EP0779161B1 - Wärmeempfindliches Aufzeichnungselement und Verfahren zur Herstellung von Flachdruckformen damit - Google Patents

Wärmeempfindliches Aufzeichnungselement und Verfahren zur Herstellung von Flachdruckformen damit Download PDF

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Publication number
EP0779161B1
EP0779161B1 EP19950203494 EP95203494A EP0779161B1 EP 0779161 B1 EP0779161 B1 EP 0779161B1 EP 19950203494 EP19950203494 EP 19950203494 EP 95203494 A EP95203494 A EP 95203494A EP 0779161 B1 EP0779161 B1 EP 0779161B1
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EP
European Patent Office
Prior art keywords
imaging element
heat sensitive
layer
adhesive layer
thermo
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EP19950203494
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English (en)
French (fr)
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EP0779161A1 (de
Inventor
Marc Van Damme
Joan Vermeersch
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Agfa Gevaert NV
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Agfa Gevaert NV
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Priority to DE1995617815 priority Critical patent/DE69517815T2/de
Priority to EP19950203494 priority patent/EP0779161B1/de
Priority to US08/762,441 priority patent/US6010817A/en
Priority to JP35178996A priority patent/JP2901235B2/ja
Publication of EP0779161A1 publication Critical patent/EP0779161A1/de
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/48—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • 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
    • B41C1/1091—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by physical transfer from a donor sheet having an uniform coating of lithographic material using thermal means as provided by a thermal head or a laser; by mechanical pressure, e.g. from a typewriter by electrical recording ribbon therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/36—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties
    • B41M5/368—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties involving the creation of a soluble/insoluble or hydrophilic/hydrophobic permeability pattern; Peel development

Definitions

  • the present invention relates to a heat sensitive material for making a lithographic printing plate.
  • the present invention further relates to a method for preparing a printing plate from said heat sensitive material.
  • Lithography is the process of printing from specially prepared surfaces, some areas of which are capable of accepting lithographic ink, whereas other areas, when moistened with water, will not accept the ink.
  • the areas which accept ink form the printing image areas and the ink-rejecting areas form the background areas.
  • a photographic material is made imagewise receptive to oily or greasy ink in the photo-exposed (negative working) or in the non-exposed areas (positive working) on a hydrophilic background.
  • lithographic plates also called surface litho plates or planographic printing plates
  • a support that has affinity to water or obtains such affinity by chemical treatment is coated with a thin layer of a photosensitive composition.
  • Coatings for that purpose include light-sensitive polymer layers containing diazo compounds, dichromate-sensitized hydrophilic colloids and a large variety of synthetic photopolymers. Particularly diazo-sensitized systems are widely used.
  • the exposed image areas become insoluble and the unexposed areas remain soluble.
  • the plate is then developed with a suitable liquid to remove the diazonium salt or diazo resin in the unexposed areas.
  • EP-A 708 373 discloses a negative-working photosensitive imaging element comprising on a hydrophilic surface of a support in the order given (i) a hydrophobic photopolymerizable composition capable of being irradiated with actinic light through the support and/or through the front and containing at least one unsaturated compound with at least one polymerizable ethylenically unsaturated group, at least one hydrophobic thermoplastic polymer and at least one photoinitiator, and (ii) optionally a receptor layer, characterized in that said hydrophobic photopolymerizable composition comprises in the order given (i) a polymerizable layer contiguous to said hydrophilic surface and comprising at least part of said at least one unsaturated compound and (ii) a hydrophobic photosensitive layer contiguous to said polymerizable layer comprising at least part of said at least one hydrophobic thermoplastic polymer and of said at least one photoinitiator and the peeling
  • a particular disadvantage of photosensitive imaging elements such as described above for making a printing plate is that they have to be shielded from the light.
  • thermosensitive imaging element comprising
  • a method for obtaining a lithographic printing plate comprising the steps of:
  • lithographic printing plates of high quality can be obtained according to the method of the present invention using an imaging element as described above. More precisely it has been found that said printing plates are of high quality and are provided in a convenient way, thereby offering economical and ecological advantages.
  • Suitable thermo-adhesive layers for use in the present invention have a glass transition temperature T g between 10 °C and 100 °C as measured with a 1090 THERMOANALIZER of Du Pont Co..
  • T g glass transition temperature
  • the T g of the TAL is preferably below 60 °C.
  • the T g value of the TAL can be determined by the T g value of the polymer(s) used and/or by the addition of polymeric or low-molecular plasticizers or thermosolvents.
  • the adherance of the TAL to the receptor layer is also determined by the flow properties of the TAL while heating above the T g .
  • a parameter for describing this property is the melt viscosity.
  • a TAL for use in accordance with the present invention has a melt viscosity of more than 3000 Poise measured at 120 °C with a VISCOELASTIC MELT TESTER of Rheometrics Co, Surrey, UK..
  • a TAL is preferably used with a T g value between 20 °C and 45 °C, a melt viscosity greater than 7000 Poise and an elasticity corresponding to a (tg ⁇ ) -1 value greater than 1.30 measured at 120 °C with a VISCOELASTIC MELT TESTER of Rheometrics Co, Surrey, UK..
  • the (tg ⁇ ) -1 value is a measure for the elasticity as described in "Polymer Chemistry : the Basic Concept" by P.C. Hiemenz, 1984, edit. by M. Dekker Inc., New York.
  • the TAL is preferably coated from an aqueous medium. Therefore the polymers are preferably incorporated as latices.
  • Preferred latices are latices of styrene, styrene-butadiene, styrene-(meth)acrylate and n.butylacrylate-methylmethacrylate-acrylonitrile. These latices can contain other comonomers which improve the stablitity of the latex, such as acrylic acid, methacrylic acid and acrylamide.
  • latices include polyvinylacetate, polyethylene-vinylacetate, polyacrylonitrile-butadiene-acrylic acid, polymethylmethacrylate-butylmethacrylate, polymethylmethacrylate-ethylacrylate, polystyrene-butylacrylate, polymethylmethacrylate-butadiene, polyester of terephtalic acid-sulphoisophtalic acid-ethyleneglycol, copolyester of terephtalic acid-sulphoisophtalic acid-hexanediol-ethyleneglycol.
  • Particularly suitable polymers for use in the TAL layer are the BAYSTALTM polymer types, marketed by Bayer AG, Germany, which are on the basis of styrene-butadiene copolymers with a weight ratio between 40/60 and 80/20. If desired a few weight % (up to about 10 %) of acrylamide and/or acrylic acid can be included.
  • Other useful polymers are the EUDERMTM polymers, also from Bayer AG, which are copolymers comprising n.-butylacrylate, methylmethacrylate, acrylonitrile and small amounts of methacrylic acid.
  • additives can be present in the TAL to improve the layer formation or the layer properties, e.g. thickening agents, surfactants, levelling agents, thermal solvents and pigments.
  • thermo-adhesive layer Apart from the thermo-adhesive layer to which the receptor layer will be laminated and which must comply with the requirements described above the material can contain one or more supplementary thermo-adhesive layer(s) positioned between the upper TAL and the hydrophobic photosensitive composition e.g. to optimize the adherance to the hydrophobic heat sensitive composition in view of obtaining a better image quality after the delamination process.
  • This (these) other TAL(s) can have a composition and/or physical properties different from those imposed to the upper TAL.
  • This (these) layer(s) can contain one polymer or a mixture of polymers, optionally in combination with low-molecular additives like plasticizers or thermosolvents.
  • Other ingredients which can be incorporated include waxes, fillers, polymer beads, glass beads, silica etc.
  • the thickness of the thermo-adhesive layer is important for the adherence during the lamination/delamination process.
  • the thickness of said thermo-adhesive layer lies between 0.1 and 50 ⁇ m, more preferably between 0.1 and 15 ⁇ m.
  • the support of the imaging element according to the present invention has a hydrophilic surface and should be stable at the processing conditions.
  • Said support with a hydrophilic surface may be a hydrophilic metallic support, preferably a grained and anodized aluminum support.
  • an anodized aluminum support may be treated to improve the hydrophilic properties of its surface.
  • said support with a hydrophilic surface comprises a hardened hydrophilic layer, containing a hydrophilic binder and a hardening agent coated on a flexible support.
  • Such hydrophilic binders are disclosed in e.g. EP-A 450,199.
  • Preferred hardened hydrophilic layers comprise partially modified dextrans or pullulan hardened with an aldehyde as disclosed in e.g. EP-A 514,990.
  • More preferred hydrophilic layers are layers of polyvinyl alcohol hardened with a tetraalkyl orthosilicate and preferably containing SiO 2 and/or TiO 2 wherein the weight ratio between said polyvinylalcohol and said tetraalkyl orthosilicate is between 0.5 and 5 as disclosed in e.g. GB-P 1,419,512, FR-P 2,300,354, US-P-3,971,660, US-P 4,284,705, EP-A 405,016 and EP-A 450,199.
  • Said hardened hydrophilic layer in an imaging element used in accordance with the present invention preferably also contain substances that increase the mechanical strength and the porosity of the layers.
  • colloidal silica may be used.
  • the colloidal silica employed may be in the form of any commercially available water-dispersion of colloidal silica for example having an average particle size upto 40 nm, e.g. 20 nm.
  • inert particles of larger size than the colloidal silica can be added e.g. silica prepared according to Stöber as described in J. Colloid and Interface Sci., Vol. 26, 1968, pages 62 to 69 or alumina particles or particles having an average diameter of at least 100nm which are particles of titanium dioxide or other heavy metal oxides.
  • the surface of the hardened hydrophilic layer is given a uniform rough texture consisting of microscopic hills and valleys, which serve as storage places for water in background areas.
  • the thickness of a hardened hydrophilic layer in a material according to this invention may vary in the range from 0.2 to 25 ⁇ m, preferably in the range from 1 to 10 ⁇ m.
  • the above mentioned flexible supports may be opaque or transparent, e.g. a paper support or resin support.
  • a paper support preference is given to one coated at one or both sides with an Alpha-olefin polymer, e.g. a polyethylene layer which optionally contains an anti-halation dye or pigment.
  • an organic resin support e.g. cellulose esters such as cellulose acetate, cellulose propionate and cellulose butyrate; polyesters such as poly(ethylene terephthalate); polyvinyl acetals, polystyrene, polycarbonates; polyvinylchloride or poly-Alpha-olefins such as polyethylene or polypropylene.
  • One or more subbing layers may be coated between the support and the hardened hydrophilic layer for use in accordance with the present invention in order to get an improved adhesion between these two layers.
  • a preferred subbing layer for use in connection with the present invention is a subbing layer comprising a hydrophilic binder and silica.
  • hydrophilic binder in said subbing layer usually a protein, preferably gelatin may be used.
  • Gelatin can, however, be replaced in part or integrally by synthetic, semi-synthetic, or natural polymers.
  • Synthetic substitutes for gelatin are e.g. polyvinyl alcohol, poly-N-vinyl pyrrolidone, polyvinyl imidazole, polyvinyl pyrazole, polyacrylamide, polyacrylic acid, and derivatives thereof, in particular copolymers thereof.
  • Natural substitutes for gelatin are e.g. other proteins such as zein, albumin and casein, cellulose, saccharides, starch, and alginates.
  • the semi-synthetic substitutes for gelatin are modified natural products e.g.
  • gelatin derivatives obtained by conversion of gelatin with alkylating or acylating agents or by grafting of polymerizable monomers on gelatin, and cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose, phthaloyl cellulose, and cellulose sulphates.
  • a preferred silica in said subbing layer is a siliciumdioxide of the anionic type.
  • the colloidal silica preferably has a surface area of at least 100 m 2 per gram, more preferably a surface area of at least 300 m 2 per gram.
  • the surface area of the colloidal silica is determined according to the BET-value method described by S. Brunauer, P. H. Emmett and E. Teller, J.Amer. Chem. Soc. 60 , 309-312 (1938).
  • the silica dispersion may also contains other substances, e.g. aluminium salts, stabilising agents,biocides etc.
  • KIESELSOL is a registered trade name of Wegriken Bayer AG, Leverkusen, West-Germany whereby the number indicates the surface area in m 2 per gram).
  • the weight ratio of the hydrophilic binder to silica in the subbing layer is preferably less than 1.
  • the lower limit is not very important but is preferably at least 0.2.
  • the weight ratio of the hydrophilic binder to silica is more preferably between 0.25 and 0.5.
  • the coverage of said subbing layer is preferably more than 200 mg per m 2 but less than 750 mg per m 2 , more preferably between 250 mg per m 2 and 500 mg per m 2 .
  • the coating of the above defined subbing layer composition preferably proceeds from an aqueous colloidal dispersion optionally in the presence of a surface-active agent.
  • Suitable hydrophobic polymeric binders for use in accordance with the present invention include :
  • the hydrophobic binders used in connection with the present invention are copolymers of styrene or vinyltoluene, more preferably copolymers of styrene and (meth)acrylates or of vinyltoluene and butadiene derivatives, most preferably copolymers of styrene and butyl methacrylate or of vinyltoluene and butadiene
  • Suitable compounds capable of converting light into heat are preferably infrared absorbing components although the wavelength of absorption is not of particular importance as long as the absorption of the compound used is in the wavelength range of the light source used for imagewise exposure.
  • Particular useful compounds are for example dyes and in particular infrared dyes, carbon black, metal carbides, borides, nitrides, carbonitrides, bronze-structured oxides and oxides structurally related to the bronze family but lacking the A component e.g. WO 2.9 .
  • conductive polymer dispersions such as polypyrrole or polyaniline-based conductive polymer dispersions. The lithographic performance and in particular the print endurance obtained depends on the heat-sensitivity of the imaging element.
  • the amount of the compounds capable of converting light into heat into the hydrophobic heat sensitive composition is preferably between 0.01 and 2 g/m 2 , more preferably between 0.1 and 1.5 g/m 2 .
  • Suitable reactive compounds can be compounds which will react with each other under the influence of heat e.g. polyols such as di-trimethylolpropane.
  • the reactive compounds are hardenable by reaction with a free radical e.g. monomers with at least one polymerizable ethylenically unsaturated group.
  • Said monomer can be a monomer having one polymerizable ethylenically unsaturated group.
  • Monomers containing at least two polymerizable ethylenically unsaturated groups are more preferably used.
  • Particularly preferred are urethane type monomers, such as those of table I and those disclosed in EP-A 502562 and unsaturated esters of polyols, especially esters of polyols and an alpha-methylene carboxylic acid.
  • esters of a polyol and an alpha-methylene carboxylic acid are: ethylene diacrylate, glycerol tri(meth)acrylate, ethylene dimethacrylate, 1,3-propanediol di(meth)acrylate, 1,2,4-butanetriol tri(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, 1,4-benzenediol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol pentaacrylate, 1,5-pentanediol di(meth)acrylate, the bis acrylates and methacrylates of polyethylene glycols of molecular weight 200-500, and the like.
  • monomers suitable for use in the hydrophobic photopolymerizable composition in accordance with the present invention are e.g. the monomers disclosed in EP-A 502562, DEOS no. 4,109,239, 4,005,231, 3,643,216, 3,625,203, 3,516,257, 3,516,256 and 3,632,657. Further types of monomers suitable for use in the hydrophobic photopolymerizable composition in accordance with the present invention are disclosed in EP-A 522,616. It will be clear that these monomers can be used in admixture.
  • a prepolymer with at least one polymerizable ethylenically unsaturated group, preferably with two or more polymerizable ethylenically unsaturated groups can be used .
  • said prepolymer has a numerical average molecular weight of not more than 25,000, more preferably of not more than 10,000.
  • the acid-sensitive compound can be a monomer capable of undergoing cationic polymerization which are well known to one skilled in the art.
  • said mixture of compounds comprises a compound with at least two hydroxyl groups and a reagent which is capable of crosslinking under the influence of an acid said compound with at least two hydroxyl groups.
  • said mixture of compounds comprises a compound comprising at least two latent or masked electrophilic groups that are transformed into electrophilic groups upon reaction with acid and a compound containing an aromatic moiety that is susceptible to electrophilic aromatic substitution.
  • Monomers capable of undergoing cationic polymerization are preferably compounds comprising at least one vinylether, propenylether or epoxy function. More preferably said compounds comprises at least two of said functions. Most preferably polyfunctional epoxy compounds are used based e.g. on the reaction product of Bisphenol A, that is 2,2-bis(4-hydroxyphenyl)propane and epichlorohydrin, for example the resins sold under the registered trademark DER by Dow Chemicals.
  • Compounds comprising at least two hydroxyl groups can be low molecular compounds but may also be polymers.
  • Reagents which are capable of crosslinking under the influence of an acid said compounds with at least two hydroxyl groups are f.i. compounds comprising at least two isocyanate groups, for example the compounds sold under the registered trade name DESMODUR by Bayer, tetraalkoxymethyl glycolurils, for example the compound sold under the registered trade name CYMEL 1170 by Dyno Cyanamid and compounds represented by the following formula wherein Z represents -NRR' or a phenyl group, R, R' and R 1 to R 4 each independently represents a hydrogen atom, CH 2 OH or CH 2 OR 5 in which R 5 represents an alkyl group.
  • Compounds comprising at least two latent or masked electrophilic groups may be aliphatic compounds comprising at least two hydroxyl functions or compounds comprising an aromatic ring substituted with at least two latent or masked electrophilic groups or compounds comprising at least two aromatic rings comprising at least one latent or masked electrophilic group.
  • the latent or masked electrophilic group is preferably -CH 2 OR 6 , wherein R 6 represents a hydrogen atom or an acyl rest. Also preferably said aromatic rings are substituted phenols.
  • Compounds containing an aromatic moiety that are susceptible to electrophilic aromatic substitution may be low molecular weight compounds but are preferably polymers, more preferably polymers containing a phenolic moiety, most preferably polyvinyl 4-hydroxy-styreen or novolac resins.
  • compounds which can undergo a hardening reaction under the influence of alkali are polyfunctional epoxy compounds. More preferably polyfunctional epoxy compounds are used based on the reaction product of Bisphenol A, that is 2,2-bis(4-hydroxyphenyl)propane and epichlorohydrin , for example the resins sold under the registered trademark DER by Dow Chemicals.
  • Said reactive compound or mixture of reactive compounds is used in an amount which surpasses the absorptive capacity of the hydrophobic polymer binder for said compound or mixture of compounds.
  • said compounds or at least one compound of said mixture of compounds is not completely dissolved in the hydrophobic polymer binder and that the hydrophobic heat sensitive composition comprises at least two phases so that preferably a thin layer of substantially free reactive compound is present at least at one surface of the hydrophobic heat sensitive composition more preferably at the interface between the hydrophobic heat sensitive composition and the hydrophilic surface.
  • an imaging element of such a layer contiguous to the hydrophilic surface of the support can be demonstrated by peeling apart the heat sensitive composition and the thermo-adhesive layer or layers from the hydrophilic surface of the support and examining said freed hydrophilic surface with ESCA or TOF-SIMS for the presence of signals, resulting from a reactive compound or mixture of compounds which is capable of reacting under the influence of heat or under the influence of a reagent obtainable by decomposition of a heat sensitive compound.
  • Said reactive compound preferably has a boiling point above 100°C at normal atmospheric pressure.
  • azo and peroxide compounds are used e.g. 2,2 -azobisisobutyronitrile and benzoylperoxide. Said compounds are preferably used in an amount ranging from 0.001 to 1 g/m 2 , more preferably in an amount ranging from 0.01 to 0.25 g/m 2 .
  • Heat sensitive acid precursors for use in connection with the present invention include sulfonium compounds, in particular benzylsulfonium compounds, as disclosed in e.g. EP 612065, EP 615233, and US 5.326.677, inorganic nitrates such as e.g. Mg(NO 3 ) 2 .6H 2 O or organic nitrates such as guanidinium nitrate, ammonium nitrate, pyridinium nitrate etc... as disclosed in EP 462763, WO 81/1755, US 4.370.401, compounds that release a sulfonic acid such as 3-sulfolenes, e.g.
  • thermolytic compounds disclosed in GB 1.204.495 2,5-dihydrothio-thiophene-1,1-dioxides as disclosed in US 5.312.721, thermolytic compounds disclosed in GB 1.204.495, co-cristalin adducts of an amine and an volatile organic acid as disclosed in US 3.669.747, aralkylcyanoforms as disclosed in US 3.166.583, benzoinetosylaat, 2-nitrobenzyltosylaat and alkyl esters of organic sulfonic acids as described in EP 542008, thermo-acids disclosed in EP 159725 and DE 3515176, squaric acid generating compounds as disclosed in US 5.278.031, acid generating compounds disclosed in US 5.225.314 and US 5.227.277 and RD 11511 of November 1973.
  • Said heat sensitive acid precursors are preferably used in an amount ranging from 0.01 to 1 g/m 2 .
  • Heat sensitive alkali precursors comprises t.-butyloxycarbonyl masked amines and dicyandiamides as described by G. Eastmond et al. in Comprehensive Polymer Science , Vol 6, Pergamon Press.
  • non-thermoplastic polymeric compounds to give certain desirable characteristics, e.g. to improve adhesion to said hydrophilic surface of the support used in accordance with the present invention, wear properties, chemical inertness, etc.
  • Suitable non-thermoplastic polymeric compounds include cellulose, phenolic resins, melamine-formaldehyde resins, etc.
  • the hydrophobic heat sensitive composition can also contain immiscible polymeric or non-polymeric organic or inorganic fillers or reinforcing agents which are essentially transparent at the wavelengths used for the exposure of the imaging element, e.g.
  • organophil-ic silicas bentonites, silica, powdered glass, colloidal carbon, as well as various types of dyes and pigments in amounts varying with the desired properties of the hydrophobic heat sensitive composition .
  • the fillers are useful in improving the strength of the composition, reducing tack and in addition, as coloring agents.
  • Agents to improve the wetting and/or adjust the adhesion of the hydrophobic heat sensitive composition may be added.
  • Suitable agents are e.g. silicons, silicon containing polymers e.g. a poly(dimethylsiloxane)-polyether copolymer, poly(dimethylsiloxane)-polyester, silicon containing surfactants, fluor containing copolymers and fluor containing surfactants etc..
  • the heat sensitive composition can also comprise additionally a reactive compound which is capable of reacting under the influence of heat or under the influence of a reagent obtainable by decomposition of a heat sensitive compound and which is present in an amount which not surpasses the absorptive capacity of the hydrophobic polymer binder for said compound.
  • the hydrophobic heat sensitive composition has preferably a dry thickness in the range of 0.3 to 5 g/m 2 , more preferably in the range of 0.5 to 3.5 /m 2 , most preferably in the range of 0.75 to 2.5 g/m 2 .
  • the imaging element may be prepared by coating the layers on each other or by laminating layers or packets of layers to each other.
  • the imaging element is prepared by the following steps:
  • the imaging element is prepared by laminating the above described imaging element with its thermo-adhesive layer onto a receptor layer or preferably onto a pressure-adhesive layer coated on a receptor layer.
  • the imaging element is prepared by the following steps:
  • the imaging element is prepared by the following steps:
  • Suitable pressure-adhesive layers (PALs) for use in the present invention comprise one or more pressure sensitive adhesives.
  • Said pressure sensitive adhesives are preferably tacky elastomers e.g. block copolymers of styrene/isoprene, styrene/butadiene rubbers, butyl rubbers, polymers of isobutylene and silicones. Particularly preferred are natural rubbers and acrylate copolymers as disclosed in US-P 3,857,731.
  • the pressure-adhesive layer comprising a pressure sensitive adhesive may contain a binder.
  • Suitable binders for use in combination with the pressure sensitive adhesives are binders that are inert towards the pressure sensitive adhesives i.e. they do not chemically attack the pressure sensitive adhesives or act as a solvent for them. Examples of such binders are nitrocellulose, urethanes, gelatin, polyvinyl alcohol etc...
  • the amount of binder should be chosen such that the pressure sensitive adhesives are effectively anchored to the hydrophobic photosensitive composition.
  • the amount of binder is lower than 2.5 parts by weight with respect to the pressure sensitive adhesives and more preferably lower than 0.6.
  • the pressure-adhesive layer comprising a pressure sensitive adhesive may also contain a tackyfier e.g. rosin soap or a terpene.
  • the imaging element containing a pressure-adhesive layer comprises preferably also a receptor element on top of said pressure-adhesive layer.
  • said receptor element is(are) (a) transparent layer(s) contiguous to said pressure-adhesive layer e.g. a transparent organic resin layer.
  • the thickness of the pressure-adhesive layer is important for the adherence during the lamination/delamination process.
  • the thickness of said pressure-adhesive layer lies between 0.1 and 50 ⁇ m, more preferably between 0.1 and 15 ⁇ m.
  • a receptor layer according to the invention is a layer which is capable of adhering to the underlying contiguous layer and which is overlying the thermo-adhesive layer and the pressure-adhesive layer when the latter is present.
  • Said receptor layer is preferably stable at the processing conditions.
  • the particular layer used is dependant on the nature of the composition of the imaging element. Suitable receptor layers include paper; cardboard; metal sheets; foils and meshes e.g. aluminum, copper, steel, bronze etc.; transparent organic resins e.g.
  • cellulose esters such as cellulose acetate, cellulose propionate and cellulose butyrate, polyvinyl acetals, polystyrene, polycarbonate or polyvinylchloride; opaque foamed or pigmented polyester; silk; cotton and viscose rayon fabrics or screens.
  • Preferred receptor layers are commercially available paper brands as disclosed in WO 95 00342, and films of polyesters such as polyethylene terephthalate or of poly-Alpha-olefins such as polyethylene or polypropylene.
  • a receptor element according to the invention comprises at least a receptor layer.
  • Said receptor element may further comprises a thin additional layer.
  • Examples of such receptor elements are supports provided with a thin metal layer e.g. polyester supports provided with a vapour deposited metal layer and most useful polyethylene coated paper.
  • a receptor element may also comprise (an) additional layer(s) such as (a) backing layer(s).
  • an imaging element according to the present invention is image-wise or information-wise exposed to actinic radiation to harden the heat sensitive composition pattern-wise.
  • the exposure is preferably an infrared exposure, more preferably by an infrared light emitting laser.
  • Preferably used lasers are semiconductor lasers or YAG lasers e.g. Nd-YAG lasers.
  • the laser may have an output between 40 and 7500 mW.
  • Said exposure can be made through the front side or the back side of the imaging element.
  • the front side of the imaging element is that side where the thermo-adhesive layer is overlying the support and the back side of the imaging element is that side where the support is overlying the thermo-adhesive layer.
  • the imaging element is exposed through the front side.
  • the imaging element according to the present invention is a negative working imaging element. Indeed the information-wise exposure to actinic radiation hardens the hydrophobic heat sensitive composition pattern-wise in correspondence to the information-wise distribution of actinic radiation. Subsequent to the information-wise exposure the image is obtained, if said imaging element comprises as upper layer a thermo-adhesive layer, by (i) laminating before or after said exposure said imaging element with its thermo-adhesive layer to a receptor layer or more preferably to a pressure-sensitive layer coated or laminated on a receptor layer and (ii) peeling away a receptor element, comprising said receptor layer from the hydrophilic surface of the support, thereby transferring the non-hardened or insufficiently hardened parts of the hydrophobic photosensitive composition and the overlying layer(s) to the receptor element and uncovering the image comprised of the hydrophilic surface of the support and the retained hardened parts of the hydrophobic heat sensitive composition.
  • said imaging element comprises as upper layers a pressure-adhesive layer laminated or coated on a receiving layer the image is obtained subsequent to the information-wise exposure, by peeling away a receptor element, comprising said receptor layer from the hydrophilic surface of the support, thereby transferring the non-hardened or insufficiently hardened parts of the hydrophobic photosensitive composition and the overlying layer(s) to the receptor element and uncovering the image comprised of the hydrophilic surface of the support and the retained hardened parts of the hydrophobic heat sensitive composition.
  • the force, needed to peel away the heat sensitive composition from the hydrophilic surface of a support is called the peeling force of the heat sensitive composition.
  • Said peeling force is mainly a function of the nature of the used reactive compound or mixture of reactive compounds which is capable of reacting under the influence of heat or under the influence of a reagent obtainable by decomposition of a heat sensitive compound, polymers and their relative amounts in the heat sensitive composition and of the nature of the hydrophilic surface of the support.
  • the heat sensitive composition, coated on the hydrophilic surface of a support is, if not comprising a laminated receptor layer of at least 63 ⁇ m thick laminated against a 6 ⁇ m thick layer consisting of Baystal P 2000, coated on a subbed polyethylene terephthalte support (having an upper subbing layer contg. gelatine and silica) of 100 ⁇ m, being then the receptor layer.
  • the lamination is effected by means of a Codor lamipacker LPA 330 at 90°C and 300 mm/min.
  • the peel test occurs at 25°C and 50% relative humidity over a guide roller with a diameter of 13 mm and a weight of 75 g with a peel angle of 180°.
  • the support of the imaging element is fixed so that it remains planar during the whole measurement.
  • Said Instron is calibrated at 0 after the guide roller is put in place in a fold of the receptor layer.
  • the receptor layer is then peeled away at a speed of 1 m/min, adjusted on said Instron for a peel of 180°.
  • the necessary force for said peeling, as indicated by said Instron is noted; the numerical average of the result of 3 measurements is taken as the peeling force of the heat sensitive composition.
  • the peeling force of the heat sensitive photopolymerizable composition ranges preferably from 0.1 N/m to 12 N/m, more preferably from 0.2 N/m to 10 N/m.
  • the laminating is effected by means of a heating step, preferably at a temperature between 40 °C and 180 °C, more preferably at a temperature between 65 °C and 120 °C. Said heating may be applied to either or both the imaging element and the receptor element before, while or after bringing the receptor layer in contact with the thermo-adhesive layer of the imaging element.
  • the imaging element comprises a pressure-adhesive layer or the receptor layer is coated or laminated with a pressure-adhesive layer
  • said laminating requires a pressure step. Said pressure is applied while the pressure-adhesive layer is in contact with the thermo-adhesive layer of the imaging element.
  • An imaging element and a receptor element may be brought in contact before exposure.
  • the imaging element according to the present invention comprises a hydrophobic heat sensitive composition contiguous to a hydrophilic surface of a support
  • the obtained image can be used as a lithographic printing plate.
  • Pattern-wise transfer of the hydrophobic heat sensitive composition to a receptor material will then result in an image-wise differentiation between hydrophilic and hydrophobic parts that can be used to print with an oily or greasy ink.
  • the hydrophobic parts will be capable of accepting lithographic ink, whereas the hydrophilic areas, when moistened with water, will not accept the ink.
  • the areas which accept ink form the printing image areas and the ink-rejecting areas form the background areas.
  • Said lithographic printing plate can further be cleaned with water or an aqueous solution e. g. by wipping with a wet sponge, rinsing with a spray of unheated water or of an aqueous solution etc..
  • a carbon black dispersion was prepared by dissolving 60 g of PLIOTONE 3015 (a trade name of GOODYEAR for a copolymer of vinyltoluene-butadiene) in 900 g of methylethylketone in a ball mill and by adding 40 g of CORAX L6 (a trade name of DEGUSSA for a carbon pigment) and 0.5 g of SOLSPERSE 24000GR (a trade name of ZENECA RESINS for a dispersing aid). After 72 hours of milling the dispersion was ready to use.
  • PLIOTONE 3015 a trade name of GOODYEAR for a copolymer of vinyltoluene-butadiene
  • CORAX L6 a trade name of DEGUSSA for a carbon pigment
  • SOLSPERSE 24000GR a trade name of ZENECA RESINS for a dispersing aid
  • the obtained dispersion was coated on a polyethylene terephthalate film support having a thickness of 175 ⁇ m (having provided thereon a hydrophilic subbing layer) at a wet coating thickness of 50 g/m2, dried at 30°C and subsequently hardened by subjecting it to a temperature of 57°C for 1 week.
  • lithographic base Onto the above obtained hydrophilic surface of a support, furtheron called lithographic base was coated a heat sensitive composition prepared by adding 5 g of a 10% solution of ditrimethylolpropane in methylethylketone to 95 g of the carbon black dispersion CBD-I. The mixture was coated to a wet coating thickness of 20 ⁇ m.
  • the above obtained imaging element was overcoated with a solution consisting of 20% aqueous dispersion of Baystal P2000 (from BAYER A.G., Germany) which is a copolymer containing styrene, butadiene and acrylic acid with a glass transition temperature of 34°C (measured with the "1090 Thermolyzer” of Dupont Co.), a melt viscosity of more than 13420 Poise and an elasticity corresponding to a tg ⁇ -1 value of 3.54 both last properties measured at 120 °C (with a "Viscoelastic melt tester" of Rheometrics Co, Surrey, UK.), to a wet coating thickness of 30 g/m 2 .
  • Baystal P2000 from BAYER A.G., Germany
  • the imaging element was exposed with a NDYLF-laser at a speed of 8.8 m/s.
  • the output power was varied from 0.29 W to 0.80 W.
  • the spot size of the laser beam at 1/e 2 yielded 14.9 ⁇ m. Single scan lines were imaged.
  • the exposed imaging element was then placed in face-to-face contact with the receptor element, being a subbed polyethylene therephthalate support (having an upper subbing layer containing gelatine and silica).
  • the contacting elements were conveyed through a roll laminator device at 90°C and at a speed of 0.3 m/min. and the elements were peeled apart whereby the non-exposed parts of the heat sensitive composition are removed and the exposed areas remain on the lithographic base, thus being a negative working system.
  • the obtained image on the lithographic base could be used to print on a conventional offset press using a commonly used ink and fountain. Good copies were obtained.
  • An imaging element was prepared similar to the imaging element of example 1 with the exception that the heat sensitive composition was coated from a mixture prepared by adding 2.5g of a 10% solution of AIBN (2,2'-azobisisobutyronitrile from AKZO) in methylethylketone and 2.5 g of a 10% solution of SARTOMER 399TM (dipentaerythritolpentaacrylate from CRAY VALLEY) in methylethylketone to 95 g of the carbon black dispersion CBD-I. The mixture was coated to a wet coating thickness of 20 ⁇ m.
  • AIBN 2,2'-azobisisobutyronitrile from AKZO
  • SARTOMER 399TM dipentaerythritolpentaacrylate from CRAY VALLEY
  • the imaging element was exposed and then laminated under similar conditions as used for example 1.
  • the obtained image on the lithographic base could be used to print on a conventional offset press using a commonly used ink and fountain. Good copies were obtained.
  • An imaging element was prepared similar to the imaging element of example 1 with the exception that the heat sensitive composition was coated from a mixture prepared by adding 3.0 g of a 10% solution of di-trimethylolpropane in methylethylketone, 0.5 g of DEGACURETM KI85 (a triphenylsulfonium salt from DEGUSSA) and 3.0 g of a 10% solution of CYMEL 301TM (melamine resin from DYNO CYANAMID) in methylethylketone to 92.5 g of the carbon black dispersion CBD-I. The mixture was coated to a wet coating thickness of 20 ⁇ m.
  • the imaging element was exposed and then laminated under similar conditions as used for example 1.
  • the obtained image on the lithographic base could be used to print on a conventional offset press using a commonly used ink and fountain. Good copies were obtained.
  • a heat sensitive composition prepared by adding 5g of a 10% solution of AIBN (2,2'-azobisisobutyronitrile from AKZO) in methylethylketone, and 10 g of a 10% solution of SARTOMER 399TM (dipentaerythritolpentaacrylate from CRAY VALLEY) in methylethylketone to 85 g of the carbon black dispersion CBD-I.
  • the mixture was coated to a wet coating thickness of 20 ⁇ m.
  • the above obtained imaging element was overcoated with a solution consisting of 20% aqueous dispersion of Baystal P2000 (from BAYER A.G., Germany) which is a copolymer containing styrene, butadiene and acrylic acid with a glass transition temperature of 34°C (measured with the "1090 Thermolyzer” of Dupont Co.), a melt viscosity of more than 13420 Poise and an elasticity corresponding to a tg ⁇ -1 value of 3.54 both last properties measured at 120 °C (with a "Viscoelastic melt tester" of Rheometrics Co, Surrey, UK.), to a wet coating thickness of 30 g/m 2 .
  • Baystal P2000 from BAYER A.G., Germany
  • the imaging element was exposed with a NDYLF-laser at a speed of 8.8 m/s.
  • the output power was varied from 0.29 W to 0.80 W.
  • the spot size of the laser beam at l/e 2 yielded 14.9 ⁇ m. Single scan lines were imaged.
  • the exposed imaging element was then placed in face-to-face contact with the receptor element, being a subbed polyethylene therephthalate support (having an upper subbing layer containing gelatine and silica).
  • the contacting elements were conveyed through a roll laminator device at 90°C and at a speed of 0.3 m/min. and the elements were peeled apart whereby the non-exposed parts of the heat sensitive composition are removed and the exposed areas remain on the lithographic base, thus being a negative working system.
  • the obtained image on the lithographic base could be used to print on a conventional offset press using a commonly used ink and fountain. Good copies were obtained.
  • a heat sensitive composition prepared by adding 5g of a 10% solution of AIBN (2,2'-azobisisobutyronitrile from AKZO) in methylethylketone, and 10 g of a 10% solution of SARTOMER 399 (dipentaerythritolpentaacrylate from CRAY VALLEY) in methylethylketone to 85 g of the carbon black dispersion CBD-I.
  • the mixture was coated to a wet coating thickness of 20 ⁇ m.
  • the above obtained imaging element was overcoated with a solution consisting of 20% aqueous dispersion of Baystal P2000 (from BAYER A.G., Germany) which is a copolymer containing styrene, butadiene and acrylic acid with a glass transition temperature of 34°C (measured with the "1090 Thermolyzer” of Dupont Co.), a melt viscosity of more than 13420 Poise and an elasticity corresponding to a tg ⁇ -1 value of 3.54 both last properties measured at 120 °C (with a "Viscoelastic melt tester" of Rheometrics Co, Surrey, UK.), to a wet coating thickness of 30 g/m 2 .
  • Baystal P2000 from BAYER A.G., Germany
  • the imaging element was exposed with a NDYAG-laser at a speed of 100 m/s.
  • the output power was varied from 0.6 W to 6.2 W.
  • the spot size of the laser beam at l/e 2 yielded 13.8 um. Single scan lines were imaged.
  • the exposed imaging element was then placed in face-to-face contact with a pressure sensitive adhesive coated on a receptor layer(PERMAGARD PG7034 from MACTAC EUROPE S.A.).
  • the contacting elements were conveyed through a roll laminator device at room temperature and at a speed of 0.3 m/min. and the elements were peeled apart wereby the non-exposed parts of the heat sensitive layer are removed and the exposed areas remain on the lithographic base, thus being a negative working system.
  • the obtained image on the lithographic base could be used to print on a conventional offset press using a commonly employed ink and fountain. Excellent copies were obtained.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Claims (10)

  1. Ein wärmeempfindliches bilderzeugendes Element, das folgende Bestandteile umfaßt :
    einen Träger mit einer hydrophilen Oberfläche,
    angrenzend an die hydrophile Oberfläche eines Trägers eine hydrophobe wärmeempfindliche Zusammensetzung mit einem hydrophoben polymeren Bindemittel, einer Verbindung, die Licht in Wärme umzuwandeln vermag, und einer härtbaren Zusammensetzung, wobei die härtbare Zusammensetzung ein Polyol ist, eine durch Reaktion eines freien Radikals härtbare Verbindung, ein Monomeres, das unter Einwirkung einer Säure eine kationische Polymerisation eingehen kann, eine Verbindung mit wenigstens zwei Hydroxylgruppen und ein Reagens, das in der Lage ist, unter der Einwirkung einer Säure die Verbindung mit wenigstens zwei Hydroxylgruppen zu vernetzen, eine Verbindung mit wenigstens zwei latenten oder maskierten elektrophilen Gruppen, die bei Reaktion mit einer Säure in elektrophile Gruppen umgewandelt werden, eine Verbindung mit einem aromatischen Anteil, bei der eine elektrophile aromatische Substitution auftreten kann, oder mehrfunktionelle Epoxyverbindungen, die unter Einwirkung eines Alkalis und eines Initiators oder eines Säurevorläufers oder Alkalivorläufers härtbar sind, wobei die Menge der härtbaren Zusammensetzung das Absorptionsvermögen des hydrophoben polymeren Bindemittels übersteigt und dadurch eine separate Phase bildet,
    eine oder mehrere beim Erwärmen klebrig werdende Schichten mit einer Stärke zwischen 0,1 und 0,50 µm, wobei wenigstens eine der beim Erwärmen klebrig werdenden Schichten an die hydrophobe wärmeempfindliche Zusammensetzung grenzt.
  2. Wärmeempfindliches bilderzeugendes Element nach Anspruch 1, dadurch gekennzeichnet, daß die beim Erwärmen klebrig werdende, an die hydrophobe wärmeempfindliche Zusammensetzung grenzende Schicht einen Einfrierpunkt Tg zwischen 20°C und 45°C, eine Schmelzviskosität von mehr als 7.000 Poise und eine Elastizität entsprechend einem (tg δ)-1-Wert von mehr als 1,30 aufweist, wobei beide letzten Werte bei einer Temperatur von 120°C gemessen sind.
  3. Wärmeempfindliches bilderzeugendes Element nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die beim Erwärmen klebrig werdende Schicht mit einer Empfangsschicht, die in der Lage ist, an der beim Erwärmen klebrig werdenden Schicht zu haften, überzogen ist.
  4. Wärmeempfindliches bilderzeugendes Element nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die beim Erwärmen klebrig werdende Schicht mit wenigstens einer selbsthaftenden Schicht überzogen ist.
  5. Wärmeempfindliches bilderzeugendes Element nach Anspruch 4, dadurch gekennzeichnet, daß die selbsthaftende Schicht mit einer Empfangsschicht überzogen ist.
  6. Wärmeempfindliches bilderzeugendes Element nach irgendeinem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Stärke der selbsthaftenden Schicht zwischen 0,1 und 50 µm liegt.
  7. Wärmeempfindliches bilderzeugendes Element nach irgendeinem der Ansprüche 3, 5 oder 6, dadurch gekennzeichnet, daß die Empfangsschicht eine lichtdurchlässige Schicht aus organischem Harz ist.
  8. Wärmeempfindliches bilderzeugendes Element nach irgendeinem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die hydrophile Oberfläche eines Trägers ein gekörnter und eloxierter Aluminiumträger ist.
  9. Wärmeempfindliches bilderzeugendes Element nach irgendeinem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß die hydrophile Oberfläche eines Trägers eine Schicht aus mit einem Tetraalkylorthosilikat gehärtetem Polyvinylalkohol ist, wobei das Gewichtsverhältnis des Polyvinylalkohols zum Tetraalkylorthosilikat zwischen 0,5 und 5 liegt.
  10. Ein Verfahren zur Herstellung einer lithografischen Druckplatte, mit folgenden Stufen :
    (a) die bildmäßige oder informationsmäßige Belichtung eines wie in irgendeinem der Ansprüche 1 bis 9 beschriebenen bilderzeugenden Elements,
    (b) die Entwicklung des belichteten bilderzeugenden Elements,
    wobei die Entwicklung der angegebenen Reihe nach folgende Stufen umfaßt :
    (i) die vor oder nach der Belichtung vorgenommene Laminierung der beim Erwärmen klebrig werdenden Schicht auf einer Empfangsschicht oder, wenn das bilderzeugende Element keine selbsthaftende Schicht enthält, die vor oder nach der Belichtung vorgenommene Laminierung der beim Erwärmen klebrig werdenden Schicht auf einer Empfangsschicht oder einer selbsthaftenden Schicht, und
    (ii) das Abziehen der Empfangsschicht von der hydrophilen Oberfläche des Trägers, wodurch die hydrophobe lichtempfindliche Zusammensetzung mustermäßig auf die Empfangsschicht übertragen wird.
EP19950203494 1995-12-14 1995-12-14 Wärmeempfindliches Aufzeichnungselement und Verfahren zur Herstellung von Flachdruckformen damit Expired - Lifetime EP0779161B1 (de)

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DE1995617815 DE69517815T2 (de) 1995-12-14 1995-12-14 Wärmeempfindliches Aufzeichnungselement und Verfahren zur Herstellung von Flachdruckformen damit
EP19950203494 EP0779161B1 (de) 1995-12-14 1995-12-14 Wärmeempfindliches Aufzeichnungselement und Verfahren zur Herstellung von Flachdruckformen damit
US08/762,441 US6010817A (en) 1995-12-14 1996-12-09 Heat sensitive imaging element and a method for producing lithographic plates therewith
JP35178996A JP2901235B2 (ja) 1995-12-14 1996-12-12 感熱性画像形成要素及びそれを用いて平版印刷版を作製する方法

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EP19950203494 EP0779161B1 (de) 1995-12-14 1995-12-14 Wärmeempfindliches Aufzeichnungselement und Verfahren zur Herstellung von Flachdruckformen damit

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JP3713920B2 (ja) * 1997-09-22 2005-11-09 コニカミノルタホールディングス株式会社 感熱性平版印刷版材料及びその製造方法、並びに、画像形成方法
JP2002023350A (ja) 2000-07-07 2002-01-23 Fuji Photo Film Co Ltd ネガ型平版印刷版原版
JP4512281B2 (ja) 2001-02-22 2010-07-28 富士フイルム株式会社 ネガ型平版印刷版原版
JP4266077B2 (ja) 2001-03-26 2009-05-20 富士フイルム株式会社 平版印刷版原版及び平版印刷方法
EP1403043B1 (de) 2002-09-30 2009-04-15 FUJIFILM Corporation Polymerisierbare Zusammensetzung und Flachdruckplattenvorläufer
JP2004126050A (ja) 2002-09-30 2004-04-22 Fuji Photo Film Co Ltd 平版印刷版原版
JP4137577B2 (ja) 2002-09-30 2008-08-20 富士フイルム株式会社 感光性組成物
EP1431032B1 (de) 2002-12-18 2015-12-09 FUJIFILM Corporation Polymerisierbare Zusammensetzung und lithographische Druckplattenvorläufer
JP4150261B2 (ja) 2003-01-14 2008-09-17 富士フイルム株式会社 平版印刷版原版の製版方法
JP2004252201A (ja) 2003-02-20 2004-09-09 Fuji Photo Film Co Ltd 平版印刷版原版
JP4299639B2 (ja) 2003-07-29 2009-07-22 富士フイルム株式会社 重合性組成物及びそれを用いた画像記録材料
JP2005099284A (ja) 2003-09-24 2005-04-14 Fuji Photo Film Co Ltd 感光性組成物及び平版印刷版原版
EP2047988B1 (de) * 2007-10-09 2014-03-12 Agfa Graphics N.V. Lithographiedruckplattenvorläufer
EP3686011A1 (de) * 2019-01-23 2020-07-29 Agfa Nv Lithographiedruckplattenvorläufer

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US3580719A (en) * 1969-08-04 1971-05-25 Agfa Gevaert Nv Thermographic recording process
JPS60101088A (ja) * 1983-11-08 1985-06-05 Ricoh Co Ltd 感光感熱記録材料
WO1995000342A1 (en) * 1993-06-25 1995-01-05 Agfa-Gevaert Naamloze Vennootschap Process for the formation of a heat mode image

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DE69517815T2 (de) 2001-02-01

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