EP0582144A1 - Laseradressierbares wärmeempfindliches Aufzeichnungsmaterial - Google Patents

Laseradressierbares wärmeempfindliches Aufzeichnungsmaterial Download PDF

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Publication number
EP0582144A1
EP0582144A1 EP93111757A EP93111757A EP0582144A1 EP 0582144 A1 EP0582144 A1 EP 0582144A1 EP 93111757 A EP93111757 A EP 93111757A EP 93111757 A EP93111757 A EP 93111757A EP 0582144 A1 EP0582144 A1 EP 0582144A1
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EP
European Patent Office
Prior art keywords
silver
recording material
thermal recording
dye
imaging system
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EP93111757A
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English (en)
French (fr)
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EP0582144B1 (de
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Stanley C. C/O Minnesota Mining And Busman
Thomas A. c/o Minnesota Mining and Isberg
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3M Co
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Minnesota Mining and Manufacturing Co
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/4989—Photothermographic systems, e.g. dry silver characterised by a thermal imaging step, with or without exposure to light, e.g. with a thermal head, using a laser
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49836—Additives
    • G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers
    • G03C1/49854—Dyes or precursors of dyes
    • 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
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/32—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers one component being a heavy metal compound, e.g. lead or iron
    • 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
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • 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
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/337—Additives; Binders
    • B41M5/3377—Inorganic compounds, e.g. metal salts of organic acids

Definitions

  • thermographic material that can be directly imaged using a high power laser diode.
  • thermographic imaging process relies on the use of heat to help produce an image.
  • a thermally sensitive image forming layer is coated on top of a suitable base or substrate material such as paper, plastics, metals, glass, and the like.
  • the resulting thermographic construction is then heated to an elevated temperature, typically in the range of about 60°-225°C for a period of tens of microseconds, e.g., 20-30 microseconds, resulting in the formation of an image.
  • the thermographic construction is brought into contact with the thermal head of a thermographic recording apparatus, such as a thermal printer, thermal facsimile, and the like.
  • an anti-stick layer is coated on top of the imaging layer to prevent sticking of the thermographic construction to the thermal head of the apparatus utilized.
  • Thermographic materials whose image-forming layers are based on silver salts of long chain fatty acids, such as silver behenate, are known. At elevated temperatures, silver behenate is reduced by a reducing agent for silver ion such as methyl gallate, hydroquinone, substituted hydroquinones, hindered phenols, catechol, pyrogallol, ascorbic acid, ascorbic acid derivatives, leuco dyes, and the like, whereby an image is formed.
  • a reducing agent for silver ion such as methyl gallate, hydroquinone, substituted hydroquinones, hindered phenols, catechol, pyrogallol, ascorbic acid, ascorbic acid derivatives, leuco dyes, and the like, whereby an image is formed.
  • thermographic constructions it is also known that other additives can be added to imaging layers of thermographic constructions to enhance their effectiveness.
  • U.S. Pat. No. 2,910,377 discloses that the silver image for such materials can be improved in color and density by the addition of toners to the imaging layer. Toners that give primarily image density enhancement are also referred to as development accelerators.
  • U.S. Pat. No. 3,080,254 discloses the use of phthalazinone as a toner in heat-sensitive copying paper.
  • U.S. Pat. No. 3,847,612 discloses an improved imaging system containing an imidazole in combination with phthalic acid and the like. Phthalazine in combination with phthalic acid and other organic acids also provide an improvement in image formation. Such disclosed combinations are particularly valuable when relatively weak reducing agents, such as hindered phenols, are used as the developer for silver soaps.
  • U.S. Pat. No. 4,585,734 discloses the achievement of good toning when a combination of phthalazine and an active hydrogen-containing heterocyclic compound such as phthalimide, naphthalimide, pyrazole, and succinimide are employed in dry silver imaging systems.
  • High power laser diodes have been used in the past to simultaneously light-expose and thermally-develop photothermographic media that contain near-infrared dyes.
  • light is used to generate a latent image in dye-sensitized silver halides while at the same time light-to-heat conversion elements (e.g., near-infrared dyes) convert near-infrared light to heat that thermally develops the silver halide latent image with an organic silver salt and reducing agent.
  • European Pat. Appl. No. 332,455 published Sept. 13, 1989
  • 5,041,369 disclose splitting a beam of near-infrared light, one portion of which passes through a second harmonic generation device to produce blue light that exposes a silver halide photothermographic medium.
  • the imaged areas are developed by exposure of the imaged areas to the remaining portion of the near-infrared beam.
  • U.S. Pat. No. 4,619,892 discloses a radiation-sensitive element comprising at least three silver halide emulsion layers, two of which are sensitized to infrared radiation by employing infrared sensitizing dyes.
  • thermographic color recording materials comprising 3,5-dihydroxybenzoic acid, a di- or triarylmethane thiolactone leuco dye, silver behenate, and a binder. Color formation is activated at temperatures of about 100°C.
  • This patent discloses a full-color imaging system using false color, near-infrared laser exposures of individual layers containing yellow, magenta, and cyan dye precursors and three different near-infrared absorbing dyes which cause development of the layer in which they are contained. Additionally, the patent does not disclose the formation of black images. In fact, the silver ions in the silver behenate are not reduced, but simply serve to irreversibly bind the thiobenzoate portion of the dye so that it cannot convert to the leuco form.
  • Japanese Kokai Application No. 1-274,129 discloses the exposure of compositions containing silver sulfonates having specified infrared (not near-infrared) absorption spectrum characteristics.
  • a carbon dioxide laser tuned to correspond to this infrared absorption wavelength is used to expose and simultaneously thermally develop this film, apparently to give a black image.
  • the silver sulfonate acts as its own light-to-heat conversion element.
  • that application requires the use of a carbon dioxide laser which is much less desirable for imaging applications than near-infrared laser diodes.
  • the black silver image that is generated by the heat produced by the light-to-heat converting near-infrared-absorbing dyes becomes its own light-to-heat conversion element since black silver also absorbs in the near-infrared region of the spectrum. Therefore, the developing black silver image becomes its own "catalyst" for production of more black silver in a silver soap system. Consequently, less near-infrared dye is needed and less background stain is left by the dye.
  • One of the dyes used is very neutral colored and is less visible in the final product, giving lower background densities.
  • thermographic material containing certain dyes and a reducing agent for silver ion is an effective laser diode addressable imaging system.
  • the present invention provides imageable materials which, when developed, have high image densities for a given development time as opposed to thermographic imaging systems which do not contain the reducing agents and dyes utilized herein.
  • the present invention provides a thermal recording material comprising a base or support coated with an imaging system, the imaging system consisting essentially of: (a) a thermally reducible source of silver; (b) reducing agent for silver ion; (c) a dye which absorbs electromagnetic radiation in the wavelength range of about 500-1100 nm; and (d) a polymeric binder.
  • the reducing agent comprises a 3-indazolinone or a urea compound of the structures disclosed later herein.
  • the dye employed is a near-infrared absorbing dye.
  • the electromagnetic radiation absorbing dye is in a layer adjacent to a layer containing the thermally reducible source of silver and reducing agent for silver ion.
  • near-infrared refers to the wavelength region between about 650 nm and 1100 nm, and preferably between about 750-1100 nm.
  • thermographic materials e.g., films or papers
  • thermographic materials can be imaged electronically using a simple laser scanner that requires no post-thermal processing step for the media.
  • Laser scanning technology gives higher resolution than a thermal stylus printhead, leading to this media's utility for high resolution applications such as graphic arts and diagnostic imaging.
  • abrasion of the thermographic media is not a problem.
  • the image forming system contains a thermally reducible source of silver.
  • the latter are materials, which in the presence of a reducing agent, undergo reduction at elevated temperatures, e.g., 60°-225°C.
  • these materials are silver salts of long chain alkanoic acids (also known as long chain aliphatic carboxylic acids or fatty acids) containing 10 to 30 carbon atoms and more preferably, 10 to 28 carbon atoms.
  • silver soaps are also known in the art as "silver soaps.”
  • Non-limiting examples of silver salts of aliphatic carboxylic acids include silver behenate, silver stearate, silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate, silver maleate, silver fumarate, silver tartarate, silver linoleate, silver butyrate, silver camphorate, and mixtures thereof.
  • Complexes of organic or inorganic silver salts wherein the ligand has a gross stability constant between 4.0-10.0 can also be used.
  • Silver salts of aromatic carboxylic acids and other carboxyl group-containing compounds include silver benzoate, a silver-substituted benzoate such as silver 3,5-dihydroxybenzoate, silver o -methylbenzoate, silver m -methylbenzoate, silver p -methylbenzoate, silver 2,4-dichlorobenzoate, silver acetamidobenzoate, silver p -phenyl benzoate, etc., silver gallate, silver tannate, silver phthalate, silver terephthalate, silver salicylate, silver phenylacetate, silver pyromellitate, silver salts of 3-carboxymethyl-4-methyl-4-thiazoline-2-thiones or the like as described in U.S. Pat.
  • Preferred examples of these compounds include silver 3-mercapto-4-phenyl-1,2,4-triazolate, silver 2-mercaptobenzimidazolate, silver 2-mercapto-5-aminothiadiazolate, silver 2-( S -ethylglycolamido)benzothiazolate; silver salts of thioglycolic acids such as silver salts of S -alkyl thioglycolic acids (wherein the alkyl group has from 12 to 22 carbon atoms); silver salts of dithiocarboxylic acids such as silver dithioacetate, silver thioamidoate, silver 1-methyl-2-phenyl-4-thiopyridine-5-carboxylate, silver triazinethiolate, silver 2-sulfidobenzoxazole; and silver salts as disclosed in U.S.
  • silver salts of a compound containing an amino group can be used.
  • Preferred examples of these compounds include silver salts of benzotriazoles, such as silver benzotriazolate; silver salts of alkyl-substituted benzotriazoles such as silver methylbenzotriazolate, etc.; silver salts of halogen-substituted benzotriazoles such as silver 5-chlorobenzotriazolate, etc.; silver salts of carboimidobenzotriazoles, etc.; silver salts of 1,2,4-triazoles and 1- H -tetrazoles as described in U.S. Pat. No. 4,220,709; silver salts of imidazoles; and the like.
  • the silver source material should constitute from about 5-50 percent by weight of the image forming system and more preferably, from about 10-30 percent by weight.
  • any reducing agent for silver ion can be used in the present invention.
  • Such reducing agents are well-known to those skilled in the art.
  • examples of such reducing agents include, but are not limited to, methyl gallate; hindered phenols; catechol; pyrogallol; hydroquinones; substituted hydroquinones; ascorbic acid; ascorbic acid derivatives; leuco dyes; and the like.
  • the reducing agent comprises a 3-indazolinone or urea compound as a development accelerator.
  • 3-indazolinone compounds used in the present invention preferably have the following structure: wherein: R is selected from the group consisting of: hydrogen; an alkyl group of 1 to 4 carbon atoms; halogen; -COOH and - R1 COOH wherein R1 is an alkyl group having from 1 to 4 carbon atoms.
  • R is hydrogen or an alkyl group having from 1 to 4 carbon atoms and most preferably, R is hydrogen.
  • 3-indazolinone compounds can be synthesized according to procedures well known to those skilled in the art of synthetic organic chemistry. Alternatively, such materials are commercially available, such as from Aldrich Chemical Company of Milwaukee, Wisconsin; Lancaster Chemical Company of Windham, New Hampshire; and K & K Laboratories of Cleveland, Ohio.
  • group is intended to include not only pure hydrocarbon substituents such as methyl, ethyl, and the like, but also such hydrocarbon substituents bearing conventional substituents in the art such as hydroxy, alkoxy, phenyl, halo (F, Cl, Br, I), cyano, nitro, amino, etc.
  • Urea compounds used in the present invention preferably have the following formula: wherein: R2 and R3 each independently represent hydrogen; a C1-C10 alkyl or cycloalkyl group; or phenyl; or R2 and R3 together form a heterocyclic group containing up to 6 ring atoms.
  • R2 and R3 represent hydrogen; a C1 to C5 alkyl or cycloalkyl group; or phenyl; or R2 and R3 together form a heterocyclic group containing up to 5 ring atoms.
  • urea compounds can be readily synthesized and are commercially available.
  • Non-limiting examples of such urea compounds include: Whatever reducing agent is employed in the present invention is preferably used in an amount of about 0.5-10.0 weight percent and more preferably, 1.0-3.0 weight percent; based upon the total weight of the imaging system.
  • the image forming system of the present invention employs a dye which absorbs electromagnetic radiation having a wavelength in the range of between about 500-1100 nm.
  • the dye employed is a near-infrared light absorbing dye which absorbs light in the wavelength range of about 650-1100 nm and more preferably, about 750-1100 nm.
  • the electromagnetic radiation absorbing dye can be employed in the same layer as the thermally reducible source of silver and reducing agent for silver ion or alternatively, the dye can be employed in a layer adjacent to the layer containing the reducible source of silver and the reducing agent for silver ion.
  • Suitable dyes include, but are not limited to, oxonol, squarylium, chalcogenopyrylarylidene, bis(chalcogenopyrylo)polymethine, bis(aminoaryl)polymethine, merocyanine, trinuclear cyanine, indene-bridged polymethine, oxyindolizine, ferrous complex, quinoid, nickel dithiolene complex, and cyanine dyes such as carbocyanine, azacarbocyanine, hemicyanine, styryl, diazacarbocyanine, triazacarbocyanine, diazahemicyanine, polymethinecyanine, azapolymethinecyanine, holopolar, indocyanine, and diazahemicyanine dyes.
  • the electromagnetic radiation absorbing dyes should be present in an amount of from about 0.1-10.0 weight present and more preferably, in an amount of from about 0.3-6.0 weight present, based upon the total weight of the imaging system employed in the present invention.
  • thermographic materials of the present invention are imaged by exposure to near-infrared laser radiation, typically from a near-infrared laser diode.
  • near-infrared laser diodes may be advantageously arranged in an array to increase imaging speed.
  • Lasers that can be used to provide near-infrared radiation include substantially any laser capable of generating light in the near-infrared region of the electromagnetic spectrum, including dye lasers; gas lasers such as krypton-ion lasers; solid state diode lasers such as aluminum gallium arsenide diode lasers that emit in the region of 750 to 870 nm; and diode pumped solid state lasers such as Nd:YAG, Nd:YLF, or Nd:Glass.
  • the imaging elements of the present invention are not light-sensitive in the traditional sense and therefore, do not need to contain photosensitive agents such as silver halides; photoinitiator; or photogenerated bleaching agents.
  • the imaging elements can have less than 1% by weight (substantially no effective amount of) these materials and perform well. They may be totally free of these materials in the imaging element.
  • the image forming element utilized in the present invention also employs a binder.
  • a binder Any conventional polymeric binder known to those skilled in the art can be utilized.
  • the binder may be selected from any of the well-known natural and synthetic resins such as gelatin, polyvinyl acetals, polyvinyl chloride, cellulose acetate, polyolefins, polyesters, polystyrene, polyacrylonitrile, polycarbonates, and the like.
  • Copolymers and terpolymers are, of course, included in these definitions, examples of which, include, but are not limited to, the polyvinyl aldehydes, such as polyvinyl acetals, polyvinyl butyrals, polyvinyl formals, and vinyl copolymers.
  • the binder should be present in the imaging layer in an amount in the range of 15-60 weight percent and more preferably, 25-50 weight percent, based upon the total weight of the imaging system.
  • toners such as phthalazinone, phthalazine, and phthalimide can also be used in the imaging system, if desired.
  • the toner should preferably be present in the imaging system in an amount in the range of 1-6 weight percent and more preferably, 2-5 weight percent, based upon the total weight of the imaging system.
  • any suitable base or substrate material known to those skilled in the art can be used in the present invention. Such materials can be opaque, translucent, or transparent. Commonly employed base or substrate materials utilized in the thermographic arts include, but are not limited to, paper; opaque or transparent polyester and polycarbonate films; and specularly light reflective metallic substrates such as silver, gold, and aluminum. As used herein, the phrase "specularly light reflecting metallic substrates" refers to metallic substrates, which when struck with light, reflect the light at a particular angle as opposed to reflecting the light across a range of angles.
  • an anti-stick layer positioned on top of the imaging system, may be used.
  • Any conventional anti-stick material may be employed in the present invention.
  • anti-stick materials include, but are not limited to waxes, silica particles, styrene-containing elastomeric block copolymers such as styrene-butadiene-styrene, styrene-isoprene-styrene, and blends thereof with such materials as cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate.
  • an anti-static or anti-stick layer may optionally be applied to the back of the support.
  • Materials for such purpose are well known in the photothermographic imaging art.
  • imaging, anti-stick, and anti-static layers employed in the present invention can be applied by any method known to those skilled in the art such as knife coating, roll coating, dip coating, curtain coating, hopper coating, etc.
  • butvar B-76 is a tradename for a polyvinyl butyral resin sold by Monsanto Chemical Co. of St. Louis, MO.
  • the near-infrared laser diode had a maximum power output of 150 mW.
  • a power supply was used to modulate the power output from the laser diode.
  • a mechanical shutter was used to modulate the exposure time.
  • the laser diode was focused to a spot size ca . 60 microns at the film plane.
  • Silver behenate homogenate may be prepared as disclosed in U.S. Pat. No. 4,210,717 (column 2, lines 55-57) or U.S. Pat. No. 3,457,075 (column 4, lines 23-45 and column 6, lines 37-44).
  • PC 364 has the structural formula :
  • IR125 has the structural formula :
  • SQ1 has the structural formula :
  • the olefin was oxidized in iodine, sodium iodide and refluxing methanol to yield, after recrystallization, the carbazolium salt 2,4,4,4a,9-pentamethyl-4,4a-dihydro-3H-carbazolium iodide.
  • SQ1 was prepared by condensing two equivalents of the free base form of the carbazolium salt with squaric acid according to the method of Kuramoto ( Dyes & Pigments , 1989, 11, 21).
  • CyasorbTM 165 dye has the structural formula :
  • Example 1-6 The formulations of Examples 1-6 were prepared by mixing 15 g of the above dispersion with additional ingredients as disclosed in Table 1.
  • Table 1 Ingredient Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Methyl gallate 0.3 g 0.3 g 0.3 g 0.3 g 0.3 g Phthalazinone 0.1 g 0.1 g 0.1 g 0.1 g 0.1 g 0.1 g 3-Indazolinone 0.1g 0.1g 0.1g 0.1g 0.1g 0.1g 0.1g IR125* 0.03 g 0.01 g NA NA NA NA NA SQ1* NA NA 0.03 g 0.01 g NA NA PC 364* NA NA NA NA 0.03 g 0.01 g Methanol 4 ml 4 ml 4 ml 4 ml 4 ml Methyl Ethyl Ketone 1 ml 1 ml 1 ml 1 ml 1 ml 1 ml "NA" means not added.
  • the dispersions were coated at 0.10 mm wet thickness and dried for 3 minutes at 60° C.
  • a topcoat layer was then applied consisting of 10 g cellulose acetate, 200 g methyl ethyl ketone, and 10 ml of a 1 weight percent hexane diisocyanate solution in methyl ethyl ketone.
  • the topcoat was coated at 0.08 mm wet thickness and dried for 3 minutes at 60°C. Upon exposure (to the laser diode) and development, the results (shown in Table 2) for the materials of Examples 1-6 were obtained.
  • Example 7 The same formulation was used as in Example 7 except that 0.01 g of 3,3'-diethylthiatricarbocyanine iodide was used as the near-infrared sensitizing dye. The following data were obtained: lowest imaging power (in milliwatts) 80 lowest exposure time (in seconds) 0.067 sec
  • thermographic imaging constructions This example demonstrates the utility of various urea compounds as reducing agents (in particular, development accelerators) for thermographic imaging constructions.
  • Silver behenate full soap (160 g) was mixed with 20 g of ButvarTM B-76.
  • the above dispersions were coated at 4 mils wet thickness and then air dried.
  • a topcoat consisting of 5 g KratonTM D1101 styrene-butadiene-styrene block copolymer (available from Shell Chemical Co.), 15 g StyronTM 685D polystyrene resin (available from Dow Chemical Co.), and 250 g methyl ethyl ketone was coated over the first coating at 2 mils wet thickness and then air dried.
  • a laser beam produced by a laser diode (Spectra-Diode Labs, 2370-H1) emitting at 810 nm was focused to a 160 ⁇ m x 45 ⁇ m spot (full width at 1/e2 value) on an image plane.
  • the power on the image plane was aperture-limited to 600 mW.
  • the beam was scanned across the media at 15 cm/sec.
  • the following laser exposure results were obtained for the samples described above: A B C D E D max 1.95 1.98 2.32 2.33 3.44 D min 0.22 0.23 0.20 0.17 0.20 Haze was measured on a Hunter hazemeter (available from Hunter Associates laboratory, Inc.; Reston, Virginia) and gave the following results: A B C D E % Haze 20% 15% 14.7% 15% 8%
  • thermographic imaging formulation using pyrogallol.
  • Silver behenate full soap 160 g, 10 weight % in methyl ethyl ketone
  • ButvarTM B-76 20 g of ButvarTM B-76.
  • 0.6 g of methyl gallate 0.2 g of pyrogallol
  • 0.2 g of phthalazinone 0.1 g of succinimide
  • 0.1 g of 2-imidazolidone a thermographic imaging formulation using pyrogallol.
  • the above dispersion was coated at 4 mils wet thickness and was dried for 3 minutes at 140° F.
  • a second coating was applied as an infrared energy absorbing layer. This was composed of 1.0 g CA 398-6 cellulose acetate (Eastman Chemicals), 20.0 g methyl ethyl ketone, and 0.03 g IR 125 infrared dye. This was coated at 2 mils wet thickness and was dried for 3 min at 60°C.
  • a black image with a D max of 3.73 and a D min of 0.09 was achieved using the same laser exposure conditions as described in Example 9.
  • thermographic imaging formulation using L-ascorbic acid palmitate 160 g of silver behenate full soap (10% in methyl ethyl ketone) was mixed with 20 g of ButvarTM B-76. To 20 g of this dispersion were added: 0.6 g of methyl gallate; 0.2 of L-ascorbic acid palmitate; 0.1 g of succinimide; and 0.1 g of 2-imidazolidone. The dispersion was coated at 4 mils wet thickness and dried for 3 minutes at 60°C.
  • a topcoat consisting of 1.0 g CA 398-6 cellulose acetate, 210 g methyl ethyl ketone, and 0.03 g of IR 125 infrared dye was coated at 2 mils wet thickness and was dried for 3 min at 60°C.
  • a D max of 2.73 and a D min of 0.10 were obtained using the same laser exposure conditions described in Example 9.
  • CyasorbTM 165 as an infrared dye in the following thermographic imaging composition: Silver behenate full soap (160 g, 10 weight % in methyl ethyl ketone) was mixed with 20 g of ButvarTM B-76. To 15 g of this dispersion were added 0.6 g of methyl gallate, 0.2 g of pyrogallol, 0.2 g of phthalazinone, 0.2 of succinimide, and 0.1 of 2-imdazolidone, all dissolved in 4 ml of methanol and 1 ml of methyl ethyl ketone. This dispersion was coated at 4 mils wet thickness and dried for 3 min at 50°C.
  • a topcoat consisting of 1.0 g CA 398-6 cellulose acetate, 20 g methyl ethyl ketone, and 0.03 g of CyasorbTM 165 infrared dye was coated at 2 mils wet thickness and dried 5 min at 50°C.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
EP19930111757 1992-08-03 1993-07-22 Laseradressierbares wärmeempfindliches Aufzeichnungsmaterial Expired - Lifetime EP0582144B1 (de)

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US92351592A 1992-08-03 1992-08-03
US923515 2001-08-07

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Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995007822A1 (en) * 1993-09-14 1995-03-23 Agfa-Gevaert Naamloze Vennootschap Method and material for the formation of a heat mode image
EP0674217A1 (de) * 1994-03-25 1995-09-27 Agfa-Gevaert N.V. Verfahren zur Herstellung eines Bildes nach dem Wärmeverfahren
EP0677775A1 (de) * 1994-03-25 1995-10-18 Agfa-Gevaert N.V. Thermotransferaufzeichnungsverfahren
EP0677776A1 (de) * 1994-03-25 1995-10-18 Agfa-Gevaert N.V. Thermotransferdruckverfahren, in dem ein Gemisch von Reduktionsmitteln zum bildmässigen Reduzieren eines Silbersalzes benutzt wird
EP0678775A1 (de) * 1994-03-25 1995-10-25 Agfa-Gevaert N.V. Thermotransferverfahren
EP0692733A2 (de) * 1994-07-07 1996-01-17 Agfa-Gevaert N.V. Direktes thermisches Aufzeichnungsverfahren
EP0692391A1 (de) 1994-07-13 1996-01-17 Agfa-Gevaert N.V. Wärmeempfindliches Aufzeichnungsmaterial
WO1996010213A1 (en) * 1994-09-27 1996-04-04 Minnesota Mining And Manufacturing Company Laser addressable thermographic elements
US5587268A (en) * 1994-03-25 1996-12-24 Agfa-Gevaert N.V. Thermal transfer imaging process
US5601962A (en) * 1994-03-25 1997-02-11 Agfa-Gevaert N.V. Thermal transfer process wherein a reducing agent and toning agent are transferred to a receiving element containing a thermoreducible silver source
GB2305509A (en) * 1995-09-19 1997-04-09 Minnesota Mining & Mfg Heat sensitive elements
EP0795997A1 (de) * 1996-03-14 1997-09-17 Agfa-Gevaert N.V. Herstellung von Bildern mit kontinuierlichen Tönen durch sequentielle Belichtung eines thermographischen Materials mittels eines Satzes von Strahlenbündeln
EP0796742A2 (de) * 1996-03-19 1997-09-24 Fuji Photo Film Co., Ltd. Infrarotlaser wärmeempfindliches Aufzeichnungsmaterial
EP0836116A1 (de) * 1996-09-06 1998-04-15 Agfa-Gevaert N.V. Empfindlichkeitssteigerndes Aufzeichnungsverfahren für ein lichtempfindliches, wärmeentwickelbares, photographisches Material
EP0849625A1 (de) * 1996-12-19 1998-06-24 Eastman Kodak Company Zusammensetzung für die thermographische Bildaufzeichnung und diese enthaltendes Element
US5840469A (en) * 1997-05-13 1998-11-24 Imation Corp. Gallic acid as a laser direct thermal developer
US5922528A (en) * 1998-03-20 1999-07-13 Eastman Kodak Company Thermographic imaging element
US5928856A (en) * 1998-03-20 1999-07-27 Eastman Kodak Company Thermographic imaging element
US5928855A (en) * 1998-03-20 1999-07-27 Eastman Kodak Company Thermographic imaging element
EP0943958A1 (de) * 1998-03-20 1999-09-22 Eastman Kodak Company Thermographisches Bildaufzeichnungselement
US7261999B2 (en) 2005-11-22 2007-08-28 Carestream Health, Inc. Photothermographic materials containing post-processing stabilizers

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0704318A1 (de) * 1994-09-27 1996-04-03 Minnesota Mining And Manufacturing Company Aufzeichnungsverfahren für wärmeempfindliches Material
JPH10120928A (ja) * 1996-10-22 1998-05-12 Fuji Photo Film Co Ltd 熱現像感光材料、新規な２，３−ジヒドロチアゾール誘導体およびハロゲン化銀写真感光材料
JP6584913B2 (ja) * 2015-10-22 2019-10-02 株式会社日本触媒 オキソカーボン系化合物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0280284A2 (de) * 1987-02-25 1988-08-31 Jujo Paper Co., Ltd. Wärmeempfindliches Aufzeichnungsmaterial
US4824759A (en) * 1985-02-07 1989-04-25 Fuji Photo Film Co., Ltd. Method for forming an image
EP0332455A2 (de) * 1988-03-11 1989-09-13 Canon Kabushiki Kaisha Photoempfindliches Material und Verfahren zur Bildherstellung

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4824759A (en) * 1985-02-07 1989-04-25 Fuji Photo Film Co., Ltd. Method for forming an image
EP0280284A2 (de) * 1987-02-25 1988-08-31 Jujo Paper Co., Ltd. Wärmeempfindliches Aufzeichnungsmaterial
EP0332455A2 (de) * 1988-03-11 1989-09-13 Canon Kabushiki Kaisha Photoempfindliches Material und Verfahren zur Bildherstellung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J.W.CARPENTER ET AL.: "PHOTOTHERMOGRAPHIC SILVER HALIDE SYSTEMS", RESEARCH DISCLOSURE, no. 170, 1 June 1978 (1978-06-01), HAVANT GB, pages 9 - 15 *

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995007822A1 (en) * 1993-09-14 1995-03-23 Agfa-Gevaert Naamloze Vennootschap Method and material for the formation of a heat mode image
US5587268A (en) * 1994-03-25 1996-12-24 Agfa-Gevaert N.V. Thermal transfer imaging process
EP0677775A1 (de) * 1994-03-25 1995-10-18 Agfa-Gevaert N.V. Thermotransferaufzeichnungsverfahren
EP0677776A1 (de) * 1994-03-25 1995-10-18 Agfa-Gevaert N.V. Thermotransferdruckverfahren, in dem ein Gemisch von Reduktionsmitteln zum bildmässigen Reduzieren eines Silbersalzes benutzt wird
EP0678775A1 (de) * 1994-03-25 1995-10-25 Agfa-Gevaert N.V. Thermotransferverfahren
EP0674217A1 (de) * 1994-03-25 1995-09-27 Agfa-Gevaert N.V. Verfahren zur Herstellung eines Bildes nach dem Wärmeverfahren
US5601962A (en) * 1994-03-25 1997-02-11 Agfa-Gevaert N.V. Thermal transfer process wherein a reducing agent and toning agent are transferred to a receiving element containing a thermoreducible silver source
EP0692733A2 (de) * 1994-07-07 1996-01-17 Agfa-Gevaert N.V. Direktes thermisches Aufzeichnungsverfahren
EP0692733A3 (de) * 1994-07-07 1996-03-20 Agfa Gevaert Nv Direktes thermisches Aufzeichnungsverfahren
EP0692391A1 (de) 1994-07-13 1996-01-17 Agfa-Gevaert N.V. Wärmeempfindliches Aufzeichnungsmaterial
WO1996010213A1 (en) * 1994-09-27 1996-04-04 Minnesota Mining And Manufacturing Company Laser addressable thermographic elements
GB2305509A (en) * 1995-09-19 1997-04-09 Minnesota Mining & Mfg Heat sensitive elements
US5766828A (en) * 1995-09-19 1998-06-16 Imation Corp. Laser addressable imaging elements
EP0795997A1 (de) * 1996-03-14 1997-09-17 Agfa-Gevaert N.V. Herstellung von Bildern mit kontinuierlichen Tönen durch sequentielle Belichtung eines thermographischen Materials mittels eines Satzes von Strahlenbündeln
EP0796742A3 (de) * 1996-03-19 1998-02-04 Fuji Photo Film Co., Ltd. Infrarotlaser wärmeempfindliches Aufzeichnungsmaterial
EP0796742A2 (de) * 1996-03-19 1997-09-24 Fuji Photo Film Co., Ltd. Infrarotlaser wärmeempfindliches Aufzeichnungsmaterial
EP0836116A1 (de) * 1996-09-06 1998-04-15 Agfa-Gevaert N.V. Empfindlichkeitssteigerndes Aufzeichnungsverfahren für ein lichtempfindliches, wärmeentwickelbares, photographisches Material
EP0849625A1 (de) * 1996-12-19 1998-06-24 Eastman Kodak Company Zusammensetzung für die thermographische Bildaufzeichnung und diese enthaltendes Element
US6066445A (en) * 1996-12-19 2000-05-23 Eastman Kodak Company Thermographic imaging composition and element comprising said composition
US5840469A (en) * 1997-05-13 1998-11-24 Imation Corp. Gallic acid as a laser direct thermal developer
US5928855A (en) * 1998-03-20 1999-07-27 Eastman Kodak Company Thermographic imaging element
US5928856A (en) * 1998-03-20 1999-07-27 Eastman Kodak Company Thermographic imaging element
EP0943960A1 (de) * 1998-03-20 1999-09-22 Eastman Kodak Company Thermographisches Aufzeichnungsmaterial
EP0943959A1 (de) * 1998-03-20 1999-09-22 Eastman Kodak Company Thermographisches Aufzeichnungsmaterial
EP0943957A1 (de) * 1998-03-20 1999-09-22 Eastman Kodak Company Thermographisches Aufzeichnungsmaterial
EP0943958A1 (de) * 1998-03-20 1999-09-22 Eastman Kodak Company Thermographisches Bildaufzeichnungselement
US5994052A (en) * 1998-03-20 1999-11-30 Eastman Kodak Company Thermographic imaging element
US5922528A (en) * 1998-03-20 1999-07-13 Eastman Kodak Company Thermographic imaging element
US7261999B2 (en) 2005-11-22 2007-08-28 Carestream Health, Inc. Photothermographic materials containing post-processing stabilizers

Also Published As

Publication number Publication date
EP0582144B1 (de) 1997-04-23
DE69310045D1 (de) 1997-05-28
JPH06194781A (ja) 1994-07-15
DE69310045T2 (de) 1997-12-11

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