissolved in the developer and the top layer is dissolved and/or dispersed in the developer.
  • High pH developers can be used. High pH developers typically have a pH of at least about 11, more typically at least about 12, even more typically from about 12 to about 14. High pH developers also typically comprise at least one alkali metal silicate, such as lithium silicate, sodium silicate, and/or potassium silicate, and are typically substantially free of organic solvents.
  • the alkalinity can be provided by using a hydroxide or an alkali metal silicate, or a mixture. Preferred hydroxides are ammonium, sodium, lithium and, especially, potassium hydroxides.
  • the alkali metal silicate has a SiO 2 to M 2 O weight ratio of at least 0.3 (where M is the alkali metal), preferably this ratio is from 0.3 to 1.2, more preferably 0.6 to 1.1, most preferably 0.7 to 1.0.
  • the amount of alkali metal silicate in the developer is at least 20 g SiO 2 per 100 g of composition and preferably from 20 to 80 g, most preferably it is from 40 to 65 g.
  • High pH developers can be used in an immersion processor.
  • Typical high pH developers include PC9000, PC3000, Goldstar TM , Greenstar TM , ThermaIPro TM , PROTHERM®, MX 1813, and MX1710, aqueous alkaline developers, all available from Kodak Polychrome Graphics LLC.
  • Another useful developer contains 200 parts of Goldstar TM developer, 4 parts of polyethylene glycol (PEG) 1449, 1 part of sodium metasilicate pentahydrate, and 0.5 part of TRITON® H-22 surfactant (phosphate ester surfactant).
  • the imaged imageable elements can be developed using a solvent based developer in an immersion processor or a spray on processor.
  • solvent based developers include 956 Developer, 955 Developer and SP200 (Kodak Polychrome Graphics, Norwalk, CT, USA).
  • spray on processors include the 85 NS (Kodak Polychrome Graphics).
  • immersion processors include the Mercury TM Mark V processor (Kodak Polychrome Graphics); the Global Graphics Titanium processor (Global Graphics, Trenton, NJ, USA); and the Glunz and Jensen Quartz 85 processor (Glunz and Jensen, Elkwood, VA, USA).
  • 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.
  • 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 is 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.
  • the imageable elements of the invention are a multi-layer, positive working, thermally imageable, bakeable lithographic printing precursors that produce lithographic printing plates that have a long press runlength and are resistant to press chemistries. They are especially useful for use with ultraviolet curable inks, in which aggressive washes that contain organic solvents (UV wash) are used.
  • UV wash organic solvents
  • the ink is taken up by the imaged regions, i . e ., 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.
  • coating solution refers to the mixture of solvent or solvents and additives coated, even though some of the additives may be in suspension rather than in solution
  • total solids refers to the total amount of nonvolatile material in the coating solution even though some of the additives may be nonvolatile liquids at ambient temperature. Except where indicated, the indicated percentages are percentages by weight based on the total solids in the coating solution.
  • This example illustrates preparation of a copolymer containing 41.5 mol% N-phenylmaleimide, 21 mol% methacrylic acid, and 37.5 mol% N-(isobutoxymethyl)acrylamide.
  • N-Phenylmaleimide (19.31 g) methacrylic acid (4.86 g), N-( iso -butoxymethyl)acrylamide (15.84 g) (Cytec Industries, Charlotte, NC, USA), and 50:50 (v:v) dioxolane/ethanol (126.01 g) were placed in a 1 L reaction kettle fitted with a reflux condenser, nitrogen supply, thermometer, stirrer, and heating mantle. Nitrogen was bubbled through the reaction mixture for one hour.
  • This example illustrates preparation of a copolymer containing 41.5 mol% N-phenylmaleimide, 21 mol% methacrylic acid, 19 mol% methacryamide, and 18.5 mol% N-( iso -butoxymethyl)acrylamide.
  • the procedure of Example 1 was repeated except that N-phenylmaleimide (21.26 g), methacrylic acid (5.35 g), methacrylamide (4.78 g), N-(isobutoxymethyl)acrylamide (8.60 g) and 50:50 (v:v) dioxolane/ethanol (126.01 g) were used to prepare the copolymer. Yield: 75%.
  • This example illustrates preparation of a copolymer containing 41.5 mol% N-phenylmaleimide, 21 mol% methacrylic acid, 19 mol% methacryamide, and 18.5 mol% N-(butoxymethyl)acrylamide.
  • the procedure of Example 1 was repeated except that N-phenylmaleimide (21.26 g), methacrylic acid (5.35 g), methacrylamide (4.78 g), N-(butoxymethyl)-acrylamide (8.60 g) (Cytec Industries, Charlotte, NC, USA) and 50:50 (v:v) dioxolane/ethanol (126.01 g) were used to prepare the copolymer. Yield: 72%.
  • the supernatant was decanted from the tacky solid that formed in the bottom of the reaction flask.
  • Acetone (354 g) was added, and the reaction mixture stirred until a clear solution was obtained.
  • Water/ice (160 g) and acetic acid (1.2 g, 20.02 millimoles) were added over several minutes and the reaction mixture stirred for 5 min below 15°C.
  • the supernatant was decanted from the tacky solid.
  • Additional acetone (354 g) was added and the reaction mixture stirred until a clear solution was obtained. 25% of the acetone solution was added to a mixture of ice (460 g), water (460 g) and acetic acid (0.5 g).
  • Example 2 illustrates preparation of a copolymer containing 41.5 mol% N-phenylmaleimide, 21 mol% methacrylic acid, and 37.5% methacrylamide
  • N-phenylmaleimide 23.59 g
  • methacrylic acid 5.93 g
  • methacrylamide 10.48 g
  • dioxolane/ethanol 50:50 (v:v); 126.01 g
  • the copolymer was washed with about 1 L of 80:20 ethanol/water containing about 5 drops of concentrated hydrochloric acid, filtered again, washed with about 1 L of 80:20 ethanol/water, filtered again, and dried for two days at 50°C. Yield: 80%.
  • Comparative Example 2 is an ELECTRA EXCEL® thermally sensitive, positive working, single layer, conditioned, inhibited novolac-containing plate printing plate precursor. It develops in high pH developer, is bakeable, but has poor resistance to press chemicals. Comparative Examples 3 and 4 and Examples 5 to 10 were prepared by the following procedure.
  • Underlayer Coating solutions containing the components listed in Table 1 in methyl ethyl ketone/1-methoxypropan-2-ol/butyrolactone/water (65/15/10/10, w:w:w:w) were coated onto substrate A using a wire wound bar.
  • the resulting element comprising the underlayer and the substrate was dried at 135°C for 35 sec.
  • the coating weight of each of the resulting underlayers was 1.3 g/m 2 .
  • Each imageable element was imaged with 830 nm radiation with an internal test pattern (plot 0), on a CREO® 3230 Trendsetter at 100 to 180 mJ/cm 2 , in 20 mJ/cm 2 increments (at 9W).
  • Each imaged imageable element was machine processed with Goldstar TM developer in a Kodak Polychrome Graphics Mercury TM Mark V Processor (750 mm/min processing speed, 23°C developer temperature). The resulting printing plates were evaluated for cleanout (first imaging exposure where exposed regions dissolve completely in developer) and best resolution (imaging exposure where plate performs best).
  • Solvent resistance drop test on complete imageable element A large drop of either diacetone alcohol/water (80:20, v:v) or 2-butoxyethanol/water (80:20, v:v) was placed on each imageable element at 22°C. The time required to dissolve the layers was noted, and the amount of material removed after 1 min was assessed.
  • Deletion gel test A Kodak Polychrome Graphics positive deletion gel (contains hydrofluoric acid) was applied to the baked imageable elements for up to 3 min, and the amount of time required for removal of the baked layer ("coating") was noted.
  • This example illustrates preparation of a copolymer having 40 mol% N-phenylmaleimide, 25 mol% methacrylic acid, 25 mol% methacrylamide and 10 mol% N-(Isobutoxymethyl)acrylamide.
  • the procedure of Example 1 was repeated except that N-phenylmaleimide (21.68 g), methacrylic acid (6.74 g), methacrylamide (6.66 g), N-( iso -butoxymethyl)acrylamide (4.92 g) and dioxolane/ethanol (50:50 (v:v); 126.01 g) were used to prepare the copolymer. Yield: 79%
  • This example illustrates preparation of a copolymer having 40 mol% N-phenylmaleimide, 25 mol% methacrylic acid, 25 mol% methacrylamide and 10 mol% N-(butoxymethyl)acrylamide.
  • the procedure of Example 1 was repeated except that N-phenylmaleimide (21.68 g), methacrylic acid (6.74 g), methacrylamide (6.66 g), N-(butoxymethyl)acrylamide (4.92 g), and dioxolane/- ethanol (50:50 (v:v); 126.01 g) were used to prepare the copolymer. Yield: 82%.
  • This example illustrates preparation of a copolymer having 30 mol% N-phenylmaleimide, 20 mol% methacrylic acid, 35 mol% methacrylamide and 15 mol% N-(isobutoxymethyl)acrylamide.
  • the procedure of Example 1 was repeated except that N-phenylmaleimide (16.96 g), methacrylic acid (5.62 g), methacrylamide (9.72 g), N-(butoxymethyl)acrylamide (7.70 g), and dioxolane/- ethanol (50:50 (v:v); 126.01 g) were used to prepare the copolymer. Yield: 83%.
  • Imageable elements were prepared as in Examples 5 to 10, except that the ingredients listed in Table 3 were used in the underlayer.
  • This example illustrates preparation of a copolymer containing 40 mol% N-phenylmaleimide, 25 mol% methacrylic acid, and 35 mol% methacrylamide.
  • This example illustrates preparation of a polymeric material containing 35 mol% N-phenylmaleimide, 20 mol% methacrylic acid, 20 mol% methacrylamide, and 25 mol% N-methoxymethylmethacrylamide.
  • the procedure of Comparative Example 5 was repeated except that 250 ml of a mixture of methacrylic acid (17.22 g), N-phenylmaleimide (60.61 g), methacrylamide (17.02 g) and N-methoxymethymethacrylamide (32.25g) and 1.65 g of AIBN was used.
  • the copolymer formed in Comparative Example 5 (2.12 g) and IR Dye A (0.38 g) were dissolved in 30 g of a mixture of 2-butanol (65%), PM (15%), ⁇ -butyrolatone (10%), and water (10%), coated onto a Substrate B, and dried to give an underlayer with a coating weight of 1.40 g/m 2 .
  • Example 20 The procedure was repeated except that the polymeric material prepared in Example 20 was used in the underlayer.
  • the coating weight of the underlayer was 1.51 g/m 2
  • the coating weight of the top layer was 0.80 g/m 2 .
  • the imaged imageable element developed with GOLDSTARTM DC Developer had good resistance to the developer. The element showed good developability in the imaged areas, giving a clean background and good resolution.
  • the imaged imageable element developed with 956 Developer showed a clean background and good resolution.
  • the copolymer formed in Comparative Example 5 and the polymeric material formed in Example 20 were each coated onto Substrate B as described above to form an element consisting of the underlayer on the substrate.
  • the underlayers were evaluated as follows.
  • each element consisting of the underlayer on the substrate was soaked in BC/water (80/20) for 5 min and the weight loss determined.
  • the soak losses were: 30% for the element containing the copolymer formed in Comparative Example 5, and 21% for the element containing the polymeric material formed in Example 20.
  • the single layer of an ELECTRA EXCEL® printing plate precursor was completely removed (100% soak loss).
  • Bakeability of the underlayer was determined by baking the elements consisting of the underlayer on the substrate at 235°C for 8 min and applying Deletion Fluid 243 to the surface of the underlayer.
  • the underlayer consisting of the copolymer formed in Comparative Example 5 deleted completely within 1 min.
  • the underlayer consisting of the polymeric material formed in Example 20 showed no deletion after 8 min.

Claims (10)

  1. Bebilderbares Element mit:
    einem Substrat;
    einer über dem Substrat angeordneten unteren Schicht; und
    einer über der unteren Schicht angeordneten oberen Schicht;
    worin:
    das Element ein fotothermisches Umwandlungsmaterial umfasst;
    die obere Schicht im Wesentlichen frei von fotothermischem Umwandlungsmaterial ist;
    die obere Schicht Tinte aufzunehmen vermag;
    die obere Schicht vor der thermischen Bebilderung nicht mithilfe eines alkalischen Entwicklers entfernbar ist;
    nach der thermischen Bebilderung zur Ausbildung bebilderter Bereiche in der oberen Schicht die bebilderten Bereiche mithilfe eines alkalischen Entwicklers entfernbar sind;
    die untere Schicht mithilfe des alkalischen Entwicklers entfernbar ist, und
    die untere Schicht ein Polymermaterial umfasst, das in polymerisierter Form Folgendes umfasst:
    etwa 5 Mol% bis etwa 30 Mol% Methacrylsäure;
    etwa 20 Mol% bis ca. 75 Mol% N-Phenylmaleimid, N-Cyclohexylmaleimid, N-Benzylmaleimid oder eine Mischung daraus; und
    etwa 3 Mol% bis etwa 50 Mol% einer Verbindung (a),
    dargestellt durch folgende Formel:

            CH2C(R2)C(O)NHCH2OR1,

    worin R1 für C1 bis C12 Alkyl, Phenyl, C1 bis C12 substituiertes Phenyl, C1 bis C12 Aralkyl oder Si(CH3)3 steht und R2 für H oder Methyl steht.
  2. Element nach Anspruch 1, worin R1 für C1 bis C4 Alkyl, Phenyl, Benzyl, 2-Phenylethyl oder Si(CH3)3 steht und R2 für Methyl steht und das Polymermaterial etwa 10 Mol% bis etwa 30 Mol% Methacrylsäure, etwa 35 Mol% bis etwa 60 Mol% von N-Phenylmaleimid und etwa 10 Mol% bis etwa 40 Mol% einer Verbindung (a) umfasst.
  3. Element nach Anspruch 2, worin das Polymermaterial zudem etwa 15 Mol% bis etwa 40 Mol% Methacrylamid umfasst.
  4. Element nach einem der vorausgehenden Ansprüche, worin die untere Schicht zudem ein Harz mit aktivierten Methylol-oder aktivierten, alkylierten Methylolgruppen umfasst.
  5. Element nach einem der vorausgehenden Ansprüche, worin die untere Schicht zudem ein erstes zugegebenes Copolymer umfasst, und worin das erste zugegebene Copolymer in polymerisierter Form etwa 1 Gew.-% bis etwa 30 Gew.-% N-Phenylmaleimid, etwa 1 Gew.-% bis etwa 30 Gew.-% Methacrylamid, etwa 20 Gew.-% bis etwa 75 Gew.-% Acrylonitril und etwa 20 Gew.-% bis etwa 75 Gew.-% einer Verbindung (b) umfasst, dargestellt durch folgende Formel:

            CH2C(R4)CO2CH2CH2-NH-CO-NH-p-C6H4-R3,

    worin R3 für OH, COOH oder SO2NH2 und R4 für H oder Methyl stehen.
  6. Element nach Anspruch 5, worin das erste zugegebene Copolymer zudem in polymerisierter Form etwa 1 Gew.-% bis etwa 30 Gew.-% der Verbindung (c) umfasst, dargestellt durch die Formel:

            CH2C(R6)CO-NH-p-C6H4-R5

    worin R5 für OH, COOH oder SO2NH2 und R6 für H oder Methyl stehen.
  7. Element nach Anspruch 5, worin die untere Schicht zusätzlich ein zweites zugegebenes Copolymer umfasst und worin das zweite zugegebene Copolymer in polymerisierter Form etwa 25 Mol% bis etwa 75 Mol% N-Phenylmaleimid, etwa 10 Mol% bis etwa 50 Mol% Methacrylamid und etwa 5 Mol% bis etwa 30 Mol% Methacrylsäure umfasst.
  8. Verfahren zur Ausbildung eines Bildes mit folgenden Schritten:
    a) thermisches Bebildern des bebilderbaren Elements nach einem der Ansprüche 1 bis 7 und Ausbilden eines bebilderten, bebilderbaren Elements aus bebilderten Bereichen und komplementären unbebilderten Bereichen;
    b) Entwickeln des bebilderten, bebilderbaren Elements mit einem Entwickler und Entfernen der bebilderten Bereiche, ohne im Wesentlichen die unbebilderten Bereiche zu beeinträchtigen.
  9. Verfahren nach Anspruch 8 mit dem zusätzlichen Schritt des Einbrennens des bebilderten, bebilderbaren Elements nach Schritt b).
  10. Bild, hergestellt gemäß dem Verfahren nach Anspruch 8.
EP04780824A 2003-08-14 2004-08-11 Mehrlagige abbildbare elemente Expired - Fee Related EP1654119B1 (de)

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US7291440B2 (en) * 2005-05-16 2007-11-06 Eastman Kodak Company Bakeable multi-layer imageable element
EP1738902A1 (de) * 2005-06-30 2007-01-03 Agfa-Gevaert Verfahren zur Herstellung eines lithographischen Druckplattenvorläufer
US7144661B1 (en) * 2005-11-01 2006-12-05 Eastman Kodak Company Multilayer imageable element with improved chemical resistance
US7223506B1 (en) 2006-03-30 2007-05-29 Eastman Kodak Company Imageable members with improved chemical resistance
US7300726B1 (en) * 2006-10-20 2007-11-27 Eastman Kodak Company Multi-layer imageable element with improved properties
US20100227269A1 (en) 2009-03-04 2010-09-09 Simpson Christopher D Imageable elements with colorants
ATE555904T1 (de) 2009-08-10 2012-05-15 Eastman Kodak Co Lithografische druckplattenvorläufer mit betahydroxy-alkylamid-vernetzern
US8383319B2 (en) 2009-08-25 2013-02-26 Eastman Kodak Company Lithographic printing plate precursors and stacks
EP2293144B1 (de) 2009-09-04 2012-11-07 Eastman Kodak Company Verfahren zum Trocknen von Lithographiedruckplatten nach einer Einstufenverarbeitung

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US5705322A (en) 1996-09-30 1998-01-06 Eastman Kodak Company Method of providing an image using a negative-working infrared photosensitive element
US5705308A (en) 1996-09-30 1998-01-06 Eastman Kodak Company Infrared-sensitive, negative-working diazonaphthoquinone imaging composition and element
US6358669B1 (en) 1998-06-23 2002-03-19 Kodak Polychrome Graphics Llc Thermal digital lithographic printing plate
US6534238B1 (en) * 1998-06-23 2003-03-18 Kodak Polychrome Graphics, Llc Thermal digital lithographic printing plate
EP1074887B1 (de) * 1999-08-02 2004-10-06 Kodak Polychrome Graphics GmbH Strahlungsempfindliche Zusammensetzungen für Druckplatten mit verbesserter chemischer Beständigkeit und Entwickler-Beständigkeit und mit diesen Zusammensetzungen hergestellte Druckplatten
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